Diacetal Composition, Process for the Preparation of the Same, Nucleating Agent for Polyolefins Cont

专利摘要:
The present invention (a) at least one diacetal such as 1,3: 2,4-O-dibenzylidene-D-sorbitol and its nuclear substituents, and (b) neutral to weakly acidic monovalent organic acids, neutral to weakly acidic polyvalent organic acids, partial salts of neutral to weakly acidic polyvalent organic acids, sulfuric acid ester salts, sulfonates, phosphate ester salts, phosphate esters, phosphorous acid esters and neutral to weakly acidic ones. At least one binder selected from the group consisting of aluminum salts of organic acids A granular or powdery diacetal composition comprising: a composition in which the binder is uniformly dispersed on and inside the particle surface of the granular or powdery diacetal composition; A method of preparing this composition; Nucleating agent for polyolefin resin containing this composition; It is to provide a resin composition and a polyolefin resin molding agent containing the nucleating agent and a polyolefin resin.
公开号:KR20000069250A
申请号:KR1019997004849
申请日:1998-07-07
公开日:2000-11-25
发明作者:도시아끼 고바야시；마사히데 이시까와；하루또모 노모또；도시히로 미즈따니
申请人:후지타 기요시；신닛폰 리카 가부시키가이샤；
IPC主号:

专利说明:

Diacetal composition, preparation thereof, nucleating agent for polyolefin, polyolefin resin composition and molded article comprising the composition.
Diacetals represented by dibenzylidene sorbitol and its nuclear substituents are widely used as nucleating agents for polyolefin resins or gelling agents of various fluids. In order to express these characteristics, the diacetal needs to be dissolved or molecularly dispersed once in a molten polyolefin resin or a fluid.
By the way, these diacetal powder particles have strong magnetic cohesion and have a high melting point, so that it is not industrially easy to dissolve or disperse uniformly. For this reason, measures for improving the solubility or dispersibility were necessary.
As a method for improving the solubility or dispersibility of diacetal, a method of treating diacetal at a high temperature above its melting point or above a melting temperature is known. However, when the diacetal is treated for a long time at a high temperature, it causes problems such as thermal decomposition or coloring of the diacetal, and thus it is mechanically troubled because it cannot exhibit sufficient performance, which is also a problem in terms of energy saving.
In addition, Japanese Patent Application Laid-Open No. 94-145431 proposes a method in which diacetal is made into fine particles to improve dispersibility and facilitate dissolution. However, the method of finely dicing the diacetal solid has a deterioration of the working environment, such as dust explosion, impact on the human body by dust inhalation, reagglomeration during storage, fluidity deterioration and transportability (when transferring the diacetal powder through piping). Ease of use), resulting in deterioration of workability, causing industrially important problems. In addition, this technique brings the particle size distribution close to a single dispersion and requires a special and expensive grinding device.
Moreover, the method of improving compatibility of diacetal and polyolefin resin by using organic carboxylic acid together in diacetal is known (Japanese Patent Publication No. 76-122150, Japanese Patent Publication No. 89-413, Japanese Patent Publication No. 85) -101131).
According to the method described in Japanese Patent Laid-Open No. 76-122150, the compatibility with resin is increased by adding dibenzylidene sorbitol and organic carboxylic acid directly to the polyolefin resin separately. However, this method does not lower the melting point inherent in dibenzylidene sorbitol, so it is insufficient to solve the problem that undissolved dibenzylidene sorbitol remains as a white precipitate.
According to the method described in Japanese Patent Publication No. 89-413 or Japanese Patent Application Laid-Open No. 85-101131, all of the powder surface of dibenzylidene sorbitol is previously coated with a higher fatty acid or terephthalic acid, and the coating is added to the polyolefin resin. have. This method can improve the compatibility with molten resin compared with the method of mix | blending uncoated dibenzylidene sorbitol directly with a polyolefin resin. However, even with this technique, undissolved white precipitates remain unsatisfactory. Therefore, the effect of transparency modification is insufficient, and the value of the product is impaired in the appearance of the product. This phenomenon also applies to the surface coating of higher fatty acids on the surface of the diacetal particles by simply using an organic solvent.
In addition, a fatty acid carboxylic acid amide and / or an aromatic carbamide as a transparent nucleating agent for polyolefin resin with improved moldability, which enables molding at a temperature lower than the conventional molding temperature (hereinafter referred to as "cold molding"). A nucleating agent has been proposed in which an acid amide is mixed with dibenzylidene sorbitol or the surface of powder particles of dibenzylidene sorbitol is coated (Japanese Patent Laid-Open No. 96-245843). However, since the said method of miscible forms a hard gel at the time of solvent removal, industrialization is very difficult, and the manufacturing method is not specified and its utility is inferior. In addition, the coating method does not obtain a sufficient melting point drop of diacetal in comparison with a large amount of coating agent such as aliphatic carboxylic acid amide and / or aromatic carboxylic acid amide, and the amide compound is bleeded in the polyolefin molded body. Since the coating agent has many properties, there exists a problem of the adhesive strength of the polyolefin resin molding obtained from the acetal and polyolefin resin coat | covered with this coating agent falling, etc., It is insufficient in practical use, and the room for improvement is recognized.
<Start of invention>
The present invention improves the solubility and dispersibility of diacetal in various molten resins or various liquids, and its fluidity and transferability (when the diacetal is transported through a pipe, the friction between the liquid particles is small and the conveyance is easy. It is one object of the present invention to provide a method for improving dust resistance and suppressing dust generation and adhesion to base walls such as piping and hoppers.
Another object of the present invention is to easily exhibit the nucleating agent function of a polyolefin resin by low temperature molding.
The present inventors earnestly examined in order to achieve this object and found that the following advantages in use were obtained by uniformly dispersing a specific compound in a diacetal swelled with a solvent or dissolved in a polar organic solvent, followed by drying and granulation or powdering. Found that
(1) The melting point of diacetal is effectively lowered.
(2) The diacetal composition obtained by uniformly dispersing the specific compound in the diacetal powder particles, regardless of its shape, can greatly improve the solubility, dispersibility and dissolution rate in the molten resin or various liquids.
(3) the apparent density of the diacetal composition can be arbitrarily adjusted to 0.2 g / cm 3 or more by the binder effect (i.e., the effect of promoting aggregation or aggregation of particles) of the specific compound, and thereby the fluidity of the diacetal powder, Mobility can be improved, dust generation can be suppressed, and adhesion to substrate walls such as equipment piping and hoppers can be suppressed.
(4) It exhibits the nucleating agent characteristic which the diacetal nucleating agent has inherently very easily without generating the contamination of the extrusion die | dye by the sublimation of a nucleating agent at the time of pellet molding of a polyolefin resin, and a contamination of a molded object.
Generally, when the apparent density of the diacetal composition is increased, the liquid flowability is improved, but the dissolution rate is lowered. Conversely, lowering the apparent density improves the dissolution rate but lowers the liquid flowability. The present inventors succeeded in dramatically lowering the melting point of the diacetal composition, thereby increasing the apparent density to simultaneously solve the improvement of the powder flowability and the dissolution rate.
The present invention has been completed based on this invention.
The present invention, (a) at least one diacetal represented by the formula (1) and
(b) neutral to weakly acidic monovalent organic acids, neutral to weakly acidic polyvalent organic acids, partial salts of neutral to weakly acidic polyvalent organic acids, salts of strongly acidic organic acids (particularly sulfuric acid ester salts, sulfonate and phosphate ester salts), phosphate esters, Binder comprising at least one member selected from the group consisting of phosphorous acid esters and aluminum salts of neutral to weakly acidic monovalent organic acids
A granular or powdery diacetal composition comprising a, wherein the binder is to provide a composition in which the binder is uniformly dispersed in the particles of the granular or powdery diacetal composition.
In the formula,
R ¹ and R ² are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom,
a and b each represent an integer of 1 to 5,
c represents 0 or 1,
When a is 2, two R ¹ may be bonded to each other to form a tetralin ring together with the benzene ring to which they are bonded. When b is 2, two R ² may be bonded to each other and together with the benzene ring to which they are bonded. You can also form a tetralin ring.
The organic acid may have a bond other than a carbon-carbon bond in the molecule (for example, an ether bond, an ester bond, a thioether bond, an amide bond, etc.) or a functional group (for example, a halogen atom, an amino group, a hydroxyl group, a heterocyclic group, a carbonyl group, etc.). One or more may be present. In addition, in neutral to weakly acidic divalent organic acids (i.e., organic acids having two or more monovalent acid groups in a molecule), a part of the acid portion thereof is an alkali metal (lithium, potassium, sodium, etc.) or an alkaline earth metal (calcium, etc.). And salts with amines (such as tri (C1-C4 alkyl) amines such as triethylamine and trimethylamine), ammonium and the like. Strongly acidic organic acids are usually used in the form of salts (ie, as neutral to weakly acidic to weakly basic salts). In addition, the aluminum salt is a salt of monovalent organic acid and aluminum monoatoms of 1,2 or 3 molecules.
The form of the diacetal composition of the present invention is generally powdery or granular, particularly preferably in the form of a powder having an average particle diameter of 3 to 2000 μm or in the form of a granular or cylindrical shaped molding or the like. .
According to the present invention, the melting point of the diacetal composition of the present invention is lowered as ① the degree of swelling of the diacetal at the time of preparation of the composition is decreased, ② is significantly reduced compared to the simple coating of the diacetal particles, and ③ is significantly reduced by applying a specific compound. It is based on the discovery of an unexpected fact. The degree of swelling depends on the degree of heat mixing in the solvent described later, and is particularly promoted by heat mixing in the presence of a polar organic solvent coexistence as described later.
The diacetal composition of the present invention is prepared by uniformly mixing the diacetal sufficiently swollen with a solvent (for example, alcohol, water, etc.) and the binder, and powdering or granulating the obtained swelling diacetal composition while drying. It is obtained.
The solid diacetal is composed of a plurality of diacetal fibrous crystals. On the other hand, in a diacetal swelled with a solvent such as water or an organic solvent, a solvent penetrates between a plurality of fibrous crystals gathered into a solid phase, the fibrous crystals are released, and the aggregate state becomes coarse, and the apparent volume is increased. have. When the swelled diacetal and the binder are uniformly mixed, the binder penetrates between the fibrous crystals of the diacetal to uniformly disperse molecules.
Then, the homogeneous dispersion is granulated while drying, and after drying the homogeneous dispersion, the dried product is pulverized, the powder obtained by pulverizing the dried product is granulated, and the granulated product is pulverized by a method such as pulverizing the granulated product. Or granulated to obtain a composition in which the binder is uniformly dispersed between the diacetal fibrous crystals (hereinafter, simply referred to as "diacetal composition").
As a result, in the granular or powdery diacetal composition of the present invention, the binder is uniformly distributed not only on the surface of the diacetal particles but also inside the diacetal particles. That is, this binder is uniformly distributed among the diacetal fibrous crystals constituting the diacetal particles.
In this regard, the present invention is different from the diacetal of Japanese Patent Application Laid-Open No. 96-245843 obtained by simply admixing diacetal particles with a carboxylic acid amide without swelling the solvent, or by coating the surface of the diacetal particles with carboxylic acid amide. It is fundamentally different in the concentration distribution of the binder and below the melting point of the acetal.
The present invention also provides a method for producing the diacetal composition.
Moreover, this invention also provides the nucleating agent for polyolefin resins containing the said diacetal composition.
Moreover, this invention provides the polyolefin resin composition or pellet obtained from this nucleating agent and polyolefin resin, and the molded object formed by shape | molding this polyolefin resin composition.
Moreover, this invention also provides the shaping | molding method of the said polyolefin resin composition.
According to one embodiment of the present invention, (a) R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, and an alkoxy of 1 to 4 carbon atoms An essential component comprising at least one diacetal and (b) at least one organic acid represented by the formula (1), which represents a carbonyl group or a halogen atom, a and b each represent an integer of 1 to 5, and c represents 0 or 1. A powdery uniform dispersion diacetal composition (i.e., a composition in which the binder is uniformly dispersed in a diacetal) comprising a binder, wherein the average value of the particle diameter thereof is 3 to 500 µm. This is provided.
In the above embodiment, the organic acid is preferably a compound capable of lowering the melting point of the diacetal by 7 ° C or more when 10 parts by weight of the organic acid is uniformly dispersed with respect to 90 parts by weight of the diacetal.
In a preferred embodiment of the above embodiment, the apparent density of the composition is 0.2 to 0.9 g / cm 3. Moreover, it is preferable that the acid value of the said organic acid is 60-1200 mgKOH / g.
In the said embodiment, the nucleating agent for polyolefin resins containing the said diacetal composition is provided.
Hereinafter, the present invention will be described in detail.
<Diacetal>
In Formula 1, examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ² include methyl, ethyl, propyl, isopropyl, butyl, and the like. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, and pro Foxy, isopropoxy, butoxy and the like are exemplified. Examples of the alkoxycarbonyl group having 1 to 4 carbon atoms include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and isopropoxycarbonyl group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are illustrated.
a and b are the integers of 1-5, respectively, Preferably they are 1, 2 or 3. c is preferably 1. Although the substitution position of the substituent represented by R <^1> and R <^2> is not specifically limited, When a and b are 1, it is o-, m- or p-position, and when a and b are 2, 2, 4- Position, 3,4-position, 3,5-position, etc. can be illustrated, and when a and b are 3, 2,4,5-position, 3,4,5-position etc. can be illustrated.
The diacetals represented by the general formula (1) are all known or known methods such as Japanese Patent Publication No. 73-43748, Patent Publication No. 78-5165, Patent Publication No. 82-185287, and Patent Publication No. 90-231488. It can be manufactured easily accordingly.
The following can be illustrated as a representative example of the diacetal represented by General formula (1).
1,3: 2,4-O-dibenzylidene-D-sorbitol,
1,3: 2,4-bis-O- (m-methylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-ethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-isopropylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-n-propylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-n-butylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-isopropylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-n-propylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-n-butylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2,3-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2,4-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2,5-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3,4-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3,5-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2,3-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2,4-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2,5-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3,4-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3,5-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2,4,5-trimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3,4,5-trimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2,4,5-triethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3,4,5-triethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-methyloxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-ethyloxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-isopropyloxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-n-propyloxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-n-butylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-chlorobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-chlorobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O-[(5,6,7,8-tetrahydro-1-naphthalene) -1-methylene] -D-sorbitol,
1,3: 2,4-bis-O-[(5,6,7,8-tetrahydro-2-naphthalene) -1-methylene] -D-sorbitol,
1,3-O-benzylidene-2,4-O-p-methylbenzylidene-D-sorbitol,
1,3-O-p-methylbenzylidene-2,4-O-benzylidene-D-sorbitol,
1,3-O-benzylidene-2,4-O-p-ethylbenzylidene-D-sorbitol,
1,3-O-p-ethylbenzylidene-2,4-O-benzylidene-D-sorbitol,
1,3-O-benzylidene-2,4-O-p-chlorobenzylidene-D-sorbitol,
1,3-O-p-chlorobenzylidene-2,4-O-benzylidene-D-sorbitol,
1,3-O-benzylidene-2,4-O- (2,4-dimethylbenzylidene) -D-sorbitol,
1,3-O- (2,4-dimethylbenzylidene) -2,4-O-benzylidene-D-sorbitol,
1,3-O-benzylidene-2,4-O- (3,4-dimethylbenzylidene) -D-sorbitol,
1,3-O- (3,4-dimethylbenzylidene) -2,4-O-benzylidene-D-sorbitol,
1,3-O-p-methyl-benzylidene-2,4-O-p-ethylbenzylidenesorbitol,
1,3-p-ethyl-benzylidene-2,4-p-methylbenzylidene-D-sorbitol,
1,3-O-p-methyl-benzylidene-2,4-O-p-chlorobenzylidene-D-sorbitol and
1,3-O-p-chloro-benzylidene-2,4-O-p-methylbenzylidene-D-sorbitol.
These are used individually or in combination of 2 or more types, respectively.
The crystal form of the diacetal is not limited as long as the result of the present invention is obtained, and any crystal form such as hexagonal crystal, monoclinic crystal or cubic crystal can be used. Such crystals can also be prepared according to known methods.
Although the raw material diacetal used by this invention may be 100% of the purity of the 1,3: 2,4- body represented by General formula (1), it may contain a little impurity. In general, the raw material diacetal should be at least 90% by weight, preferably at least 95% by weight, particularly preferably at least 97% by weight of the 1,3: 2,4-body represented by the formula (1).
Produced by a condensation reaction with a pentahydric or hexavalent polyhydric alcohol such as D-sorbitol, which is a reaction raw material for the synthesis of the diacetal represented by Formula 1, and an aromatic aldehyde which may have a substituent (especially benzaldehyde which may have a substituent) As the acetal compound, in addition to 1,3: 2,4-diacetal represented by the formula (1), other acetal compounds (by-products), for example, 1,2-body, 3,4-body, 2,4-body , Monoacetals such as 1,3-form, triacetals such as 1,3: 2,4: 5,6-form, 1,3: 3,4: 5,6-form, and 1,2: 3,4 -Diacetal isomers, such as a sieve, are mentioned.
The diacetal composition of the present invention may contain at least one monoacetal, triacetal and diacetal isomers of these impurities in addition to the diacetal represented by the formula (1), in which case the total amount of the impurities is represented by the total amount of acetal (Formula 1) Total amount of 1,3: 2,4-diacetal, monoacetal, triacetal and diacetal isomers) up to 10% by weight, in particular from 0.05 to 10% by weight, preferably from 0.1 to 5% by weight, more preferably Is present in an amount of 0.1 to 3% by weight or less, and is not particularly problematic, and is rather preferable for the purpose of low melting point of the diacetal composition of the present invention. However, when it becomes 10 weight% or more, there exists a tendency for a nucleating agent characteristic to fall.
Binder
Examples of the binder of the present invention include partial salts of neutral to weakly acidic monovalent organic acids, neutral to weakly acidic polyvalent organic acids, and neutral to weakly acidic polyvalent organic acids, and salts of strongly acidic organic acids, such as sulfuric acid ester salts and sulfonic acids. Salts, phosphate ester salts, and even aluminum salts of phosphate esters, phosphite esters, and neutral to weakly acidic monovalent organic acids can also be exemplified. These can be used individually by 1 type and can also use 2 or more types together.
The binder according to the present invention effectively lowers the melting point of the diacetal by homogeneously dispersing it in the diacetal swelled according to the manufacturing method described below, and increases the apparent density of the powder. These two effects can greatly improve the solubility or dispersibility of the molten resin or various liquids, and at the same time improve the fluidity and transportability of the diacetal composition in the form of powder or granules or moldings, and the generation of dust Control the adhesion to the base wall of the pipe, hopper and the like.
In addition, as described above, the melting point of the diacetal composition according to the present invention is significantly lower than the melting point of the diacetal itself constituting the diacetal composition, when the present invention is added to the polyolefin resin and molded, the present invention Since the polyolefin resin pellets obtained from the molten polyolefin resin can be dissolved or dispersed in the molten polyolefin near the melting point of the diacetal composition, the resin temperature is set at the temperature near the melting point of the diacetal composition of the present invention, mixed, cooled and The cutting method becomes possible. Therefore, extrusion molding at a lower temperature is possible more sharply than in the past, and as a result, there is no need to refine the nucleating agent. Moreover, since the sublimation property of a nucleating agent also loses with the fall of extrusion temperature, a nucleating agent characteristic is exhibited very easily, and the productivity of a polyolefin resin pellet improves.
For the same reason, the resin powder, the diacetal composition of the present invention, and a resin powder composition containing other resin additives, if necessary, can be used as injection molding, extrusion molding, or the like without using the polyolefin resin pellets. At this time, not only low temperature molding is possible but also contamination of a mold or contamination of a molded body such as a sheet due to sublimation of diacetal is suppressed.
As a compounding quantity of a binder, 0.01-100 weight part is illustrated with respect to 100 weight part of diacetal represented by General formula (1), Preferably it is 0.1-70 weight part, More preferably, it is 0.2-25 weight part. If it is less than 0.01 part by weight, the effect of lowering the melting point is hardly obtained and the binder effect is also hard to be obtained. On the other hand, even when blended in excess of 100 parts by weight, no particular advantage in the effect of the melting point drop and the binder effect is hardly found, and when used as a nucleating agent, may also be a cause of impairing the transparency of the resin. As will be described later, in the case of using hydroxycarboxylic acid as a binder, even if the amount is very small, the melting point of the diacetal composition is significantly lower than that of the diacetal itself.
Among the above-mentioned binders, in particular, when 10 parts by weight of the binder is uniformly dispersed in 90 parts by weight of the diacetal represented by Formula 1 according to the present invention, the melting point of the obtained diacetal composition constitutes the diacetal composition. The binder which can lower | fall 7 degreeC or more, Preferably it is 20 degreeC or more, More preferably, it is 40 degreeC or more, More preferably, it is 90 degreeC or more than melting | fusing point of the diacetal to be encouraged. It is also encouraged that the melting point and / or softening point of the binder itself is below the melting point of the diacetal that uniformly disperses it. The said binder may be used independently and may be used in combination of 2 or more type as appropriate.
From the viewpoint of the melting point drop, an organic acid having an acid value of about 60 to 1200 mgKOH / g, particularly mono or polycarboxylic acid, is preferable, and an organic acid, especially mono or polycarboxylic acid, which is about 80 to 1000 mgKOH / g, is more preferable. Organic acids having an acid value of 60 mgKOH / g or more are more likely to obtain the effect of lowering the melting point. When it exceeds 1200 mgKOH / g, melting | fusing point fall does not become large normally according to it.
In particular, as a preferable binder used by this invention,
(1) monocarboxylic acid,
(2) polycarboxylic acids,
(3) partial salts of polycarboxylic acids,
Partial salts of neutral to weakly acidic monovalent organic acids, neutral to weakly acidic polyvalent organic acids, neutral to weakly acidic polyvalent organic acids, and the like, and esters of phosphoric acid or phosphorous acid, for example,
(4) esters of at least one selected from the group consisting of monohydric aliphatic alcohols having 1 to 30 carbon atoms and polyhydric aliphatic alcohols having 2 to 30 carbon atoms, and phosphoric acid;
(5) esters of at least two selected from the group consisting of monohydric aliphatic alcohols having 1 to 30 carbon atoms and polyhydric aliphatic alcohols having 2 to 30 carbon atoms and phosphorous acid;
(6) esters of at least one selected from the group consisting of monovalent aromatic alcohols having 6 to 30 carbon atoms and polyvalent aromatic alcohols having 6 to 30 carbon atoms, and phosphoric acid;
(7) Ester of at least 1 sort (s) chosen from the group which consists of a C6-C30 monovalent aromatic alcohol and a C6-C30 polyhydric aromatic alcohol, and phosphorous acid can be used.
Also,
(8) Salts of neutral to weakly basic to weakly acidic sulfonic acids such as taurine may also be used.
Furthermore, as salts of weakly acidic organic acids, for example, sulfuric acid ester salts, sulfonates, phosphate ester salts can also be used, and in particular,
(9) alkanesulfonates having 4 to 30 carbon atoms or alkenesulfonates having 4 to 30 carbon atoms,
(10) (C1-C30 alkyl) benzenesulfonate,
(11) (C1-C30 alkyl) naphthalenesulfonate,
(12) sulfuric acid ester salts of saturated aliphatic alcohols having 4 to 30 carbon atoms or sulfuric acid ester salts of unsaturated aliphatic alcohols having 1 to 3 unsaturated bonds having 4 to 30 carbon atoms,
(13) Sulfuric acid ester salts of saturated aliphatic alcohols having 4 to 30 carbon atoms to which 1 to 10 moles of ethylene oxide are added or unsaturated aliphatic alcohols having 1 to 3 unsaturated bonds having 4 to 30 carbon atoms to which 1 to 10 moles of ethylene oxide are added. Sulfuric acid ester salts,
(14) sulfosuccinic acid diester salts wherein the alcohol moiety of the ester is a C2-C16 alkyl group, a cyclohexyl group, or a C1-C5 alkyl group substituted cyclohexyl group;
(15) Phosphoric acid ester salt whose alcohol residue of ester is a C4-C30 unsaturated hydrocarbon group which has a C4-C30 alkyl group or an unsaturated bond, or a polyvalent 5--12 polyvalent having 4-12 hydroxyl groups. Ester salts of alcohols and phosphoric acid,
(16) C1-C10 alkyl ester salts of α-sulfo fatty acid salts having 6 to 30 carbon atoms or α-sulfo fatty acids having 3 to 30 carbon atoms
Can be illustrated. Also
(17) mono, di or tri (C6-C30 fatty acid) aluminum salts
Can also be used.
These can be used individually or in combination of 2 or more types. Moreover, when these organic acids have subsidiary carbon, any of D-form, L-form, and racemate can be used.
Among these, partial salts of neutral to weakly acidic monovalent organic acids, neutral to weakly acidic polyvalent organic acids, and neutral to weakly acidic polyvalent organic acids, for example
(1) monocarboxylic acid,
(2) polycarboxylic acids,
(3) partial salts of polycarboxylic acids,
Sulfuric acid ester salts, sulfonates, phosphate ester salts, for example
(9) alkanesulfonates having 4 to 30 carbon atoms or alkenesulfonates having 4 to 30 carbon atoms,
(10) (C1-C30 alkyl) benzenesulfonate,
(11) (C1-C30 alkyl) naphthalenesulfonate,
(12) sulfuric acid ester salts of saturated aliphatic alcohols having 4 to 30 carbon atoms or sulfuric acid ester salts of unsaturated aliphatic alcohols having 1 to 3 unsaturated bonds having 4 to 30 carbon atoms,
(13) Sulfuric acid ester salts of saturated aliphatic alcohols having 4 to 30 carbon atoms to which 1 to 10 moles of ethylene oxide are added or unsaturated aliphatic alcohols having 1 to 3 unsaturated bonds having 4 to 30 carbon atoms to which 1 to 10 moles of ethylene oxide are added. Sulfuric acid ester salts,
(14) sulfosuccinic acid diester salts wherein the alcohol moiety of the ester is a C2-C16 alkyl group, a cyclohexyl group, or a C1-C5 alkyl group substituted cyclohexyl group;
(15) Phosphoric acid ester salt whose alcohol residue of ester is a C4-C30 unsaturated hydrocarbon group which has a C4-C30 alkyl group or an unsaturated bond, or a polyvalent 5--12 polyvalent having 4-12 hydroxyl groups. Ester salts of alcohols and phosphoric acid,
(16) C1-C5 alkyl ester salts of α-sulfo fatty acid salts having 6 to 30 carbon atoms or α-sulfon fatty acids having 6 to 30 carbon atoms
Can be illustrated as being preferred. Also
(17) Mono, di or tri (C6-C30 fatty acid) aluminum salts may also be used.
The organic acid or derivative thereof used in the present invention may have a bond other than a carbon-carbon bond (e.g., an ether bond, an ester bond, a thioether bond, an amide bond, etc.) or a functional group (for example, a halogen atom, an amino group, Hydroxyl groups, heterocyclic groups, carbonyl groups, etc.) may be present.
In addition, in neutral to weakly acidic divalent or higher organic acids (i.e., organic acids having two or more monovalent acid groups in a molecule), some of the acid portions thereof are alkali metals (lithium, potassium, sodium, etc.) or alkaline earth metals (calcium, etc.). ), Amines (such as tri (C1-C4 alkyl) amines such as triethylamine and trimethylamine), and ammonium may be formed. Strongly acidic organic acids are usually used in the form of salts (ie, as neutral to weakly acidic salts).
Among organic acids, mono and polycarboxylic acids are particularly effective. Many of these compounds are also industrially available, and many of them are safe, hygienic, easy to handle and easy to handle, and are industrially advantageous over phosphorous or phosphate compounds or taurine.
Specific examples of such mono or polycarboxylic acids include aliphatic monocarboxylic acids having 80 or less carbon atoms (preferably having 3 to 35 carbon atoms), aliphatic polycarboxylic acids having 80 or less carbon atoms (preferably having 4 to 30 carbon atoms), and The alkyl (carbon 1 to 22) partial esters, aromatic monocarboxylic acids having 80 or less carbon atoms (preferably having 7 to 35 carbon atoms), aromatic polycarboxylic acids having 80 or less carbon atoms (preferably 8 to 30 carbon atoms), and their Alkyl (C1-C22) partial esters, carboxylic acids having a halogen atom of up to 80 carbon atoms (preferably from 4 to 35 carbon atoms), carboxylic acids having an amino group of up to 80 carbon atoms (preferably from 4 to 35 carbon atoms) Carboxylic acid having an amide bond having 80 or less carbon atoms (preferably having 4 to 35 carbon atoms), and a carboxylic acid having a hydroxyl group having 80 carbon atoms or less (preferably having 4 to 35 carbon atoms) Carboxylic acid having a carbonic acid having a carbonyl group of 80 or less (preferably 4 to 35 carbon atoms), a carboxylic acid having an ether bond of 80 or less carbon atoms (preferably 4 to 35 carbon atoms), 80 or less carbon atoms, Preferably a carboxylic acid having an ester bond of 4 to 35 carbon atoms, a carboxylic acid having an amide bond and an amino group of 80 or less carbon atoms (preferably 4 to 35 carbon atoms), 80 or less carbon atoms (preferably 4 to 35 carbon atoms) Carboxylic acid having an amide bond and a hydroxyl group, a heterocyclic containing carboxylic acid having 80 or less carbon atoms (preferably having 4 to 35 carbon atoms), and a thioether bond having 80 or less carbon atoms (preferably having 4 to 35 carbon atoms) Carboxylic acid which has, etc. are illustrated. When the carbon number exceeds 80, since the molecular weight usually increases, the acid value tends to be small, so that the effect of lowering the melting point tends to be difficult to be sufficiently obtained.
Examples of aliphatic monocarboxylic acids having 80 or less carbon atoms include propionic acid, butyric acid, isobutyric acid, valeric acid, n-capronic acid, cyclohexyl monocarboxylic acid, caprylic acid, 2-ethylhexanoic acid, nonanoic acid, capric acid, Undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, isostearic acid, nonadecanoic acid, octylundecanoic acid, eicosanoic acid, behenic acid, doco Sahexanoic acid, montanic acid, naphthenic acid, koranic acid, deoxycholic acid, lithocholic acid, p-tolylacetic acid, diphenylacetic acid, phenoxyacetic acid, benzyl acid, sorbic acid, palm oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, Unsaturated fatty acids such as carboxylic acids having 22 to 36 carbon atoms obtained by saponifying a Uji fatty acid, rice bran wax, carnava wax, candelilla wax, and beeswax, oleic acid, linoleic acid, linoleic acid, and fatty acids obtained by saponifying fish oil, and the like Geometric isomers of these are exemplified, among them lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, isostearic acid, eicosanoic acid, behenic acid, docosa Hexanoic acid, montanic acid, benzyl acid, sorbic acid, oleic acid, linoleic acid, linoleic acid are encouraged.
Examples of the aliphatic polycarboxylic acid having 80 or less carbon atoms include aliphatic di-, tri-, tetracarboxylic acids, and the like, glutaric acid, succinic acid, malonic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, Dodecane diacid, itaconic acid, maleic acid, fumaric acid, citraconic acid, aconitic acid, tricarballylic acid, 1,2,3,4-butanetetracarboxylic acid, citrazinic acid, 1,2,3, 4-cyclopentanetetracarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, alkyl group (C1-8) substituted cyclohexanedicarboxylic acid, 4,4 '-Dicyclohexyldicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, dimer acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, up to 6 to 80 carbon atoms Of (meth) acrylic acid oligomers and (meth) methyl oligomers having from 7 to 80 carbon atoms Carboxylic acid etc. which are obtained by chemical decomposition are exemplified, among others, succinic acid, glutaric acid, malonic acid, adipic acid, suveric acid, azelaic acid, sebacic acid, dodecane diacid, itaconic acid, tricarvalic acid, 1,2,3,4-butanetetracarboxylic acid, citric acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexane Dicarboxylic acids, 4,4'-dicyclohexyldicarboxylic acid, cyclohexanetetracarboxylic acid are encouraged.
Examples of the aromatic monocarboxylic acid having 80 or less carbon atoms include benzoic acid, p-toluic acid, p-ethylbenzoic acid, cuminic acid, p-tert-butylbenzoic acid, p-isobutylbenzoic acid, p-phenylbenzoic acid, 3,5-dimethylbenzoic acid, and the like. Benzoic acid, 1-naphthoic acid, 2-naphthoic acid, tetralinocarboxylic acid, alkyl group having 1 to 4, preferably 1 to 12, alkyl groups having 1 to 4 carbon atoms or 1 to 2 phenyl groups. For example, C1-C12) substituted tetralin monocarboxylic acid etc. are illustrated, Especially, a benzoic acid, p-methylbenzoic acid, p-ethylbenzoic acid, pn-propylbenzoic acid, cuminic acid, p-tert- butylbenzoic acid, p-isobutylbenzoic acid, p-phenylbenzoic acid, 3,5-dimethylbenzoic acid, 1-naphthoic acid 2-naphthoic acid, tetralinocarboxylic acid are encouraged.
Examples of the aromatic polycarboxylic acid having 80 or less carbon atoms include aromatic di-, tri- and tetracarboxylic acids, and o-phthalic acid, m-phthalic acid, p-phthalic acid, trimellitic acid, trimesic acid and pyromellitic acid , Diphenic acid, benzenehexacarboxylic acid, biphenyldicarboxylic acid, biphenyltetracarboxylic acid, ethylene glycol-4,4'-bistrimellitate, glycyric acid, naphthalenedicarboxylic acid, diphenylsulfone Tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylmethane tetracarboxylic acid, diphenyl propane tetracarboxylic acid, etc. are illustrated, and among these, o-phthalic acid, m-phthalic acid, p-phthalic acid, trimellitic acid , Trimesic acid, pyromellitic acid, diphenic acid, biphenyldicarboxylic acid, biphenyltetracarboxylic acid, naphthalenedicarboxylic acid, diphenylsulfontetracarboxylic acid, diphenylethertetracarboxylic acid, diphenyl Methanetetracarboxylic acid, diphenyl The ropan tetracarboxylic acid, ethylene glycol-4,4'-bis trimellitic diethyl tree Tate is encouraged.
As the carboxylic acid having a halogen atom having 80 or less carbon atoms, mono-, di, tri, or tetracarboxylic acids having 3 to 24 carbon atoms having 1 to 3 halogen atoms such as chlorine and bromine are preferable, and chloropropionic acid and bromopropionic acid , o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, 4-chloro-3-nitrobenzoic acid, diflunisal, triphenic acid and the like are exemplified.
As the carboxylic acid having an amino group having 80 or less carbon atoms, mono, di, tri, or tetracarboxylic acids having 2 to 24 carbon atoms having 1 to 5 amino groups are preferable, and glycine, alanine, β-alanine, phenylalanine, and α-amino are preferred. Acrylic acid, β-aminobutyric acid, γ-aminobutyric acid, alloisolecin, γ-amino-α-methylene butyric acid, α-aminoisobutyric acid, β-aminoisobutyric acid, norvarin, δ-amino-n-valeric acid, β Aminocrotonic acid, isoleucine, varine, 2-amino-4-pentenoic acid, norleucine, 6-aminocaproic acid, leucine, 7-aminoheptanoic acid, α-amino-n-caprylic acid, 8-amino Caprylic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, sarcosine, proline, aminomaronic acid, 2-aminoadipic acid, arginine, aspartic acid, asparagine, cystine, ethionine , Cystacionine, lanchione, glutamine, article Ttamic acid, theanine, S- (carboxymethyl) cystine, 2,4-diaminobutyric acid, cannavanine, kynurenine, histidine, 1-methylhistidine, 3-methylhistidine, tryptophan, lysine, ornithine, creatine, citrulline, D, such as azaserine, allothreonine, threonine, δ-hydroxylysine, homoserine, methionine, ergothioneine, cysteine, cysteinic acid, threonine, β- (3,4-dihydroxyphenyl) -alanine, tyrosine, etc. Sieve, L form, DL form, 1-aminocyclohexanecarboxylic acid, 2-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, p-aminomethylcyclohexane Carboxylic acid, 2-amino-2-norbornanecarboxylic acid, 3,5-diaminocyclohexanecarboxylic acid, 1-amino-1,3-cyclohexanedicarboxylic acid, α-aminophenylacetic acid, α-amino-β-phenylpropionic acid, 2-amino-2-phenylpropionic acid, 3-amino-3-phenylpropionic acid, α-a Nocinnamic acid, 2-amino-4-phenylbutyric acid, 4-amino-3-phenylbutyric acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-4-methylbenzoic acid, 2-amino-6-methyl Benzoic acid, 3-amino-4-methylbenzoic acid, 2-amino-3-methylbenzoic acid, 2-amino-5-methylbenzoic acid, 4-amino-2-methylbenzoic acid, 4-amino-3-methylbenzoic acid, 2-amino 3-methoxybenzoic acid, 3-amino-4-methoxybenzoic acid, 4-amino-2-methoxybenzoic acid, 4-amino-3-methoxybenzoic acid, 2-amino-4,5-dimethoxybenzoic acid, o -Aminophenylacetic acid, m-aminophenylacetic acid, p-aminophenylacetic acid, 4- (4-aminophenyl) butyric acid, 4-aminomethylbenzoic acid, 4-aminomethylphenylacetic acid, o-aminocinnamic acid, m-aminocinnamic acid , p-aminocinnamic acid, p-aminohypurinic acid, 2-amino-1-naphthoic acid, 3-amino-1-naphthoic acid, 4-amino-1-naphthoic acid, 5-amino-1-naphthoic acid, 6-amino-1-naphthoic acid, 7-amino-1-naphthoic acid, 8-amino- 1-naphthoic acid, 1-amino-2-naphthoic acid, 3-amino-2-naphthoic acid, 4-amino-2-naphthoic acid, 5-amino-2-naphthoic acid, 6-amino-2-naphthoic acid, 7-amino-2-naphthoic acid, 8-amino-2-naphthoic acid, 3,5-diaminobenzoic acid, 4,4'-diamino-3,3'-dicarboxydiphenylmethane, ethylenediamine tetraacetic acid, etc. This is illustrated. Among these, L-glutamine is especially preferable.
As the carboxylic acid having a hydroxyl group having 80 or less carbon atoms, mono, di, tri, or tetracarboxylic acids having about 2 to 30 carbon atoms having 1 to 5 hydroxyl groups regardless of D-, L- or racemates are preferable. Tartaric acid, lactic acid, malic acid, citric acid, gluconic acid, pantothenic acid, 12-hydroxystearic acid, mandelic acid, cholic acid, β-oxynaphthoic acid, ricinolic acid, quinic acid, sikimic acid, salicylic acid, protocatenic acid, cumalic acid, and the like. Phenolic acid, gallic acid, α, β-dihydroxyhexahydrophthalic acid, and the like, among them tartaric acid, lactic acid, malic acid, citric acid, gluconic acid, pantothenic acid, 12-hydroxystearic acid, mandelic acid, cholic acid, β- Oxynaphthoic acid, ricinolic acid, quinic acid, cykimic acid, salicylic acid, α, β-dihydroxyhexahydrophthalic acid are encouraged. Among these, tartaric acid having a large melting point drop of 70 to 100 ° C., with an addition amount of 5% by weight or less (particularly 0.01 to 5% by weight), more preferably 1% by weight or less (particularly 0.1 to 2% by weight), based on diacetal, Lactic acid, malic acid, citric acid and α, β-dihydroxyhexahydrophthalic acid are particularly encouraged.
Examples of the resin acid include dehydroabietic acid, abiotic acid, isopymic acid, levofimaic acid, dihydroabietic acid, neoabietic acid, tetrahydroavietic acid, eletinoic acid, parastriic acid, pymal acid, sandaracofimal acid, Grapecarpic acid, agatenedicarboxylic acid, cinnamic acid, p-oxycinnamic acid and the like are exemplified, among which dehydroabietic acid, abietic acid, dihydroabietic acid, neoavietic acid and tetrahydroabietic acid Back is encouraged.
As the carboxylic acid having a carbonyl group having 80 or less carbon atoms, mono, di, tri or tetracarboxylic acids having 6 to 30 carbon atoms having 1 to 3 carbonyl groups are preferable, and levulinic acid, pyruvic acid, o-benzoylbenzoic acid and the like are exemplified. do.
As the carboxylic acid having an ether bond having 80 or less carbon atoms, mono, di, tri or tetracarboxylic acids having 4 to 18 carbon atoms having 1 to 3 ether bonds are preferable, and 4-methoxycyclohexane carboxylic acid and 4- Ethoxycyclohexane carboxylic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, p-phenoxybenzoic acid, 2-methoxy-naphthalenecarboxylic acid and the like are encouraged.
As the carboxylic acid having an ester bond having 80 or less carbon atoms, mono, di, tri, or tetracarboxylic acids having 6 to 30 carbon atoms having 1 to 4 ester bonds are preferable, and acetyl citric acid, stearoyl citric acid and acetyl ricinolic acid , Polys such as stearoyl lactic acid, citric acid monocytearyl ester, citric acid distearyl ester, adipic acid mono-2-ethylhexyl ester, adipic acid monooctyl ester, terephthalic acid mono octyl ester, terephthalic acid monostearyl ester Polycarboxylic acid etc. which have partial ester or ester bond of carboxylic acid in a molecule | numerator are illustrated, Among these, acetyl citric acid, stearoyl citric acid, acetyl ricinolic acid, stearoyl lactic acid, a citric acid monostearyl ester, adipic acid Mono-2-ethylhexyl ester and adipic acid monooctyl ester are encouraged.
As the carboxylic acid having an amide bond and an amino group having 80 or less carbon atoms, mono, di, tri or tetracarboxylic acid having about 1 to 4 carbon atoms having 1 to 4 amide bonds and 1 to 4 amino groups is preferable, and aspartic acid amide , Glycyl-alanine, glycyl-α-aminobutyric acid, glycyl-astagragin, glycyl-glutamine, glycyl-glycine, glycine-glycyl-glycine, glycyl-glycyl-glysil-glycine, article Lysyl-leucine, glycyl-norroicine, glycyl-norvaline, glycyl-α-phenylalanine, glycyl-sarcosine, glycyl-tryptophan, allyl-alanine, alanyl-glutamine, alanyl-glycine, allah D, L, DL, etc., such as a silyl- glycyl- glycine, (beta) -alanyl- histidine, alanyl-phenylalanine, alanine-tyrosine, glycineanhydro, etc. are illustrated.
As the carboxylic acid having an amide bond and a hydroxyl group having 80 or less carbon atoms, mono, di, tri or tetracarboxylic acid having about 1 to 4 carbon atoms having 1 to 4 amide bonds and 1 to 4 hydroxyl groups is preferable, and pantothenic acid, And partial amides of polyvalent carboxylic acids having hydroxyl groups such as citric acid monostearylamide and citric acid distearylamide.
Examples of the carboxylic acid containing a heterocyclic ring having 80 or less carbon atoms include mono-, di and tri-carbon having 4 to 18 carbon atoms having 1 to 2 heterocyclic rings having 1 to 2 N and S as hetero atoms in the hetero ring. Or tetracarboxylic acid is preferable, For example, nicotinic acid, a thioctic acid, a proline acid, an oxyproline acid, a suprofen, a thiapropenic acid, etc. are illustrated.
As a carboxylic acid which has a C80 or less thioether bond, a C6-C30 thing which has 1-4 thioether groups is preferable, and dithiooctylic acid, thioctic acid, etc. are illustrated.
Tartaric acid, malic acid, citric acid as the partial salt of the polycarboxylic acid (i.e., a polycarboxylate in which a portion of the carboxyl group of the polycarboxylic acid is -OCCM (M is an alkyl metal, or an alkaline earth metal or a cation)) And partial salts such as succinic acid, glutaric acid, adipic acid, azelaic acid and sebacic acid are preferred.
In the present invention, aluminum salts of neutral to weakly acidic monovalent organic acids are encouraged, in particular mono, di or tri (C6-C30, preferably C8-C22) fatty acid aluminum salts. These aluminum salts are represented by the formula (RCOO) ₃ Al, (RCOO) ₂ Al (OH) or (RCOO) Al (OH) ₂ (wherein RCOO represents a fatty acid residue having 6 to 30 carbon atoms). Among these, mono, di or tri (capronic acid) aluminum, mono, di or tri (enanthate) aluminum, mono, di or tri (caprylic acid) aluminum, mono, di or tri (perargonate) aluminum, mono, di Or tri (capric acid) aluminum, mono, di or tri (undecylic acid) aluminum, mono, di or tri (lauric acid) aluminum, mono, di or tri (tridecylic acid) aluminum, mono, di or tri ( Myristic acid) aluminum, mono, di or tri (pentadecylate) aluminum, mono, di or tri (palmitic acid) aluminum, mono, di or tri (heptadecyl acid) aluminum, mono, di or tri (stearic acid) Aluminum, mono, di or tri (oleic acid) aluminum, mono, di or tri (nonadecanoic acid) aluminum, mono, di or tri (arachinic acid) aluminum, mono, di or tri (behenic acid) aluminum, mono, Di or tri (lignoseric acid) aluminum, wool , Di or tri (serotinic acid) aluminum, mono, di or tri (montanic acid) aluminum, mono, di or tri (erridine) aluminum, mono, di or tri (erucanoic acid) aluminum, mono, di or tri ( Linoleic acid) aluminum, and the like. Among these, the mono or di (carboxylic acid) aluminum salt in the said specific example is encouraged.
Moreover, as a sulfonate used as a binder in this invention, the alkylbenzene sulfonate or alkylnaphthalene sulfonate of 1-30, especially 6-14, preferably 8-14 of carbon atoms of an alkyl group; Alkanesulfonates having 6 to 30 carbon atoms, preferably 12 to 22 carbon atoms or alkenesulfonates having 6 to 30 carbon atoms, preferably 12 to 22 carbon atoms; Dialkyl sulfosuccinate salt whose alkyl part is a C3-C12 alkyl group, a cyclohexyl group, a C1-C3 alkyl substituted cyclohexyl group, etc. can be illustrated.
Examples of the sulfuric acid ester salts include sulfuric acid ester salts of saturated or unsaturated aliphatic alcohols, sulfuric acid ester salts of ethylene oxide adducts (additional moles 1 to 10) of saturated or unsaturated aliphatic alcohols, and the like. As this saturated or unsaturated aliphatic alcohol, a C4-30, especially 6-30, Preferably 8-20 thing can be illustrated. Moreover, as said unsaturated aliphatic alcohol, what has 1-3 unsaturated bonds (especially double bond) in a molecule | numerator is preferable.
Salts of α-sulfo fatty acids or salts of α-sulfo fatty acids C1-C10 alkyl (particularly C1-C5 alkyl) esters may also be used, and examples of the fatty acids constituting this may include saturated or unsaturated fatty acids having 6 to 30 carbon atoms. Especially as this (alpha)-sulfo fatty acid salt or its ester salt, salt, such as (alpha)-sulfo-stearic acid, (alpha)-sulfo-stearic acid, and (alpha)-sulfo-stearic acid butyl, etc. can be illustrated.
Examples of these sulfonic acid or sulfuric acid ester salts include alkali metal salts such as lithium, sodium and potassium, alkaline earth metal salts such as ammonium salts, calcium and magnesium, and the like.
Examples of the phosphoric acid ester salt include alkali metal salts or alkaline earth metal salts of phosphate esters in which the alcohol residue of the ester is an alkyl group having 4 to 30 carbon atoms or an unsaturated hydrocarbon group having 4 to 30 carbon atoms having 1 to 3 unsaturated bonds, or a hydroxyl group having 4 to 12 hydroxyl groups. Alkali metal salts or alkaline earth metal salts of esters of polyhydric alcohols having 5 to 12 carbon atoms and phosphoric acid, particularly alkali metal salts or alkaline earth metal salts of pentaerythritol or esters of dipentaerythritol and phosphoric acid can be exemplified. As this alkali metal, sodium, potassium, lithium can be illustrated, and as this alkaline earth metal, calcium, magnesium, etc. can be illustrated.
Among the above binders, the following are preferable in terms of melting point lowering action.
(a) aliphatic monocarboxylic acids having 8 to 30 carbon atoms, among them lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, isostearic acid and eicosanoic acid; , Behenic acid, docosahexanoic acid, montanic acid, benzyl acid, sorbic acid, oleic acid, linoleic acid, linoleic acid, etc.,
(b) aliphatic dicarboxylic acids having 3 to 18 carbon atoms or aliphatic tricarboxylic acids having 6 to 30 carbon atoms or aliphatic tetracarboxylic acids having 8 to 30 carbon atoms, among them succinic acid, glutaric acid, and maronic acid; Adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid, itaconic acid, tricarvalylic acid, 1,2,3,4-butanetetracarboxylic acid, citrazinic acid, 1,2,3 , 4-cyclopentanetetracarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4,4'-dicyclohexyldicarboxylic acid, cyclohexanetetracarboxylic Mountain lighthouse,
(c) aromatic monocarboxylic acids having about 7 to 15 carbon atoms, among which benzoic acid and benzoic acid having 1 to 2 alkyl or 1 phenyl groups substituted with benzoic acid and 1 to 4 carbon atoms (for example, p-methylbenzoic acid and p-ethyl) Benzoic acid, n-propylbenzoic acid, cuminic acid, p-tert-butyl benzoic acid, p-isobutylbenzoic acid, p-phenylbenzoic acid), 1-naphthoic acid, 2-naphthoic acid, tetralinmono Carboxylic acid, etc.
(d) di, tri or tetracarboxylic acids having 8 to 20 carbon atoms, among which o-phthalic acid, m-phthalic acid, p-phthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, dipenic acid and biphenyldica Leic acid, biphenyl tetracarboxylic acid, naphthalenedicarboxylic acid, diphenyl sulfone tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylmethane tetracarboxylic acid, diphenyl propane tetracarboxylic acid, ethylene Glycol-4,4'-bistrimellitic acid trimellitate, and the like,
(e) carboxylic acids having 3 to 20 carbon atoms having halogen atoms, in particular aliphatic dicarboxylic acids having 3 to 18 carbon atoms having 1 to 3 halogen atoms or having 6 to 30 carbon atoms having 1 to 3 halogen atoms; Aliphatic tetracarboxylic acids having 8 to 30 carbon atoms having 1-3 aliphatic tricarboxylic acids or halogen atoms (wherein halogen atoms are chlorine, bromine, etc.), among others chloropropionic acid, bromopropionic acid, o -Chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, 4-chloro-3-nitrobenzoic acid,
(f) mono and dicarboxylic acids having 5 to 12 carbon atoms having 1 to 3 amino groups, among them, glutamine, especially L-glutamine,
(g) mono, di or tri (C6-C30 fatty acid) aluminum salts, in particular di and mono (carboxylic acid) aluminum salts, inter alia di and mono (perargonate) aluminum, di and mono (lauric acid) aluminum, Di and mono (myritic) aluminum, di and mono (stearic acid) aluminum, di and mono (oleic acid) aluminum, and the like,
(h) mono, di, tri, and tetracarboxylic acids having 1 to 5 carbon atoms having 1 to 5 hydroxyl groups, among them tartaric acid, lactic acid, malic acid, citric acid, gluconic acid, pantothenic acid, 12-hydroxystearic acid, and only Delic acid, cholic acid, β-oxynaphthoic acid, ricinolic acid, quinic acid, sikimic acid, salicylic acid, α, β-hydroxyhexahydrophthalic acid, and the like,
(i) resinic acid, inter alia, dehydroabietic acid, abietic acid, dihydroabietic acid, neoabietic acid, tetrahydroabietic acid, and the like,
(j) mono and dicarboxylic acids having about 4 to 18 carbon atoms having 1 to 3 carbonyl groups, and those having about 5 to 14 carbon atoms having 1 to 2 carbonyl groups, for example, levulinic acid, pyruvic acid, o -Benzoyl benzoic acid, etc.
(k) mono and dicarboxylic acids having about 8 to 15 carbon atoms having 1 to 2 ether bonds (especially mono and dicarboxyl having 1 to 2 alkoxy groups having 1 to 4 carbon atoms and having 8 to 15 carbon atoms in total) Acid), inter alia 4-methoxycyclohexanecarboxylic acid, 4-ethoxycyclohexanecarboxylic acid, 4-ethoxycyclohexanecarboxylic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, p-phenoxy Sibenzoic acid, etc.
(l) mono and dicarboxylic acids having 5 to 26 carbon atoms having 1 to 2 ester bonds, inter alia acetyl citric acid, stearyl citric acid, acetyl ricinolic acid, stearoyl lactic acid, citric acid monostearyl ester, adipic Acid mono-2-ethylhexyl ester, adipic acid monooctyl ester,
(m) alkali metal salts, ammonium salts and calcium salts of (m-1) alkanesulfonic acids having 6 to 30 carbon atoms, alkenesulfonic acids having 6 to 30 carbon atoms, (C1-C22 alkyl) benzenesulfonic acid and (C1-C14 alkyl) naphthalenesulfonic acid; Alkaline earth metal salts such as magnesium salts, and the like (m-2) sulfuric acid ester salts of saturated or unsaturated aliphatic alcohols having 6 to 30 carbon atoms; Sulfuric acid ester salts of saturated or unsaturated aliphatic alcohols having 6 to 30 carbon atoms to which 1 to 10 mol of ethylene oxide is added; Sulfosuccinic acid diester salts (in particular sulfosuccinic acid diester salts in which the alcohol moiety of the ester is a C2-C16 alkyl group, a cyclohexyl group, or a C1-C5 alkyl group substituted cyclohexyl group); α-sulfo fatty acid salts or α-sulfo fatty acid ester salts (particularly α-sulfofatty acids having 6 to 30 carbon atoms or C 1 -C 10 alkyl ester salts of α-sulfo fatty acids having 6 to 30 carbon atoms), the cations constituting these salts Examples thereof include alkali metals such as potassium and sodium, and alkaline earth metals such as ammonium and calcium and magnesium, among which (mm) potassium or sodium salt of C18 alkanes or alkenesulfonic acids, sodium dodecylbenzenesulfonate and sodium dode Silsulfate, sodium dodecyl ether sulfate (i.e., sodium salt of sulfuric acid ester of dodecyl alcohol to which 1 mol of ethylene oxide is added), sodium dioctyl sulfosuccinate, sodium methyl α-sulfostearate, and the like.
The binders of (a) to (m) may be used singly or in combination of two or more kinds.
Among the above (h) at least one mono, di, tri and tetracarboxylic acid having 4 to 24, preferably 4 to 12, carbon atoms having 1 to 5, preferably 1 to 4, hydroxyl groups, in particular tartaric acid and lactic acid , Malic acid, citric acid, gluconic acid, pantothenic acid, 12-hydroxystearic acid, mandelic acid, cholic acid, β-oxynaphthoic acid, ricinolic acid, quinic acid, sikimic acid, salicylic acid, α, β-hydroxyhexahydrophthalic acid, and the like, or The binder as described in said (m) is preferable.
Further, for example, at least one selected from the group consisting of (ha) tartaric acid, lactic acid, malic acid, citric acid and β-dihydroxyhexahydrophthalic acid, the binder described in the above (m), in particular the binder described in (mm) Preference is given to at least one selected from the group or mixtures of (ha) and (mm).
The binder described in (a) to (m), in particular the binder described in (h) or the binder described in (m), is usually about 0.01 to 8 parts by weight, preferably about 100 parts by weight of the diacetal represented by the formula (1). The melting point drop effect is exhibited by using about 0.1 to 5 parts by weight, more preferably 0.1 to 1.0 part by weight.
As a binder used by this invention, the following are mentioned as a preferable example.
(1) at least one binder selected from the group consisting of the binder described in (h) and the binder described in (a) above
(2) at least one binder selected from the group consisting of the binder described in (h) and the binder described in (b) above
(3) at least one binder selected from the group consisting of the binder described in (h) and the binder described in (m) above
④ at least one binder selected from the group consisting of the binder described in the above (m) and the binder described in the above (a)
⑤ at least one binder selected from the group consisting of the binders described in the above (m)
(6) at least one binder selected from the group consisting of the binder described in the above (m) and the binder described in the above (g)
⑦ at least one binder selected from the group consisting of the binder described in the above (g) and the binder described in the above (a)
The amount of the binder used in the present invention is not particularly limited as long as the effect of the present invention is obtained, whether one type of binder is used or two or more types are used in combination, and the types of diacetals and organic acids and derivatives thereof. It can select suitably according to. The amount of the binder is usually 0.01 to 100 parts by weight, preferably 0.1 to 70 parts by weight, and more preferably 0.1 to 25 parts by weight based on 100 parts by weight of the diacetal represented by the formula (1). If the amount is less than 0.01 part by weight, the effect of lowering the melting point is hardly obtained, and no binder effect is obtained. Moreover, when it uses more than 100 weight part, the advantage that the effect of a binder effect and melting | fusing point fall is better is hard to be recognized, and it tends to generate the tendency which lowers a polyolefin nucleating agent effect.
In addition, the binder described in the above (h) or the binder described in the above (m) exhibits a melting point lowering effect and a binder effect even in a small amount.
<Granular or powdery diacetal composition>
The granular or powdery diacetal composition of the present invention comprises the diacetal of the formula (1) and the binder, as a result of uniform infiltration between the fibrous crystals of the diacetal, as well as the surface of the diacetal particles, It is evenly distributed inside the acetal particles. As the uniform distribution of the binder increases, a significant melting point drop effect is exerted.
In general, it is well known that when the second substance Y is added to the pure substance X, the melting point of the pure substance X is lowered (the solidification point decrease). This falling melting point depends on the molar concentration of (Y). When 10 weight part (Y) is added to 90 weight part of diacetals represented by General formula (1), the melting | fusing point will fall only about 2-3 degreeC, even if it catches large.
In contrast, the diacetal composition obtained by uniformly distributing the binder in the diacetal represented by the formula (1) according to the present invention has a melting point drop of 70 ° C. or higher, preferably lower than that of the diacetal itself contained in the composition. 20 ° C. or higher, more preferably 40 ° C. or higher, particularly 50 ° C. or higher, even more particularly 70 ° C. or higher, and most preferably 90 ° C. or higher, so that the melting point is due to a mechanism due to an unusual interaction different from the normal freezing point drop. You can think that you have descended. In particular, the melting point lowering mechanism of 50 DEG C or higher is unclear. In any case, the binder according to the present invention must swell the fibrous crystals of the diacetal represented by the formula (1) and distribute them evenly between the crystals until it is at least 7 ° C, preferably at least 20 ° C, more preferably at least 90 ° C. It expresses a lowering effect. The maximum value of the melting point drop may vary depending on the type of binder, the amount used, the production method, and the like, but is not particularly limited, but is generally about 100 ° C. As a result, the melting point of the diacetal composition of the present invention is usually about 185 to 230 ℃.
According to the present invention, lowering the melting point of diacetal by at least 7 ° C, preferably at least 20 ° C, more preferably at least 40 ° C, even more preferably at least 90 ° C, is the dissolution of diacetal in molten resin or various liquids. It will speed up dramatically. This is because the mixing of the molten polyolefin liquid and the diacetal solid is converted to the mixing of the liquids at a temperature above the melting point of the polyolefin. That is, in the prior art, although the solid high melting point diacetal was dissolved in a liquid such as a molten polyolefin resin during molding processing, in the present invention, the melting point of the diacetal was drastically lowered. The melting point is higher than the melting point, and as a result, the diacetal is melted within a very short time after adding the diacetal composition of the present invention to the molten polyolefin, in some cases at the same time or substantially immediately after the addition, and the melted diacetal is melted. This is because the polyolefin is dissolved in the liquid-liquid mixture.
In addition, since it can be dissolved at a considerably low temperature, for example, diacetal does not cause decomposition or sublimation or coloring in forming a polyolefin resin. Moreover, energy saving by low temperature shaping | molding can be aimed at.
The form of the diacetal composition according to the present invention extends from powder to granules of any shape such as noodle or granules or tablets. In the case of powder form, the average value of the particle diameter is 3-2000 micrometers, Preferably it is 3-200 micrometers, Especially 5-500 micrometers, More preferably, it is 7-250 micrometers. When smaller than 3 micrometers, the fluidity | liquidity, conveyance, and suppression of dust may be hard to be obtained enough, and a special grinding | pulverization apparatus is needed.
Here, the average value of the particle diameter of the said powder is the median diameter measured using distilled water as a dispersion medium using the laser diffraction / scattering particle size distribution measuring apparatus (The Horiba company make, brand name "LA-910"). In this specification, the average value of this particle diameter is simply called "average particle diameter."
The particle size distribution may be widely distributed and does not have to be a single dispersion in particular. That is, the particle size distribution obtained by a normal industrial grinding device is sufficient.
In the case of granules, a cylindrical or noodle having a diameter of 0.2 to 5 mm, preferably 0.5 to 2 mm and a length of 0.2 to 15 mm or granules or flakes having a diameter of 0.2 to 5 mm, preferably 0.5 to 2 mm Can be illustrated.
As an encouraged apparent density of the diacetal composition according to the present invention, 0.2 to 1.1 g / cm 3 is exemplified, more preferably 0.2 to 0.75 g / cm 3. When the apparent density is less than 0.2 g / cm 3, the effects of fluidity, transportability, dust suppression and adhesion prevention of the powder may not be sufficiently obtained. When it exceeds 1.1 g / cm <3>, powder characteristics will improve remarkably, but the melt | dissolution rate to a molten resin or various fluids may become somewhat small. The apparent density can be arbitrarily adjusted according to the drying temperature and drying mode or granulation method when preparing the diacetal composition of the present invention. That is, when the drying rate is small and the drying temperature is high, the apparent density tends to be high, and when the drying rate is large and the drying temperature is low, the apparent density tends to be low. Moreover, when the compression ratio at the time of granule shaping | molding is large, apparent density will become high.
If necessary, the granular diacetal composition of the present invention may contain various additives such as an antistatic agent, a neutralizer to a stabilizer, a lubricant, a polymer, and the like in addition to the binder.
In the present invention, the antistatic agent increases the degree of swelling during the preparation of the diacetal composition to improve the uniformity, thereby improving the effect of the binder effect and the melting point drop and at the same time improving the quality stability, or losing the chargeability of the diacetal composition. To increase the apparent density. This is important for further improving quality stability, transportability and flowability.
Specific antistatic agents include glycerin fatty acids (8 to 22 carbon atoms) mono, di or triesters, sorbitan fats (4 to 22 carbon atoms) mono, di, tri and tetraesters, polypropylene glycol fatty acids (8 to 22 carbon atoms), penta Erythritol fatty acid (C8-22) ester, trimethylolpropane fatty acid (C8-22) ester, polyglycerol fatty acid (C8-22) ester, (polyoxyethylene 4-50 mol) alkyl (7-22 carbon) phenyl Ether, polyoxyethylene (4 to 50 moles) alkyl (12 to 22 carbon atoms) ether, N, N-bis (2-hydroxyethyl) alkyl (8 to 22 carbon atoms) amine, polyoxyethylene (4 to 50 moles) Monoalkyl (7 to 22 carbon atoms) amine, polyethylene glycol (4 to 50 moles) fatty acid (8 to 22 carbon atoms) ester, sulfate (sodium, potassium, ammonium salt) ester, sorbitan mono, di and tri fatty acids (carbon number 4-22) ester etc. are illustrated.
Among these antistatic agents, in particular, glycerin fatty acid (C8-C22) mono, di and triesters, N, N-bis (2-hydroxyethyl) alkyl (C8-C22) amine, polyoxyethylene (4-50 mole) alkyl ( C12-C22) ether, polyoxyethylene (4-50 mol) alkyl (C7-C22) phenyl ether, pentaerythritol fatty acid (C8-C22) ester is preferable.
The antistatic agent is preferably blended in an amount of 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the diacetal represented by the formula (1). By incorporating an antistatic agent, not only the chargeability is lost, but the increase in the binder effect by increasing the degree of swelling also helps to increase the apparent density effectively.
As a neutralizer or stabilizer, calcium stearate, lithium stearate, potassium stearate, sodium stearate, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate ] Metal soaps, phenolic compounds, phosphorus compounds, sulfur compounds and the like typified by methane, tris (2,4-di-t-butylphenyl) phosphite, 3,3'-thiodipropionate distearyl, etc. The amount is about 5 to 100 parts by weight, preferably about 15 to 70 parts by weight based on 100 parts by weight of the diacetal represented by the formula (1).
As said lubricant, hardening oil, for example, hardened castor oil, hardened rapeseed oil, hardened palm oil, hardened tallow, hardened cottonseed oil, hardened soybean oil, etc. can be illustrated. The amount of the lubricant is about 1 to 20 parts by weight, preferably about 3 to 10 parts by weight based on 100 parts by weight of the diacetal represented by the formula (1).
Examples of the polymer include polyethylene or polypropylene having a molecular weight of 10,000 or less, hydrogenated petroleum resin, ethylene-propylene rubber, etc., and the amount of the polymer is about 5 to 10,000 parts by weight based on 100 parts by weight of diacetal represented by the formula (1), Preferably it is about 100-5000 weight part.
The diacetal composition of the present invention can improve the binder effect in addition to the effect of lowering the melting point by using at least one selected from the group consisting of the binder, the antistatic agent, the neutralizer or the stabilizer and the lubricant. In this case, any of the above can be used as the binder, and in particular, the binders described in the above items (a) to (m) can be used alone, or two or more kinds can be used in combination.
In particular, at least one binder selected from the group consisting of (I) the binder described in (ha), the binder described in (m), the binder described in (a) and the binder described in (g), and (II) It is preferable to use together the hardening oil which is the said lubricant.
In this case, although the use ratio of (I) and (II) is not specifically limited, Generally, it is encouraged to use about 10-10000 weight part of (II) with respect to 100 weight part of (I).
When using a combination of the above (I) and (II), the amount of (I) is about 0.1 to 30 parts by weight, preferably about 0.4 to 20 parts by weight based on 100 parts by weight of the diacetal represented by the formula (1). (II) is encouraged to be used in an amount of about 0.5 to 25 parts by weight, preferably about 2 to 10 parts by weight, thereby exhibiting an excellent melting point lowering effect and a binder effect.
It is preferable to use together at least 1 sort (s) of hardening oil chosen from the group which consists of a binder as described in said (h-a), the binder as described in (m), and the binder as described in (a) among the said combination used together.
And it is also preferable to use together at least 1 sort (s) and hardening oil chosen from the group which consists of a binder as described in said (m), and a binder as described in (a).
Moreover, it is also preferable to use together at least 1 sort (s) selected from the group which consists of a binder as described in said (a), a binder as described in (g), and a binder as described in (m), and hardened oil.
<Method for Producing Diacetal Composition>
In the preparation of the diacetal composition according to the present invention, in order to exhibit the effect of the present invention, the binder must be uniformly distributed within or inside the crystal powder, that is, between the fibrous crystals of the diacetal.
Therefore, in the preferred production method of the present invention, the raw diacetal crystal is made to be sufficiently swollen with a solvent, and then mixed with a binder and additives such as an antistatic agent (you may take the form of a melt or a solution), if necessary ( The solvent or water must be removed.) The granules are dried to granulate the diacetal composition, and if necessary, the granulated diacetal composition is pulverized or classified or the granulated diacetal composition is granulated again. .
In particular, the granular or powdered diacetal composition of the present invention
(Iii) preparing a slurry containing a diacetal represented by Formula 1 swelled with a solvent,
(Ii) uniformly mixing the slurry and the binder,
(Iv) (a) removing the solvent from the resulting homogeneous mixture to obtain a dried product, or
(b) granulate with removal of solvent from the resulting homogeneous mixture, or
(c) classifying or pulverizing the dried product obtained in the step (a) or the granulated product obtained in the step (b), or
(d) By the method containing the process of granulating or classifying the pulverized product obtained by said (c), it can obtain as a product of a preferable particle size distribution.
The following three methods can be mentioned as a preferable manufacturing method of the diacetal composition of this invention as a preferable manufacturing method.
〈Method (1)〉
The slurry of the organic solvent capable of swelling the diacetal represented by the general formula (1) and the diacetal represented by the general formula (1) is near the reflux temperature of the organic solvent at 20 to 200 ° C, preferably 100 ° C or lower (for example, 60 to 100 Heated to a sufficient temperature, sufficiently stirred and mixed to swell the diacetal, and then additives such as a binder and an antistatic agent, if necessary, are dissolved and sufficiently dispersed therein, followed by addition of water as necessary. For example, the organic solvent and water are removed in a temperature range of 20 to 180 ° C., granulated by drying with stirring, and then the granules are classified, and the granules are pulverized as necessary to classify the powder obtained. Or a method of granulating the obtained powder again.
In this method, for example, a powdery diacetal can be used as the raw material diacetal. Each particle of this powdery diacetal is comprised by dense aggregation of fibrous diacetal microcrystals. When such aggregated diacetal microcrystals are sufficiently swollen with the organic solvent under the above temperature conditions, they are substantially dispersed into individual fibrous crystals so that the solvent invades between the fibrous crystals and the crystals swell.
Thus, the diacetal crystal is swollen with an organic solvent, and additives such as a binder and an antistatic agent are added to the slurry dispersed in the organic solvent to individual fibrous crystals, and the swollen diacetal crystal and the dissolved binder ( And additives such as dissolved or dispersed antistatic agents) are mixed until uniform, and then the solvent is removed to granulate. In this way, the diacetal composition of this invention in which the binder and additives, such as an antistatic agent, are disperse | distributed uniformly in diacetal particle | grains as needed is obtained.
Sufficient swelling of the fibrous crystals of diacetal is particularly important in order to obtain the maximum melting point drop. When diacetal is disperse | distributed to nonpolar solvents, such as a cyclohexane solvent, at room temperature and fully stirred, a viscosity does not increase rapidly with time. That is, nonpolar solvents, such as a cyclohexane solvent, do not invade in large quantities between the fibrous crystals of diacetal, and swelling of diacetal does not occur. In this state, even if it is dried after adding a binder, the said melting | fusing point fall does not arise largely as mentioned above.
On the other hand, when diacetal is disperse | distributed to the mixed solvent of a nonpolar solvent, for example, a cyclohexane solvent and a polar solvent, and stirred with heat, a viscosity will increase rapidly with time. That is, the mixed solvent infiltrates in large quantities between the fibrous crystals of the diacetal and the degree of swelling of the diacetal develops. The desired melting point drop is obtained by adding the binder in a state of sufficient swelling of the diacetal and then drying. As the degree of swelling of the diacetal develops, a greater melting point drop is obtained. Naturally, swelling of the diacetal is possible only with a polar solvent.
Therefore, in the present invention, a polar organic solvent alone or an aromatic hydrocarbon solvent alone is used as the solvent for the swelling, or (a) at least one member selected from the group consisting of a polar organic solvent and an aromatic hydrocarbon, and ( b) at least one mixture selected from the group consisting of aromatic hydrocarbons and alicyclic hydrocarbons is used.
Examples of the polar solvent include aliphatic alcohols having 1 to 18 carbon atoms, preferably 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms such as methanol, ethanol, isopropanol and butanol; Alicyclic alcohols having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms such as cyclobutanmethanol, cyclohexanol and methylcyclohexanol; Perfuryl alcohol; Cyclic ethers such as dioxane; Ethers such as anisole; Ketones such as acetone and methyl ethyl ketone; Aliphatic amines having about 3 to 6 carbon atoms; Acetonitrile; Glycol ethers such as ethylene glycol monomethyl ether; Dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and the like are exemplified.
As said aromatic hydrocarbon, C6-C18, Preferably 6-12 aromatic hydrocarbons, such as toluene, xylene, mesitylene, ethylbenzene, and isopropylbenzene, can be illustrated.
Examples of the aliphatic hydrocarbons and alicyclic hydrocarbons include aliphatic hydrocarbons having 6 to 18, preferably 6 to 12, carbon atoms such as n-hexane, heptane, nonane, and decane, cyclohexane, methylcyclohexane, and ethylcyclo. C6-C18, preferably C6-C12 alicyclic hydrocarbons, such as hexane, etc. are illustrated.
As the slurry concentration, 1 to 60% by weight, preferably 5 to 60% by weight, more preferably 10 to 40% by weight in diacetal terms are encouraged. Less than 1% by weight is difficult to produce efficiently and uneconomical. When it exceeds 65 weight%, swelling will become inadequate and it will become difficult to stir.
Confirmation of whether or not the diacetal was sufficiently swollen in the slurry is a significant increase in the low tip velocity of the slurry viscosity, the slurry does not separate into two phases even when standing, or is absorbed between the solvent-free fibrous crystals by microscopic observation. Or it can carry out easily by confirming that it is impregnated.
After the diacetal is swollen, the predetermined amount of the binder and, if necessary, additives such as the predetermined amount of the antistatic agent, are dissolved or dispersed in the organic solvent in the slurry. The resulting mixture is mixed and stirred until homogeneous.
The binder and the additive used as necessary may be added as it is, but may be added in the form of a solution previously dissolved in an organic solvent capable of dissolving them or in a form dispersed in an organic solvent or after making them molten. good. As an organic solvent at this time, the organic solvent and water used for the said swelling can be illustrated.
The amount of the binder added is generally 0.01 to 100 parts by weight, preferably 0.1 to 70 parts by weight, more preferably 0.2 to 25 parts by weight based on 100 parts by weight of the diacetal represented by the formula (1). When using additives, such as an antistatic agent, a neutralizing agent, or a stabilizer, a lubricating agent, and a polymer, these are used by said quantity. For example, the antistatic agent is used in an amount of preferably 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight based on 100 parts by weight of the diacetal represented by the formula (1).
Moreover, although the temperature of the slurry at this time is not specifically limited, Generally, room temperature-150 degreeC, Preferably it is encouraged to be about room temperature-100 degreeC.
The organic solvent is then removed from the slurry. In order to remove an organic solvent, the following method can be employ | adopted, for example.
(a) Required for slurries containing such swollen diacetals, binders and, if necessary, additives such as antistatic agents, neutralizing or stabilizing agents, lubricants, polymers (hereinafter simply referred to as "additives such as antistatic agents") in organic solvents. Water is added, and the organic solvent and, if applicable, the water are completely distilled off, for example, at a temperature of 30 to 150 캜, preferably 40 to 120 캜 and dried. The dried product thus obtained is the diacetal composition of the present invention.
(b) water is added to a slurry containing additives such as the swelled diacetal, binder, and antistatic agent in an organic solvent, if necessary, and if necessary, almost all of the organic solvent is heated (for example, 40 to 150 ° C). By distilling off, preferably at a temperature of 40 to 120 ° C., to obtain a residue once wetted with water, and heating this wet residue, if necessary, under heating (for example, about 40 to 150 ° C., preferably at a temperature of 40 to 120 ° C.). Granulate by drying while mixing. The granule obtained in this way is the diacetal composition of this invention.
In addition, in the said method (a), the reason of adding water as needed or the reason of adding water in the said method (b) is iii) easy to control the apparent density of a diacetal composition, and to obtain a large density, ii This is because the organic solvent loses the flammability during drying by efficiently recovering the granules without flammability. When using water from such a viewpoint, the usage-amount is not specifically limited, About 20-1000 weight part with respect to 100 weight part of diacetal represented by General formula (1), Preferably it is about 40-600 weight part.
In the present invention, if necessary, the diacetal composition of the present invention in the form of the dried product obtained in the above method (a) or the granule obtained in the above method (b) may be classified or pulverized, or further, the pulverized product may be classified. If necessary, the dried product or the pulverized product obtained in the above (a) may be granulated again with or without adding a volatile organic solvent such as methanol or ethanol or water.
<Method (2)>
Polyhydric alcohols, such as sorbitol or xylitol, and aromatic aldehydes, such as benzaldehyde and substituted benzaldehyde, are cyclohexane or saturated hydrocarbons according to conventional methods (for example, Japanese Patent Publication No. 73-43748, Patent Publication No. 90-231488). Lower (for example, C1-C4) alcohol (for example, methanol), dimethylformamide (DNF), dimethyl in an organic solvent such as benzene, cyclohexane or benzene having 1 to 3 alkyl groups having 1 to 4 carbon atoms. Reaction mixture obtained by the method of obtaining diacetal by condensation reaction in the presence of a polar solvent such as acetamide (DMAc), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and, if necessary, in the presence of an acid catalyst. (It is preferable to neutralize an acid catalyst and wash with water as needed.) It becomes a slurry containing the diacetal swollen with the said solvent.
Or diacetal in an organic solvent such as a lower aliphatic ketone or a lower aliphatic alcohol according to a known purification method of diacetal (for example, purification methods such as JP-A-78-5165 and JP-A-82-185287). In the course of the process of refining, the slurry in which diacetal is swollen with the said organic solvent is obtained.
In the present invention, to the slurry containing the diacetal represented by the swelling formula (1), additives such as a binder and an antistatic agent (you may take the form of a melt or a solution or a homogeneous dispersion), if necessary, are sufficiently uniformly dispersed. Let's do it.
Thereafter, (i) the slurry containing the binder and an additive such as an antistatic agent is added as is or water to the slurry, and the organic solvent and, if applicable, water in a temperature range of 20 to 180 ° C. The residue is distilled off and the residue is granulated under heating (for example, at a temperature of about 40 to 150 ° C., preferably at a temperature of 40 to 100 ° C.) as necessary. If necessary, the granules are subsequently classified. The classified granules may be pulverized again, and further, the pulverized matter may be classified. Moreover, the obtained milled product can also be granulated.
Or (ii) water is added to the slurry containing a binder and, if necessary, an additive such as an antistatic agent, and made into an aqueous dispersion system by distilling an organic solvent out of the system using an azeotropy of water and an organic solvent. The aqueous dispersion is granulated with or without filtration, for example, in a temperature range of 20 to 180 ° C. If necessary, the granules are classified, ground or classified again. Or granulate the mill again.
When water is used in the above (iii) and (ii), the amount of water used is about 20 to 1000 parts by weight based on 100 parts by weight of the diacetal represented by the formula (1).
In this manufacturing method, it is not specifically limited if the effect of this invention is acquired as a timing of adding an additive, such as a binder and an antistatic agent as needed. Usually, after completion of the acetalization reaction of the diacetal, the acid catalyst is neutralized, and the diacetal after undergoing a water washing step is promoted as a diacetal in a swelling state with the organic solvent. In addition, when adding a binder and an additive, such as a charge control agent, as needed in a refinement | purification process, it is preferable to add, after a system becomes slurry and swells.
The usage-amount of additives, such as a binder and the antistatic agent added as needed, is the same as that of the said method (1). After adding a binder and an additive, such as an antistatic agent, if necessary, the same operation as in the method (1) above (solvent is removed (dry) to obtain a dried product, granulated while removing the solvent (dry), or obtained The present invention in which additives such as binders and additives such as antistatic agents are uniformly dispersed in acetal particles by performing classification or grinding of dried or granulated materials, or granulating or classifying the obtained ground products. To obtain a diacetal composition.
<Method (3)>
Synthesis of the diacetal represented by the formula (1) by water-based reaction and neutralization and washing of the reaction mixture to obtain an aqueous slurry of diacetal swollen with water, to which additives such as a binder and an antistatic agent, if necessary, at room temperature Or uniformly mixed by heating to obtain a uniformly mixed slurry, and if necessary, the uniformly mixed slurry is filtered to obtain a wet cake. The homogeneous mixed slurry or wet cake is dried to obtain a dry product. Or granulate by drying while mixing the homogeneous mixed slurry or wet cake. The resulting dried or granulated product is the diacetal composition of the present invention. If necessary, the diacetal composition of the present invention in the form of a dried product or granulated product obtained above may be classified or pulverized, or the obtained pulverized product may be classified or granulated.
The aqueous reaction is, for example, a method described in US Pat. No. 5,023,354. In brief, a polyhydric alcohol such as benzaldehyde and sorbitol, which may be substituted, is used as water as a solvent and 10% by weight or more based on the reaction substrate. It is characterized by reacting in the presence of a large amount of acid catalyst.
The aqueous slurry is obtained by neutralizing the reaction mixture obtained by the aqueous reaction and washing the neutralized reaction mixture. This aqueous slurry is in a swollen state consisting of a diacetal-specific fibrous crystal and a large amount of water infiltrated between the crystals.
Moreover, it is preferable that it is hydrophilic as additives, such as a binder which should be uniformly disperse | distributed to the aqueous slurry of diacetal obtained by the said aqueous reaction, and an antistatic agent added as needed.
As said hydrophilic binder, a divalent or more hydroxyl group containing polycarboxylic acid can be illustrated, Especially di-, tri-, or tetracarboxylic acid of 3 to 10 carbon atoms which has 1-3 hydroxyl groups is preferable. Among these, in particular, L-tartaric acid, D-tartaric acid, DL-tartaric acid, D-, L- or DL-lactic acid, D-, L- or DL-malic acid, D-, L- or DL-citric acid, α, β-di Hydroxyhexahydrophthalic acid and the like are preferable. Moreover, alkyl (average chain length 12) benzenesulfonic acid soda which may contain alkyl (C6-14) sulfate, sodium sulfate, etc. are preferable.
As the hydrophilic additive, an antistatic agent, for example, stearic acid monoglyceride, stearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, myristic acid monoglyceride, myristic acid diglyceride, lauric acid monoglyceride, lauric acid dilauric acid Glyceride, polyethyleneglycol monostearate, etc. can be illustrated.
In this case, the amount of the hydrophilic binder is preferably about 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight based on 100 parts by weight of the diacetal represented by the formula (1). Moreover, 0.01-8 weight part is preferable with respect to 100 weight part of diacetals represented by General formula (1), and, as for the usage-amount of additives, such as a hydrophilic antistatic agent, 0.1-5 weight part is more preferable.
However, even if the binder and the additive used as needed are lipophilic, it can be used.
In the said methods (1)-(3), as a method of drying and granulating with mixing, if an organic solvent or water can be removed, it will not specifically limit, Generally, the method used industrially can be used. For example, the mixture is warmed to 20 to 180 ° C. with steam or a thermal solvent, and granulated while stirring and drying for about 1 to 20 hours under normal pressure or reduced pressure.
Moreover, although the method of drying in a stationary state can also be illustrated as one kind of drying method, it is industrially preferable to granulate, drying under stirring.
In addition, the method of granulating with the powder after drying is not specifically limited as long as the effect of this invention is acquired, but can be granulated using the granulation apparatus generally used industrially. At this time, water or an organic solvent may be used to wet the diacetal powder. As a granulator, compression granulators, such as various extrusion granulators or a tablet machine, are mentioned, for example.
The grinding method is not particularly limited as long as the effect of the present invention is obtained, and generally a industrially used grinding device can be used. For example, an atomizer, a pulverizer, a nibbler, a hammer mill, a micron mill, a cross flow mill, a pin mill, etc. are mentioned.
<Nucleating agent for polyolefin resin>
The powdered or granulated diacetal composition obtained by the above method has a significantly lower melting point than the melting point of diacetal by the melting point lowering action of the binder uniformly dispersed in the diacetal particles.
Thereby, the dissolution rate with respect to molten resin or various liquids rises, and the solubility and dispersibility improve remarkably. At the same time, the apparent density can be increased by the binder effect to form a compact package. That is, in this powdery diacetal composition, granules of any shape and size can be obtained again by using various extruded granulators or compressed granulators as necessary. The powder or granular diacetal composition improves the fluidity or transportability of the diacetal composition, dust generation, and improves solid properties such as inhibition of adhesion to glass or metal. Moreover, the handleability as a solid improves more by containing additives, such as an antistatic agent.
As a result, by using the diacetal composition of the present invention as a nucleating agent for polyolefin resin, it satisfies the good addition transportability compared to the case of adding the usual diacetal to the polyolefin resin, and at the same time kneaded at a significantly low kneading temperature, productivity It is possible to extrude well. Production of a highly concentrated master batch pellet made of diacetal and polyolefin resin becomes very easy. Moreover, the heat residence time at the time of kneading is shortened and productivity improves significantly. In addition, since the sublimation property of diacetal is lost by low-temperature molding and thermal decomposition property is suppressed, the problem of contamination or odor at the time of molding is solved. In addition, the microdispersion in the polyolefin resin composition is dramatically reduced, leading to a dramatic improvement in productivity or quality.
In addition, confirmation of whether the binder is uniformly distributed on the particle surface and inside of the granular diacetal composition can be easily confirmed by polarization microscopy under cross nicol.
Into the nucleating agent for polyolefin resin containing the diacetal composition of the present invention, if necessary, other components, for example, metal soap or pigment such as calcium stearate commonly used as a neutralizing agent of the resin, stabilizers such as radical inhibitors, etc. You may.
The powdered or granulated diacetal composition of this invention or the master batch pellet obtained from this acetal composition and polyolefin resin can be manufactured, and this can also be used for injection molding or extrusion molding. The compounding quantity of 2-20%, preferably 5-15% of masterbatch pellets to polyolefin resin is not specifically limited as long as the effect of this invention is acquired, It can select suitably. Usually, about 0.01 to 5 parts by weight, preferably about 0.05 to 3 parts by weight, in terms of diacetal represented by the general formula (1) relative to 100 parts by weight of the polyolefin resin is blended. By mix | blending within such range, the effect of this invention can fully be acquired.
<Polyolefin resin composition>
The polyolefin resin composition of this invention mix | blends the diacetal composition of the said invention with polyolefin resin.
As described above, since the diacetal composition of the present invention is dissolved at a temperature lower than the melting point of the diacetal itself represented by the formula (1) constituting the diacetal composition, the diacetal composition of the present invention is used as a nucleating agent for polyolefin resin. By using it, it becomes possible to knead | mix and extrude at the remarkably low kneading temperature compared with the case where ordinary diacetal participates in a polyolefin resin. Moreover, the heat residence time at the time of kneading is shortened and productivity improves significantly.
The polyolefin resin according to the present invention is a crystalline resin having a crystallinity of 5 to 100%, preferably 15 to 95%, specifically, a polyethylene resin, a stereoregular polypropylene resin, a stereoregular polybutene resin, or a steric resin Terpolymer resins such as regular ethylene-propylene-butadiene and the like are exemplified.
As polyethylene-type resin, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, and ethylene copolymer containing 50 weight% or more of ethylene are illustrated.
As a polypropylene resin, a propylene copolymer containing propylene homopolymer and propylene containing 50% by weight or more is exemplified.
Examples of the polybutene resin include butene homopolymers and butene copolymers having a butene content of 50% by weight or more.
Each copolymer may be a random copolymer or a block copolymer. Moreover, the stereoregularity of such resin may be isotactic or syndiotactic.
Specific examples of comonomers that can form each of the copolymers include α-olefins such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene and dodecene, and 1,4-endo. Bicyclo-type monomers, such as methylene cyclohexene, (meth) acrylic acid ester, such as methyl (meth) acrylate and ethyl (meth) acrylate, vinyl acetate, maleic acid, etc. can be illustrated.
As a catalyst used to prepare such a polymer, conventionally known catalysts can be used without particular limitation, and generally used radical polymerization catalysts or Ziegler-Natta type catalysts, as well as transition metal compounds (for example, titanium trichloride and titanium tetrachloride). Catalysts or metalocene catalysts formed by combining a catalyst formed by supporting a titanium halide such as titanium halide) on a carrier containing magnesium halide such as magnesium chloride and an alkylaluminum compound (such as triethylaluminum, diethylaluminium chloride, etc.) Can be used.
The encouraged methyl flowrate of the polyolefin-based resin according to the present invention (hereinafter abbreviated as "MFR". JIS K 7210-1976) is appropriately selected depending on the molding method used and the physical properties of the molded article, and usually 0.01 to 200 g. / 10 minutes, preferably 0.05 to 100 g / 10 minutes. If it is in the range of this MFR, the mixture of polyolefin resin from which the kind of resin or MFR differs is also encouraged.
The compounding quantity as a nucleating agent with respect to the polyolefin resin of the powdery or granulated diacetal composition of this invention is not specifically limited as long as the effect of this invention is acquired, It can select suitably. Usually, about 0.01 to 5 parts by weight, preferably about 0.05 to 3 parts by weight, in terms of diacetal represented by the general formula (1) relative to 100 parts by weight of the polyolefin resin is blended. By containing within this range, the effect of this invention can fully be acquired.
Moreover, you may mix | blend a metal soap with the polyolefin resin composition of this invention as needed. As the metal soap suitably blended with the polyolefin resin, lithium salts, sodium salts, potassium salts and calcium salts of fatty acids having 16 to 22 carbon atoms (preferably having 16 to 18 carbon atoms) or 12-hydroxystearic acid are known. The use of salts, lithium salts and calcium salts is particularly encouraged in terms of improving transparency.
The powdery or granulated diacetal composition according to the present invention may be in the form of a master batch by using various resin additives in combination without impairing the object of the present invention. Moreover, you may produce the pellet of the compounding ratio of a normal concentration. That is, when preparing and mold-forming a polyolefin resin composition, instead of blending each of powdery or granulated diacetal composition and another resin additive separately to a polyolefin resin, it is a powdery or granulated di-die which contains various resin additives previously. By manufacturing an acetal composition and adding it to a polyolefin resin to produce a resin composition or shaping | mixing with polyolefin resin, the operation efficiency of polyolefin resin molding can be improved significantly.
As such other resin additives, various resin additives described as additives of polypropylene, polyethylene, or polybutenyo are exemplified in Japanese Hygiene Consultation Participant "Positive List Additive Cradle" (January 1995), and more specifically, such as polyolefin, Examples of stabilizers include phosphorus compounds such as distearyl pentaerythritol phosphite or irgafos 168, metal compounds such as 2-ethylhexane zinc, epoxy compounds such as epoxidized soybean oil and epoxidized linseed oil, melamine and the like. Phosphorus compounds such as nitrogen compounds and trisnonylphenylphosphate, sulfur compounds such as 3,3'-thiodipropionate dialkyl (12 to 18 carbon atoms)], ultraviolet absorbers [for example, 2,2'-dihydroxy Benzotriazole type, such as benzophenone type compounds, such as 4-methoxy benzophenone and 2-hydroxy-4-n-octoxy benzophenone, and 2- (2'-hydroxy-5'-methylphenyl) benzotriazoleCompound], antioxidant [eg 2,6-di-tert-butyl-4-methylphenol, tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenol) Propionate] phenol compounds such as methane, phosphorus compounds such as 2,4-di-tert-butylphenylphosphite], silicone oils [eg dimethylpolysiloxane, methylphenylpolysiloxane], fillers [eg cray, kaolin , Talc, hydrotalcite, mica, zeolite, perlite, diatomaceous earth, calcium carbonate, glass (beads, fibers), wood flour] and various resin additives such as foaming agents, foaming aids, crosslinking agents, crosslinking accelerators, flame retardants, dispersants, processing Is illustrated.
When preparing the polyolefin resin composition of the present invention, a polyolefin resin (powder or flake), a nucleating agent containing the diacetal composition of the present invention, and a powdery polyolefin blended with the metal soap and the various resin additives as necessary. The method of obtaining a resin composition, or again this powdery polyolefin resin composition is subsequently heated (for example at 150 to 300 ° C, preferably at 170 to 240 ° C, more preferably at 180 to 220 ° C, in particular the diacetal composition Melt-kneaded and extruded, the extruded strand is cooled (e.g., added to water, for example, cooled to about 80 to 20 ° C), and the resulting strand is cut to cut white based on fine powder diacetal. The method of making a pellet without a spot can be illustrated.
In addition, the polyolefin resin and the diacetal composition are kneaded and extruded at a temperature lower than the melting point of the diacetal composition, and when the extruded strand is cooled, a polyolefin resin composition pellet having a white spot based on undispersed diacetal is obtained. Lose.
As will be described later, a molded product having no white spot can be obtained by injection molding, extrusion molding or the like even using any pellet.
<Polyolefin resin molded body>
The diacetal composition of the present invention is melted at a temperature considerably lower than the melting point of the diacetal itself represented by the formula (1) containing the diacetal composition, so that the resin composition of the present invention is molded according to a conventional method. Molding is possible at a lower temperature than the molding method using diacetal.
Therefore, since the sublimation property of diacetal is lost and pyrolysis is suppressed by shaping | molding at low temperature conventionally, the problem of generation | occurrence | production of the contamination or smell at the time of shaping is solved. In addition, the microdispersion in the polyolefin resin composition is dramatically reduced, leading to a dramatic productivity or quality improvement.
This molding method is also suitable for molding using resin pellets, and is also very suitable for a direct molding method using a powdery polyolefin resin composition without passing through pellets of resin.
The polyolefin resin composition pellets of the present invention without white spots based on the fine dispersion of diacetal become polyolefin resin molded articles having good transparency using molding methods such as conventional extrusion molding, injection molding, blow molding, and injection-blowing molding. In addition, the polyolefin resin composition pellets of the present invention in which white spots based on undispersed diacetals are present become a polyolefin resin molded article having good transparency using the same molding method at a resin temperature equal to or higher than the melting point of the diacetal composition. Since the polyolefin resin composition pellets are produced at a low temperature, the polyolefin resin molded article is not only good in transparency, but also has no coloration (yellowing) and may look good.
By setting the resin temperature above the melting point of the diacetal composition, the powdery polyolefin resin composition is formed into a polyolefin resin molded article using a molding method such as an ordinary extrusion molding method, an injection molding method, a blow molding method, or an injection-blow molding method.
In any of the above cases, the transparent sheet obtained by the extrusion molding method may be secondarily processed by ordinary pneumatic molding or the like to produce a molded article having good transparency.
As described above, the diacetal composition in the powdery polyolefin resin composition can make the melting point very low, preferably 185 to 230 ° C. Therefore, the white spots based on the diacetal composition or the undispersed diacetal by the above-mentioned conventional molding method become liquid at the melting point of the diacetal composition at the time of molding, and are easily dissolved or molecularly dispersed in the resin, resulting in good transparency. It is thought that it becomes a polyolefin resin molded object. It is a surprising result that the melting point of 255 to 280 DEG C usually uses a single diacetal alone.
As a result, it is not necessarily necessary to produce the polyolefin resin composition pellets without white spots based on undispersed diacetal. Therefore, it becomes possible to manufacture the highway polyolefin resin composition pellets at a lower temperature, which is advantageous in terms of equipment and energy efficiency. In addition, the melting point of the diacetal composition changes significantly lower than the melting point of the diacetal alone, resulting in the loss of the diacetal sublimation during molding, thereby minimizing contamination during molding. Therefore, molding yield or molding efficiency or productivity is improved.
According to the present invention, the molding conditions can not only be used conventionally, but also can be molded at a lower molten resin temperature than before. Therefore, for example, in the case of injection molding, molding can be performed under conditions of a molten resin temperature of 170 to 260 ° C, particularly 180 to 245 ° C, a mold temperature of 80 to 10 ° C, particularly 60 to 20 ° C. Moreover, in the case of extrusion molding, molding can be performed under the conditions of molten resin temperature 170-260 degreeC, especially 180-245 degreeC, cooling temperature 80-10 degreeC, especially 60-20 degreeC.
The molded article obtained in this way can be made into arbitrary shapes, such as a sheet | seat, a bottle, a case, a cap, a cup, a pipe, etc., and is useful as various storage cases, containers, and also as a bumper of an automobile.
<Other Uses>
In addition, the diacetal composition according to the present invention functions as a nucleating agent for resins other than polyolefin resins as well as gelling agents, viscosity modifiers, thixotropic agents, anti-flow agents, oil separation agents, flocculants, and polyolefin resins. And conventional products such as colorants, paints, fragrances, water treatment agents, solidification and recovery of spilled oil, fragrances, cosmetics, civil engineering, building materials, lubricants, rust preventives, pesticides, medicines, pharmaceutical products, fuels, inks, pastes, etc. It is likewise used in the field.
The present invention relates to a diacetal composition. The present invention more specifically comprises a diacetal powder and a diacetal composition comprising a binder comprising at least one organic acid and a derivative thereof acting as a melting point lowering agent, the binder being in the form of a powder uniformly dispersed in the diacetal particles, Or a diacetal composition in the form of granules, and a process for preparing the same.
The present invention also provides a nucleating agent for a polyolefin resin, a polyolefin resin composition and a molded article obtained from the nucleating agent and a polyolefin resin, comprising a powdery diacetal composition or a diacetal composition in the form of granules thereof, and a polyolefin resin composition thereof. The present invention also relates to a molding processing method.
An Example is given to the following and this invention is demonstrated to it in detail. Moreover, the average value, melting | fusing point, apparent density, fluidity, uniformity, adhesiveness, dust suppression, transparency (haze), and dispersibility of the particle diameter of powdery or granular diacetal composition were measured and evaluated by the following method.
<Average particle diameter (average value of the particle diameter (median diameter))>
A laser diffraction / scattering particle size distribution analyzer ("LA-910" (trade name), Horiba Seisakusho) was used, and distilled water was used as a dispersion medium, and the average value (median diameter) of the particle diameter was calculated | required. Hereinafter, the average value (median diameter) of this particle diameter is simply called "average particle diameter."
〈Melting Point〉
The temperature was raised at a rate of 20 ° C./min using a differential scanning calorimeter “DSC-50” (trade name) manufactured by Shimatsu Seisakusho, and the peak temperature derived from diacetals was taken as the melting point. 5 mg of the sample was taken and 5 mg of silica gel was used as a standard sample.
<Apparent density>
35 g of the sample was placed in a 200 ml mass cylinder having a diameter of 38 mm under a condition of 20 ° C. and 60% humidity. The tapping was carried out 50 times on a rubber plate at a height of 10 cm, and the apparent density was measured in the volume of the sample in the mass cylinder. Calculated. This operation was performed three times, and the average value was made into the apparent density of this evaluation. The greater the apparent density, the better the flowability characteristics of the powder.
<liquidity>
1 g of sample is placed in one end of a 5 cm long, 10 cm wide, 5 cm high stainless steel container placed on a horizontal plate, and when the container is inclined, the plate and the container are formed when the surface particles begin to slide. The angle of repose was taken as the standard of fluidity. The smaller the measured angle of repose, the better the flowability.
<Uniformity (Confirmation of Uniform Dispersion of Binder in Grinding Particles)>
The powdery diacetal composition obtained by pulverization was visually observed using a polarizing microscope at room temperature and elevated temperature under cross nicol. (Circle) and the case where it is not uniform are shown with the case where the binder is disperse | distributed uniformly in the particle | grains of this powder.
<Adhesiveness>
5 g of a powdery diacetal composition was placed in a 75 ml glass bottle, covered with a lid, shaken for 1 minute, and then allowed to stand. The degree of adhesion of the inner wall of the glass was observed and evaluated in the following four steps.
(Double-circle): There is no adhesion at all.
○: There is a very small amount of adhesion.
(Triangle | delta): It is affixed.
X: It adheres considerably.
<Dust suppression degree>
10 g of the sample was dropped at a height of 50 ° C. at once, and the degree of dust generation after 5 seconds was visually observed and evaluated in the following four steps.
(Double-circle): Dust hardly generate | occur | produced.
○: Small amount of dust was generated.
(Triangle | delta): The dust generate | occur | produced.
X: Dust generate | occur | produced considerably.
<Haze value (for transparency modification)>
It measured based on JISK6714 and JISK6717 using the haze meter of Toyo Seiki Seisakusho. The smaller the obtained numerical value, the better the transparency.
<Dispersibility (dispersibility of diacetal composition in the polyolefin resin composition)>
The number of white spots (white spots) by the undispersed nucleating agent in 10 test pieces of 5 cm x 5 cm x 1 mm was visually measured and determined as an average value per sheet. The smaller the obtained numerical value, the better the dispersibility. When undispersed water exceeds 0.5 piece / sheet, it is inferior in practicality.
<Formulation amount of binder (and additives)>
The weight percentage of the amount of binder (and amount of additive, if applicable) relative to the total amount of the diacetal and the amount of binder (and amount of additive if an additive is used).
<Example 1>
1,3: 2,4-O-dibenzylidene-D-sorbitol (average particle diameter: 20 µm) in a 5-liter universal stirrer (made by Dalton) equipped with a stirrer, a cooling tube with a decanter, a thermometer and a gas inlet 45.0 g and 1500 ml of ethanol were added and stirred for 1 hour under reflux at a stirring rate of 50 to 60 rpm while flowing nitrogen (the system became a swollen paste).
Subsequently, 50 g of stearic acid (acid value: 197 mgKOH / g, same as below) was added, and it mixed and stirred for 2 hours under reflux again.
Then, after cooling to 50 ° C., the solvent was gradually removed out of the system under reduced pressure.
After most of the ethanol was removed, it was granulated while maintaining at 10 mmHg at 50 ° C. and drying under stirring for 8 hours. This dried granule was pulverized with a domestic mixer for 10 minutes to obtain a powdery diacetal composition.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 1.
<Example 2>
450 g of "D" and 1500 ml of methanol were put into a reactor similar to Example 1, and stirred for 1 hour under reflux at a stirring speed of 50 to 60 rpm while flowing nitrogen (the system became a swollen paste).
Subsequently, 13.5 g / water of DL-malic acid (acid value: 807 mgKOH / g, same as below) was added, and it mixed and stirred for 2 hours under reflux again. Subsequently, a powdery diacetal composition was obtained in the same manner as in Example 1.
The average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion, and dust inhibition degree of the obtained powdery diacetal composition were evaluated. The obtained results are shown in Table 1.
<Comparative Example 1>
Diacetal composition was obtained by treating "D" in the same manner as in Example 1 except that stearic acid was not used.
The average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition of the obtained diacetal powder were evaluated. The obtained results are shown in Table 1.
BinderAverage particle diameter (㎛)Melting Point (℃)Apparent density (g / cm3)Repose angle (degrees)UniformityAdhesionDust suppression system KindsCompounding amount (wt%) Example 1Stearic acid10252170.4460○○○ Example 2DL-Malic Acid2.9201950.3065○○○ Comparative Example 1--202270.2075 〈-××
<Example 3>
Example 1 except having changed "D" into 1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol (average particle diameter 20 micrometers hereafter abbreviated as "MD"). In the same manner as the powdery diacetal composition was obtained.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 4>
A powdery diacetal composition was obtained in the same manner as in Example 3 except that 100 g of stearic acid was applied to 400 g of "MD".
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 5>
A powdery diacetal composition was obtained in the same manner as in Example 3 except that 250 g of stearic acid was applied to 250 g of "MD".
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 6>
After adding 150 g of ethanol to 400 g of the powdery diacetal composition obtained in "MD" in Example 4, it was made into a paste form, and then used an extruded granulator ("Eck pelleter", manufactured by Fuji Denki Kogyo Co., Ltd.). A noodle-shaped solid was obtained by extruding through the filter plate which has an opening of mm.
The solid was dried at 50 ° C. and 10 mm Hg for 8 hours, and then cut to a length of about 5 mm. The cut cylindrical solid was pulverized with a home mixer for 1 minute to obtain a powdered diacetal composition.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 7>
After repulverizing the powdery diacetal composition obtained in "MD" in Example 3, the powdery diacetal composition with an average particle diameter of 5 micrometers was obtained.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 8>
After dissolving 15 g of ion-exchanged water in 273 g of D-sorbitol in the same reactor as in Example 1, 360 g of p-methylbenzaldehyde, 550 g of cyclohexane, 400 g of methanol, and 30 g of p-toluenesulfonic acid monohydrate were dissolved. Was added, and after nitrogen substitution, the temperature was raised while stirring under a nitrogen stream. The reaction temperature rose as methanol and water were taken out of the system as a gas-liquid equilibrium or an azeotrope. When the reaction temperature reached 74 ° C., 60 g of methanol was added. This operation was repeated five times. Thus, a reaction crude containing "MD" was obtained.
It was then cooled to room temperature and neutralized with a solution of 14 g of potassium hydroxide / 200 g of methanol. Subsequently, water washing was performed 5 times at a rate of 600 g / time of 60 ° C warm water.
Subsequently, 64.3 g of stearic acid and 4.0 g of L-tartaric acid (acid value: 748 mgKOH / g) were added to the diacetal slurry swollen with the cyclohexane solvent, followed by stirring at 70 ° C for 2 hours.
Subsequently, 600 g of warm water was added, cyclohexane was flowed out at the temperature of 100 degrees C or less, and it substituted by the water dispersion medium in the cyclohexane dispersion medium.
Subsequently, after reaching 100 degreeC, water flowed out out of a system gradually under reduced pressure. Finally, the granules were obtained by granulation with drying at 50 mmHg and a drying temperature of 80 ° C. for 10 hours.
The granules were ground for 10 minutes with a domestic mixer to obtain a powdery diacetal composition containing "MD".
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 9>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to behenic acid (acid value: 165 mgKOH / g).
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 10>
Stearic acid was changed to Montan acid wax (acid value: 140 mgKOH / g, manufactured by Client Japan Co., Ltd., trade name HOE-WAX S FLAKES), and 1500 ml of ethanol was mixed with a mixed solvent of 750 ml of ethanol and 750 ml of cyclohexane. A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except for the above.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 11>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to dehydroabiethanic acid (acid value: 186 mgKOH / g).
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 12>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to benzoic acid (acid value: 459 mgKOH / g).
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 13>
A powdery diacetal composition containing granulated "MD" was obtained in the same manner as in Example 3 except that 50 g of stearic acid was changed to 1.35 g of L-tartaric acid (acid value: 748 mgKOH / g). However, it did not grind by the mixer.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 14>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to succinic acid (acid value: 950 mgKOH / g).
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 15>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to DL-malic acid.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 16>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that 50 g of stearic acid was changed to 23.7 g of citric acid (acid value: 876 mgKOH / g, the same as below).
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 17>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to citric acid.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 18>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to 12-hydroxystearic acid (acid value: 187 mgKOH / g).
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 19>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to kolic acid (acid value: 137 mgKOH / g).
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 20>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to citric acid monostearate (acid value: 245 mgKOH / g).
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 21>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to citric acid distearate (acid value: 77 mgKOH / g).
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 22>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to L-glutamine (acid value: 384 mgKOH / g).
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Example 23>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to monostearyl pentaerythritol diphosphite (acid value: 131 mgKOH / g).
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Comparative Example 2>
Except not using stearic acid, the average particle diameter, melting point, apparent density, flowability, uniformity, adhesion, and dust inhibition degree of the powdery solid obtained by treating "MD" in the same manner as in Example 3 were evaluated. The obtained results are shown in Table 2.
<Comparative Example 3>
A powdery solid of "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to stearyl alcohol.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Comparative Example 4>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to cholesterol.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Comparative Example 5>
A powdery diacetal composition containing "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to abiethienyl alcohol.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Comparative Example 6>
A powdery solid of "MD" was obtained in the same manner as in Example 3 except that stearic acid was changed to distearylmethylamine.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Comparative Example 7>
The powdery form of "MD" was treated in the same manner as in Example 1 except that "D" was changed to "MD", stearic acid was changed to paraffin wax, and 1500 ml of ethanol was changed to a mixed solvent of 750 ml of ethanol and 750 ml of cyclohexane. A solid was obtained.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 2.
<Comparative Example 8>
50 g of stearic acid and 150 g of methanol were put into a 5-liter universal stirrer (manufactured by Dalton), and dissolved at 60 ° C. Subsequently, a 28 g solution of a 28.5% sodium carbonate aqueous solution was added to a methanol solution of stearic acid at 60 ° C. and stirred for 10 minutes. 500 g of ion-exchanged water was then slowly added and stirred to form an emulsion of stearic acid.
450 g of "MD" was put into the obtained emulsion, the heating was stopped, and it stirred, and obtained the white viscous emulsion. This was neutralized with diluted hydrochloric acid, filtered, washed with water and dried to obtain a dry powder. This dry powder was ground for 10 minutes with a domestic mixer to obtain a powdery solid. The average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion, and dust inhibition degree of the obtained powdery solid were evaluated. The obtained results are shown in Table 2.
<Comparative Example 9>
Except changing the ion-exchanged water from 500 g to 375 g and 450 g of 1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol ("MD") to 200 g It carried out similarly to Example 8. The average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion, and dust inhibition degree of the obtained powdery solid were evaluated. The obtained results are shown in Table 2.
<Example 24>
Except having changed "D" into 1,3: 2,4-bis-O- (3,4-methylbenzylidene) -D-sorbitol (average particle diameter 20 micrometers hereafter abbreviated "DMD".) A powdery diacetal composition was obtained in the same manner as in Example 1.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 3.
<Example 25>
A powdery diacetal composition containing "DMD" as a main component was obtained in the same manner as in Example 24 except that 13.5 g of citric acid was used instead of 50 g of stearic acid.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 3.
<Example 26>
A powdery diacetal composition was obtained in the same manner as in Example 13 except that "MD" was changed to "DMD". Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 3.
<Comparative Example 10>
"DMD" was treated in the same manner as in Example 24 except that no stearic acid was used, and the average particle diameter, melting point, apparent density, flowability, uniformity, adhesion, and dust inhibition degree of the obtained diacetal powder were evaluated. The obtained results are shown in Table 3.
<Example 27>
A powdery diacetal composition was prepared in the same manner as in Example 1 except that 50 g of stearic acid and 23.5 g of glycerin monostearate (acid value: 5 mgKOH / g, the same as below) were added to 400 g of "MD". Got it.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 4.
<Example 28>
A powdery diacetal composition was obtained in the same manner as in Example 1 except that 47.1 g of stearic acid, 1.2 g of L-tartaric acid, and 30 g of an aqueous solution of 2.0 g of sodium butylnaphthalenesulfonate were added to 400 g of "MD".
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 4.
<Example 29>
450 g of "MD" and 1500 ml of methanol were placed in the same reactor as in Example 1, and the mixture was stirred for 1 hour under reflux at a stirring speed of 50 to 60 rpm while flowing nitrogen (the system became a swollen paste).
Subsequently, 4.5 g of L-tartaric acid / 20 ml of water and 50 g of cured castor oil were added, followed by further mixing and stirring under reflux for 2 hours. Subsequently, after cooling to 50 ° C., the solvent was gradually removed out of the system under reduced pressure. After removing most of the ethanol, it was maintained at a reduced pressure of 10 mmHg at 50 ℃ and dried while stirring for 8 hours to obtain a dry powder.
This dry powder was pulverized with a domestic mixer for 10 minutes to obtain a powdery diacetal composition containing "MD" as a main component.
The average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion, and dust inhibition degree of the obtained powdery diacetal composition were evaluated. The obtained results are shown in Table 4.
<Example 30>
After dissolving 15 g of ion-exchanged water in 273 g of D-sorbitol in the same reactor as in Example 1, 360 g of p-methylenebenzaldehyde, 550 g of cyclohexane, 400 g of methanol, and 30 g of p-toluenesulfonic acid monohydrate were dissolved. It put in, substituted with nitrogen, and heated up, stirring under nitrogen stream. The reaction temperature rose as the ethanol and water were taken out of the system as a gas-liquid equilibrium or an azeotrope. When the reaction temperature reached 74 ° C., 60 g of methanol was added. This operation was repeated 15 times. It was then cooled to room temperature and neutralized with 14 g of potassium hydroxide / 200 g of methanol. Subsequently, water washing was performed 7 times at a rate of 600 g / time of hot water at 60 ° C.
Subsequently, 5.8 g of sodium dodecylbenzenesulfonate and 2.4 g of L-tartaric acid (acid value: 748 mgKOH / g) were added to the diacetal swelled with the cyclohexane solution described above, followed by stirring at 70 ° C for 2 hours.
Subsequently, 600 g of warm water was added, the mixture was heated up to 100 ° C, and cyclohexane was distilled off and replaced with a water dispersion medium in a cyclohexane dispersion medium.
Subsequently, after reaching 100 degreeC, water flowed out out of the system by gradually increasing pressure. Finally, the granules were granulated with drying at 50 mmHg and a drying temperature of 80 ° C. for 10 minutes to obtain dry granules.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 4.
<Example 31>
After dissolving 15 g of ion-exchanged water in 273 g of D-sorbitol in the same reactor as in Example 1, 402 g of 3,4-dimethylenebenzaldehyde, 550 g of cyclohexane, 400 g of methanol, and p-toluenesulfonic acid monohydrate 30 g was added, nitrogen-substituted, and it heated up, stirring under nitrogen stream. The reaction temperature rose as methanol and water were taken out of the system as a gas-liquid equilibrium or an azeotrope. When the reaction temperature reached 74 ° C., 60 g of methanol was added. This operation was repeated 10 times. It was then cooled to room temperature and neutralized with a solution of 14 g of potassium hydroxide / 200 g of methanol. Subsequently, water washing was performed 7 times at a rate of 600 g / time of hot water at 60 ° C.
Subsequently, 6.2 g of dodecylbenzenesulfonic acid and 2.5 g of L-tartaric acid (acid value: 748 mgKOH / g) were added to the diacetal swelled with the cyclohexane solvent described above, followed by stirring at 70 ° C for 2 hours. Subsequently, 600 g of warm water was added, the mixture was heated to 100 ° C, and cyclohexane was distilled off to replace the cyclohexane dispersion medium with an aqueous dispersion medium.
Subsequently, after reaching 100 degreeC, water flowed out out of the system gradually under reduced pressure. Finally, it dried and granulated at 50 mmHg and drying temperature of 80 degreeC for 10 hours, and obtained the dry granule.
Its average particle diameter, melting point, apparent density, fluidity, uniformity, adhesion and dust inhibition were evaluated. The obtained results are shown in Table 4.
<Example 32>
A granule was obtained in the same manner as in Example 31 except that instead of 6.2 g of sodium dodecylbenzenesulfonate and 2.5 g of L-tartaric acid, 3.1 g of sodium dodecylbenzenesulfonate, 3.1 g of L-tartaric acid, and 62.1 g of behenic acid were used.
The average particle diameter, melting point, apparent density, flowability, uniformity, adhesion and dust inhibition of the granules including the obtained "DMD" were evaluated. The obtained results are shown in Table 4.
<Example 33>
A granule was obtained in the same manner as in Example 30 except that instead of 5.8 g of sodium dodecylbenzenesulfonate and 2.4 g of L-tartaric acid, 5.8 g of sodium dodecylbenzenesulfonate was used.
The average particle diameter, melting point, apparent density, flowability, uniformity, adhesion and dust inhibition of the granules including the obtained "MD" were evaluated. The obtained results are shown in Table 4.
<Example 34>
A granule was obtained in the same manner as in Example 30 except that 17.4 g of sodium dodecylbenzenesulfonate was used instead of 5.8 g of sodium dodecylbenzenesulfonate and 2.4 g of L-tartaric acid.
The average particle diameter, melting point, apparent density, flowability, uniformity, adhesion and dust inhibition of the granules including the obtained "MD" were evaluated. The obtained results are shown in Table 4.
<Example 35>
A granule was obtained in the same manner as in Example 30 except that instead of 5.8 g of sodium dodecylbenzenesulfonate and 2.4 g of L-tartaric acid, 5.8 g of α-olefin (C18) sulfonic acid sodium was used.
The average particle diameter, melting point, apparent density, flowability, uniformity, adhesion and dust inhibition of the granules including the obtained "MD" were evaluated. The obtained results are shown in Table 4.
<Example 36>
A granule was obtained in the same manner as in Example 30 except that 17.4 g of sodium lauryl sulfate was used instead of 5.8 g of sodium dodecylbenzenesulfonate and 2.4 g of L-tartaric acid.
The average particle diameter, melting point, apparent density, flowability, uniformity, adhesion and dust inhibition of the granules including the obtained "MD" were evaluated. The obtained results are shown in Table 4.
<Example 37>
A granule was obtained in the same manner as in Example 30 except that 17.4 g of aluminum distearate was used instead of 5.8 g of sodium dodecylbenzenesulfonate and 2.4 g of L-tartaric acid.
The average particle diameter, melting point, apparent density, flowability, uniformity, adhesion and dust inhibition of the granules including the obtained "MD" were evaluated. The obtained results are shown in Table 4.
<Example 38>
A granule was obtained in the same manner as in Example 30 except that 62.1 g of aluminum distearate was used instead of 5.8 g of sodium dodecylbenzenesulfonate and 2.4 g of L-tartaric acid.
The average particle diameter, melting point, apparent density, flowability, uniformity, adhesion and dust inhibition of the granules including the obtained "MD" were evaluated. The obtained results are shown in Table 4.
<Example 39>
A granule was obtained in the same manner as in Example 30 except that 17.4 g of aluminum monostearate was used instead of 5.8 g of sodium dodecylbenzenesulfonate and 2.4 g of L-tartaric acid.
The average particle diameter, melting point, apparent density, flowability, uniformity, adhesion and dust inhibition of the granules including the obtained "MD" were evaluated. The obtained results are shown in Table 4.
<Example 40>
A granule was obtained in the same manner as in Example 34 except that instead of 17.4 g of sodium dodecylbenzenesulfonate, 5.8 g of sodium lauryl sulfate ester and 11.6 g of aluminum distearate were used.
The average particle diameter, melting point, apparent density, flowability, uniformity, adhesion and dust inhibition of the granules including the obtained "MD" were evaluated. The obtained results are shown in Table 4.
<Example 41>
The powdery diacetal composition obtained in Example 1 as a nucleating agent for polyolefin with respect to 100 parts by weight of isotactic random polypropylene resin (hereinafter abbreviated as "r-PP") having an ethylene content of 3.0% by weight of diacetals 0.2 parts by weight, 0.05 parts by weight of calcium stearate and tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propiolate] methane (trade name; Arganox 1010) 0.05 parts by weight of Ciba-Geigy Co., Ltd. was blended and dry blended with a Henschel mixer.
Subsequently, melt-kneading was carried out by a single screw extruder at 220 ° C to cool the extruded strand, and then cut and pelletized.
The obtained pellet was injection-molded on condition of resin temperature of 220 degreeC, and mold temperature of 40 degreeC, the test piece of thickness 1mm was created, and the haze value of this test piece and the number of the spots based on the microdispersion nucleating agent were measured. The obtained results are shown in Table 5.
<Examples 42 to 70>
About r-PP, the test piece based on Example 41 was produced using each nucleating agent composition obtained in Examples 2-29 and Example 1.
Table 5 shows the diacetal composition used in each Example, the extrusion temperature at the time of pellet manufacture, the injection molding temperature at the time of test piece preparation, and the haze value obtained by specifying this test piece, and the number of white spots based on the undispersed nucleating agent.
<Comparative Examples 11 to 20>
With respect to r-PP, each nucleating agent composition obtained in Comparative Examples 1 to 10 was applied to prepare a test piece in accordance with Example 41.
Table 5 shows the diacetal composition applied by each comparative example, the extrusion temperature at the time of pellet manufacture, the injection molding temperature at the time of test piece preparation, and the haze value obtained by specifying this test piece, and the number of white spots based on the undispersed nucleating agent.
<Comparative Example 21>
A test piece of r-PP containing no nucleating agent diacetal was produced in the same manner as in Example 41.
Table 5 shows the measurement results of the number of white spots based on the haze value of the test piece and the undispersed nucleating agent.
<Example 71>
100 parts by weight of the linear low density polyethylene resin (density = 0.2926 g / cm 3, MFR = 20 g / 10 min, hereinafter abbreviated as "LLDPE"). 0.2 colon parts were mix | blended in conversion and dry blended with the Henschel mixer.
Subsequently, melt-kneading was carried out by a single screw extruder at 200 ° C to cool the extruded strand, and then cut to obtain pellets.
The obtained pellet was injection molded on the conditions of 200 degreeC of resin temperature, and 30 degreeC of mold temperature, and the test piece of thickness 1mm was manufactured.
The number of white spots based on a haze value and a microdispersion nucleating agent was measured using the obtained test piece. The obtained results are shown in Table 6.
<Examples 72 to 74>
Test pieces were prepared in accordance with Example 71 using the respective nucleating agent compositions obtained in Examples 2, 30 and 32 for LLDPE.
Table 6 shows the diacetal composition used in each Example, the extrusion temperature at the time of pellet manufacture, the injection molding temperature at the time of test piece preparation, and the haze value obtained by specifying this test piece, and the number of white spots based on the undispersed nucleating agent.
<Comparative Example 22>
A test piece of LLDPE only was prepared by the same operation as in Example 71. Table 6 shows the measurement result of the haze value of the test piece which does not contain a diacetal composition, and the white spot number based on the undispersed nucleating agent.
According to the present invention, the melting point of diacetals can be drastically lowered, and as a result, it is possible to increase the dissolution rate for molten resin or various liquids, to shorten the melting temperature or to shorten the dissolution time, and to further reduce the amount of unsealed seafood. It can greatly improve quality and productivity.
In addition, by increasing the apparent density due to the binder effect, the generation of dust can be suppressed to greatly improve the working environment, and further, the powder properties can be improved by improving the fluidity of the powder, suppressing adhesion, and the like, thereby facilitating transport.
In addition, as a polyolefin resin nucleating agent capable of low temperature molding, moldability is improved, and sublimation, decomposition and coloring of diacetalide are suppressed.

权利要求:
Claims (44)
[1" claim-type="Currently amended] (a) at least one diacetal represented by the following formula (1) and
(b) neutral to weakly acidic monovalent organic acids, neutral to weakly acidic polyvalent organic acids, partial salts of neutral to weakly acidic polyvalent organic acids, sulfuric acid ester salts, sulfonates, phosphate ester salts, phosphate esters, phosphorous acid esters and neutral to weakly acidic ones. At least one binder selected from the group consisting of aluminum salts of organic acids
A granular or powdery diacetal composition comprising: the binder is a granular or powdery diacetal composition that is uniformly dispersed in the particles of the granular or powdery diacetal composition.
<Formula 1>

In the formula,
R ¹ and R ² are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom,
a and b each represent an integer of 1 to 5,
c represents 0 or 1,
When a is 2, two R ¹ may be bonded to each other to form a tetralin ring together with the benzene ring to which they are bonded. When b is 2, two R ² may be bonded to each other and together with the benzene ring to which they are bonded. It can also form a traline ring.
[2" claim-type="Currently amended] The granular or powdery diacetal composition according to claim 1, wherein the binder is uniformly distributed between the diacetal fibrous crystals constituting the granular or powdery diacetal composition.
[3" claim-type="Currently amended] The binder may have at least one bond or functional group selected from the group consisting of ether bonds, ester bonds, thioether bonds, amide bonds, halogen atoms, amino groups, hydroxyl groups, heterocyclic groups and carbonyl groups in a molecule. Esters of at least one selected from the group consisting of monocarboxylic acids, polycarboxylic acids, partial salts of polycarboxylic acids, monovalent aliphatic alcohols having 1 to 30 carbon atoms and polyhydric aliphatic alcohols having 2 to 30 carbon atoms, with phosphoric acid , An ester of at least one selected from the group consisting of monohydric aliphatic alcohols having 1 to 30 carbon atoms and polyhydric aliphatic alcohols having 2 to 30 carbon atoms, phosphorous acid, monovalent aromatic alcohols having 6 to 30 carbon atoms, and polyhydric acids having 6 to 30 carbon atoms. Esters of at least one member selected from the group consisting of aromatic alcohols with phosphoric acid, monovalent having 6 to 30 carbon atoms Esters, taurine, sulfate ester salts, sulfonates, phosphate ester salts and mono, di or tri (C6-C30 fatty acids) of at least one selected from the group consisting of aromatic alcohols and polyvalent aromatic alcohols having 6 to 30 carbon atoms and phosphorous acid; At least one granular or powdery diacetal composition selected from the group consisting of aluminum salts.
[4" claim-type="Currently amended] The method of claim 1,
(Iii) preparing a slurry containing a diacetal represented by Formula 1 swelled with a solvent,
(Ii) uniformly mixing the slurry and the binder,
(Iv) (a) removing the solvent from the resulting homogeneous mixture to obtain a dried product, or
(b) granulate with removal of solvent from the resulting homogeneous mixture, or
(c) classifying or pulverizing the dried product obtained in the step (a) or the granulated product obtained in the step (b), or
(d) A granular or powdery diacetal composition obtained by granulating or classifying the pulverized product obtained in the step (c).
[5" claim-type="Currently amended] The melting point of claim 1, wherein when the binder contains 10 parts by weight of the granular or powdery diacetal uniformly dispersed in 90 parts by weight of the diacetal represented by the formula (1), the melting point is lower than that of the acetal itself. It lowers by 7 degreeC or more, and monocarboxylic which may have at least 1 sort (s) or functional group selected from the group which consists of an ether bond, an ester bond, a thioether bond, an amide bond, a halogen atom, an amino group, a hydroxyl group, a heterocyclic group, and a carbonyl group in a molecule | numerator Esters of at least one selected from the group consisting of acids, polycarboxylic acids, partial salts of polycarboxylic acids, monohydric aliphatic alcohols having 1 to 30 carbon atoms and polyhydric aliphatic alcohols having 2 to 30 carbon atoms, and phosphoric acid; At least one selected from the group consisting of monohydric aliphatic alcohol of 30 to 30 and polyhydric aliphatic alcohol of 2 to 30 carbon atoms Esters of at least one selected from the group consisting of one species of esters with phosphoric acid, monovalent aromatic alcohols having 6 to 30 carbon atoms and polyvalent aromatic alcohols having 6 to 30 carbon atoms, and phosphorous acid, and monovalent aromatic alcohols having 6 to 30 carbon atoms And esters of at least one selected from the group consisting of polyvalent aromatic alcohols having 6 to 30 carbon atoms with phosphorous acid, taurine, sulfuric acid ester salts, sulfonates, phosphate ester salts and mono, di or tri (C6-C30 fatty acid) aluminum salts. At least one granular or powdery diacetal composition selected from the group consisting of:
[6" claim-type="Currently amended] The mono-monomer according to claim 1, wherein the binder may have at least one bond or functional group selected from the group consisting of ether bonds, ester bonds, thioether bonds, amide bonds, halogen atoms, amino groups, hydroxyl groups, heterocyclic groups and carbonyl groups in a molecule. Granular or at least one selected from carboxylic acids, polycarboxylic acids, partial salts of polycarboxylic acids, sulfonates, sulfuric acid ester salts, phosphate ester salts and mono, di or tri (C6-C30 fatty acid) aluminum salts; Powdery diacetal composition.
[7" claim-type="Currently amended] The binder according to claim 1, wherein the binder has an acid value of 60 to 1200 mgKOH / g, and in the group consisting of an ether bond, an ester bond, a thioether bond, an amide bond, a halogen atom, an amino group, a hydroxyl group, a heterocyclic group, and a carbonyl group in a molecule thereof. A granular or powdery diacetal composition which is a monocarboxylic acid or polycarboxylic acid which may have at least one bond or functional group selected.
[8" claim-type="Currently amended] The method of claim 1, wherein the binder is an aliphatic monocarboxylic acid having 80 or less carbon atoms, an aliphatic polycarboxylic acid having 80 or less carbon atoms, and an alkyl (C1-C22) partial ester thereof, an aromatic monocarboxylic acid having 80 or less carbon atoms, or carbon atoms. 80 or less aromatic polycarboxylic acid and its alkyl (C1-C22) partial ester, a halogen atom-containing carboxylic acid having 80 or less carbon atoms, an amino group-containing carboxylic acid having 80 or less carbon atoms, an amide bond-containing carboxyl having 80 or less carbon atoms Acid, hydroxyl group-containing carboxylic acid with 80 or less carbon atoms, resin acid, carbonyl group-containing carboxylic acid with 80 or less carbon atoms, ether bond-containing carboxylic acid with 80 carbon atoms or less, ester bond-containing carboxylic acid with 80 or less carbon atoms, 80 or less carbon atoms Amide bonds and amino group-containing carboxylic acids, amide bonds and hydroxyl group-containing carboxylic acids having up to 80 carbon atoms, carbon Heterocycle containing less than 80 carboxylic acids and thioether bond carbon number 80 or less containing at least one member selected from the group consisting of carboxylic acid granular or powdery di acetal composition.
[9" claim-type="Currently amended] The binder according to claim 1, wherein the binder is an aliphatic monocarboxylic acid having 3 to 35 carbon atoms, an aliphatic polycarboxylic acid having 4 to 30 carbon atoms, and an alkyl (carbon having 1 to 22) partial ester thereof, and an aromatic monocarboxyl having 7 to 35 carbon atoms. Acids, aromatic polycarboxylic acids having 8 to 30 carbon atoms and alkyl (1 to 22) partial esters thereof, halogen atom-containing carboxylic acids having 4 to 35 carbon atoms, amino group-containing carboxylic acids having 4 to 35 carbon atoms, and 4 to 30 carbon atoms 35 hydroxyl-containing carboxylic acid, resin acid, carbonyl group-containing carboxylic acid having 4 to 35 carbon atoms, ether bond-containing carboxylic acid having 4 to 35 carbon atoms, ester bond-containing carboxylic acid having 4 to 35 carbon atoms, 4 to 35 carbon atoms Amide bonds and amino group-containing carboxylic acids, amide bonds and hydroxyl group-containing carboxylic acids having 4 to 35 carbon atoms, heterocycle-containing carbons having 4 to 35 carbon atoms And acids having 4 to 35 is at least one member granules thioether bond-containing carboxylic acid selected from the group consisting of the di-acetal or powdery composition.
[10" claim-type="Currently amended] The method of claim 1 wherein the binder
(a) aliphatic monocarboxylic acids having 8 to 30 carbon atoms,
(b) aliphatic dicarboxylic acids having 3 to 18 carbon atoms, aliphatic tricarboxylic acids having 6 to 30 carbon atoms and aliphatic tetracarboxylic acids having 8 to 30 carbon atoms,
(c) aromatic monocarboxylic acids having 7 to 15 carbon atoms,
(d) aromatic di, tri and tetracarboxylic acids having 8 to 20 carbon atoms,
(e) carboxylic acids having 3 to 20 carbon atoms containing 1 to 3 halogen atoms,
(f) mono and dicarboxylic acids having 5 to 12 carbon atoms containing 1 to 3 amino groups,
(g) mono, di or tri (C6-C30 fatty acid) aluminum salts,
(h) mono, di, tri and tetracarboxylic acids having 4 to 24 carbon atoms containing 1 to 5 hydroxyl groups,
(i) resin acid,
(j) mono and dicarboxylic acids having 4 to 18 carbon atoms containing 1 to 3 carbonyl groups,
(k) mono and dicarboxylic acids having 8 to 15 carbon atoms containing 1 to 2 ether bonds,
(l) mono and dicarboxylic acids having 5 to 26 carbon atoms having 1 to 2 ester bonds, and
(m) alkali metal salts, ammonium salts and alkaline earth metal salts of (m-1) alkanesulfonic acids having 6 to 30 carbon atoms, alkenesulfonic acids having 6 to 30 carbon atoms, (C1-C22 alkyl) benzenesulfonic acid and (C1-C14 alkyl) naphthalenesulfonic acid And (m-2) sulfuric acid ester salts of saturated or unsaturated aliphatic alcohols having 6 to 30 carbon atoms, sulfuric acid ester salts of saturated or unsaturated aliphatic alcohols having 6 to 30 carbon atoms to which 1 to 10 moles of ethylene oxide is added, and sulfosuccinic acid diesters Salts, α-sulfofatty acid salts and α-sulfofatty acid ester salts
At least one granular or powdery diacetal composition selected from the group consisting of:
[11" claim-type="Currently amended] (A ') lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, isostearic acid, eicosanoic acid, behenic acid, docosa Hexanoic acid, montanic acid, benzyl acid, sorbic acid, oleic acid, linoleic acid, linoleic acid,
(b ') Succinic acid, glutaric acid, malonic acid, adipic acid, suveric acid, azelaic acid, sebacic acid, dodecanedioic acid, itaconic acid, tricarballylic acid, 1,2,3,4-butanetetra Carboxylic acid, citric acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4,4'- Dicyclohexyldicarboxylic acid, cyclohexanetetracarboxylic acid,
(c ') benzoic acid, p-methylbenzoic acid, p-ethylbenzoic acid, pn-propylbenzoic acid, cuminic acid, p-tert-butyl benzoic acid, p-isobutylbenzoic acid, p-phenylbenzoic acid, 3,5-dimethylbenzoic acid, 1 Naphthoic acid, 2-naphthoic acid, tetralinocarboxylic acid,
(d ') o-phthalic acid, m-phthalic acid, p-phthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, diphenic acid, biphenyldicarboxylic acid, biphenyltetracarboxylic acid, naphthalenedicarboxylic acid , Diphenyl sulfontetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylmethanetetracarboxylic acid, diphenylpropanetetracarboxylic acid, ethylene glycol-4,4'-bistrimellitic acid ditrimellitate,
(e ') chloropropionic acid, bromopropionic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, 4-chloro-3-nitrobenzoic acid,
(f ') L-glutamine,
(g ') mono and di (pelargonate) aluminum, mono and di (lauric acid) aluminum, mono and di (myritic) aluminum, mono and di (stearic acid) aluminum, mono and di (oleic acid) aluminum ,
(h ') tartaric acid, lactic acid, malic acid, citric acid, gluconic acid, pantothenic acid, 12-hydroxystearic acid, mandelic acid, cholic acid, β-oxynaphthoic acid, ricinolic acid, quinic acid, sikimic acid, salicylic acid, α, β-hydric Oxyhexahydrophthalic acid,
(i ') dehydroabietic acid, abietic acid, dihydroabietic acid, neoabietic acid, tetrahydroabietic acid,
(j ') levulinic acid, pyruvic acid, o-benzoylbenzoic acid,
(k ') 4-methoxycyclohexanecarboxylic acid, 4-ethoxycyclohexanecarboxylic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, p-phenoxybenzoic acid,
(l ') acetyl citric acid, stearoyl citric acid, acetyl ricinolic acid, stearoyl lactic acid, citric acid monostearyl ester, adipic acid mono-2-ethylhexyl ester, adipic acid monooctyl ester, and
(m ') sodium salts of potassium or sodium salts of C18 alkanes or alkenesulfonic acids, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium dodecyl ether sulfate (i.e., sulfuric acid esters of dodecyl alcohol with one mole of ethylene oxide added). ), A granular or powdery diacetal composition which is at least one compound selected from the group consisting of sodium dioctylsulfosuccinate and sodium methylα-sulfostearate.
[12" claim-type="Currently amended] The granular or powdery diacetal composition according to claim 1, wherein the binder is (h) at least one mono, di, tri and tetracarboxylic acid having 4 to 24 carbon atoms having 1 to 5 hydroxyl groups.
[13" claim-type="Currently amended] The method of claim 1, wherein the binder is tartaric acid, lactic acid, malic acid, citric acid, gluconic acid, pantothenic acid, 12-hydroxystearic acid, mandelic acid, cholic acid, β-oxynaphthoic acid, ricinolic acid, quinic acid, cykimic acid, salicylic acid and α. Granular or powdery diacetal composition which is at least 1 sort (s) chosen from the group which consists of (beta) -dihydroxyhexahydrophthalic acid.
[14" claim-type="Currently amended] The method of claim 1 wherein the binder
(h-a) tartaric acid, lactic acid, malic acid, citric acid and α, β-dihydroxyhexahydrophthalic acid, and
(m) alkali metal salts, ammonium salts and alkali metal salts of (m-1) alkanesulfonic acids having 6 to 30 carbon atoms, alkenesulfonic acids having 6 to 30 carbon atoms, (C1-C22 alkyl) benzenesulfonic acid and (C1-C14 alkyl) naphthalenesulfonic acid; And (m-2) sulfuric acid ester salts of saturated and unsaturated aliphatic alcohols having 6 to 30 carbon atoms, sulfuric acid ester salts of saturated and unsaturated aliphatic alcohols having 6 to 30 carbon atoms to which 1 to 10 moles of ethylene oxide is added, and sulfosuccinic acid diester salts Granular or powdery diacetal composition which is at least 1 sort (s) chosen from the group which consists of (alpha)-sulfo fatty acid salt and (alpha)-sulfo fatty acid ester salt.
[15" claim-type="Currently amended] The method of claim 1, wherein as a binder
(h-a) tartaric acid, malic acid, citric acid, succinic acid and α, β-dihydroxyhexahydrophthalic acid,
(m) alkali metal salts, ammonium salts and alkali metal salts of (m-1) alkanesulfonic acids having 6 to 30 carbon atoms, alkenesulfonic acids having 6 to 30 carbon atoms, (C1-C22 alkyl) benzenesulfonic acid and (C1-C14 alkyl) naphthalenesulfonic acid; And (m-2) sulfuric acid ester salts of saturated and unsaturated aliphatic alcohols having 6 to 30 carbon atoms, sulfuric acid ester salts of saturated and unsaturated aliphatic alcohols having 6 to 30 carbon atoms to which 1 to 10 moles of ethylene oxide is added, and sulfosuccinic acid diester salts , α-sulfo fatty acid salts and α-sulfo fatty acid ester salts,
(a) aliphatic monocarboxylic acids having 8 to 30 carbon atoms, and
(g) A granular or powdery diacetal composition comprising at least one member selected from the group consisting of mono, di and tri (C6-C30 fatty acid) aluminum salts, and further comprising a cured oil as a lubricant.
[16" claim-type="Currently amended] The method of claim 1, wherein as a binder
(h-a) tartaric acid, malic acid, citric acid, succinic acid and α, β-dihydroxyhexahydrophthalic acid,
(m) alkali metal salts, ammonium salts and alkali metal salts of (m-1) alkanesulfonic acids having 6 to 30 carbon atoms, alkenesulfonic acids having 6 to 30 carbon atoms, (C1-C22 alkyl) benzenesulfonic acid and (C1-C14 alkyl) naphthalenesulfonic acid; And (m-2) sulfuric acid ester salts of saturated and unsaturated aliphatic alcohols having 6 to 30 carbon atoms, sulfuric acid ester salts of saturated and unsaturated aliphatic alcohols having 6 to 30 carbon atoms to which 1 to 10 moles of ethylene oxide is added, and sulfosuccinic acid diester salts , α-sulfo fatty acid salts and α-sulfo fatty acid ester salts, and
(a) A granular or powdery diacetal composition comprising at least one member selected from the group consisting of aliphatic monocarboxylic acids having 8 to 30 carbon atoms and further comprising a curing oil as a lubricant.
[17" claim-type="Currently amended] The method of claim 1, wherein as a binder
(m) alkali metal salts, ammonium salts and alkali metal salts of (m-1) alkanesulfonic acids having 6 to 30 carbon atoms, alkenesulfonic acids having 6 to 30 carbon atoms, (C1-C22 alkyl) benzenesulfonic acid and (C1-C14 alkyl) naphthalenesulfonic acid; And (m-2) sulfuric acid ester salts of saturated and unsaturated aliphatic alcohols having 6 to 30 carbon atoms, sulfuric acid ester salts of saturated and unsaturated aliphatic alcohols having 6 to 30 carbon atoms to which 1 to 10 moles of ethylene oxide is added, and sulfosuccinic acid diester salts , α-sulfo fatty acid salts and α-sulfo fatty acid ester salts, and
(a) A granular or powdery diacetal composition comprising at least one member selected from the group consisting of aliphatic monocarboxylic acids having 8 to 30 carbon atoms and further comprising a curing oil as a lubricant.
[18" claim-type="Currently amended] The method of claim 1, wherein as a binder
(g) mono, di and tri (C6-C30 fatty acid) aluminum salts,
(a) aliphatic monocarboxylic acids having 8 to 30 carbon atoms, and
(m) alkali metal salts, ammonium salts and alkali metal salts of (m-1) alkanesulfonic acids having 6 to 30 carbon atoms, alkenesulfonic acids having 6 to 30 carbon atoms, (C1-C22 alkyl) benzenesulfonic acid and (C1-C14 alkyl) naphthalenesulfonic acid; And (m-2) sulfuric acid ester salts of saturated and unsaturated aliphatic alcohols having 6 to 30 carbon atoms, sulfuric acid ester salts of saturated and unsaturated aliphatic alcohols having 6 to 30 carbon atoms to which 1 to 10 moles of ethylene oxide is added, and sulfosuccinic acid diester salts and at least one selected from the group consisting of α-sulfo fatty acid salts and α-sulfo fatty acid ester salts, and further comprising a cured oil as a lubricant.
[19" claim-type="Currently amended] The granular or powdery diacetal composition according to claim 1, wherein the binder is present in an amount of 0.01 to 100 parts by weight based on 100 parts by weight of the diacetal represented by the formula (1).
[20" claim-type="Currently amended] The granular or powdery diacetal composition according to claim 10, wherein the binder is used in an amount of 0.01 to 8 parts by weight based on 100 parts by weight of the diacetal represented by the formula (1).
[21" claim-type="Currently amended] The granular or powdery diacetal composition according to claim 1, wherein the average particle diameter is 3 to 2000 µm.
[22" claim-type="Currently amended] The granular or powdery diacetal composition according to claim 1, wherein the cross-sectional diameter is 0.2 to 5 mm and the cylindrical form or granule or flake form is 0.2 to 5 mm in diameter or granular or flake form.
[23" claim-type="Currently amended] The granular or powdery diacetal composition according to claim 1, having an apparent density of 0.2 to 1.1 g / cm 3.
[24" claim-type="Currently amended] The granular or powdery diacetal composition according to claim 1, wherein the melting point is 20 ° C or more lower than the diacetal represented by the formula (1) contained in the diacetal composition.
[25" claim-type="Currently amended] The granular or powdery diacetal composition according to claim 1, wherein the melting point is 40 ° C or more lower than the diacetal represented by the formula (1) contained in the diacetal composition.
[26" claim-type="Currently amended] The granular or powdery diacetal composition according to claim 1, comprising at least one member selected from the group consisting of an antistatic agent, a neutralizing agent or a stabilizer, and a lubricant.
[27" claim-type="Currently amended] 27. The method of claim 26, wherein the antistatic agent is glycerin fatty acid (C8-C22) mono, di and triester, N, N-bis (2-hydroxyethyl) alkyl (C8-C22) amine, polyoxyethylene (4-50 At least one granular or powder form selected from the group consisting of mole) alkyl (C12-C22) ether, polyoxyethylene (4-50 mole) alkyl (C7-C22) phenyl ether and pentaerythritol fatty acid (C8-C22) ester Diacetal composition.
[28" claim-type="Currently amended] 27. The process of claim 26 wherein the neutralizer or stabilizer is calcium stearate, lithium stearate, potassium stearate, sodium stearate, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydride. Oxyphenyl) propionate] methane, tris (2,4-di-t-butylphenyl) phosphite and 3,3'-thiodipropionic acid distearyl; at least one granular or powdery diacetal selected from the group consisting of Composition.
[29" claim-type="Currently amended] 27. The granular or powdery diacetal composition of claim 26, wherein the lubricant is at least one cured oil.
[30" claim-type="Currently amended] The product according to any one of claims 1 to 29, wherein as a by-product by condensation of a benzaldehyde which may have a substituent with a pentahydric or hexavalent alcohol other than the 1,3: 2,4-diacetal represented by the formula (1). It contains at least one monoacetal, triacetal and diacetal isomers, which are the acetals produced, and the total amount of the monoacetal, triacetal and diacetal isomers is the total amount of acetal (1,3: 2,4- represented by the formula (1). A granular or powdery diacetal composition with 0.05 to 10% by weight relative to the diacetal, monoacetal, triacetal and diacetal isomer).
[31" claim-type="Currently amended] (I) Formula 1
At least one diacetal represented by, and
(II) neutral to weakly acidic monovalent organic acids, neutral to weakly acidic polyvalent organic acids, partial salts of neutral to weakly acidic polyvalent organic acids, sulfuric acid ester salts, sulfonates, phosphate ester salts, phosphate esters, phosphorous acid esters and neutral to weakly acidic ones. At least one binder selected from the group consisting of aluminum salts of organic acids
Wherein the binder is a method for producing a granular or powdered diacetal composition uniformly dispersed in the particles of the granular or powdered diacetal composition,
(Iii) preparing a slurry containing diacetal represented by the formula (1) in a solvent, wherein the diacetal is swelled in this solvent,
(Ii) uniformly mixing the slurry and the binder,
(Iii) (a) removing the solvent from the homogeneous mixture obtained in step (ii) to obtain a dried product, or
(b) granulate while removing solvent from this homogeneous mixture, or
(c) classifying or pulverizing the dried product obtained in the step (a) or the granules obtained in the step (b), or
(d) A method for producing a granular or powdery diacetal composition comprising the step of classifying or granulating the milled product obtained in the above (c).
<Formula 1>

In the formula,
R ¹ and R ² are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom,
a and b each represent an integer of 1 to 5,
c represents 0 or 1,
When a is 2, two R ¹ may be bonded to each other to form a tetralin ring together with the benzene ring to which they are bonded. When b is 2, two R ² may be bonded to each other and together with the benzene ring to which they are bonded. It can also form a traline ring.
[32" claim-type="Currently amended] 32. The process of claim 31 wherein the slurry comprising swelled diacetal is made by swelling the diacetal powder in an organic solvent capable of swelling the diacetal powder.
[33" claim-type="Currently amended] The organic solvent of claim 31, wherein the organic solvent is a polar organic solvent or an aromatic hydrocarbon solvent, or (a) at least one member selected from the group consisting of a polar organic solvent and an aromatic hydrocarbon, and (b) an aliphatic hydrocarbon and an alicyclic compound. A mixture with at least one member selected from the group consisting of hydrocarbons, the polar solvent being an aliphatic alcohol having 1 to 18 carbon atoms; Alicyclic alcohols having 6 to 18 carbon atoms; Perfuryl alcohol; Cyclic ethers; Ketones; Aliphatic amines having 3 to 6 carbon atoms; Acetonitrile; Glycol ethers; At least one selected from the group consisting of dimethylformamide, dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
[34" claim-type="Currently amended] 32. The reaction mixture according to claim 31, wherein the slurry containing the swollen diacetal represented by the formula (1) is a reaction mixture obtained by condensation of a corresponding sorbitol or xylitol with a replaceable benzaldehyde in an organic solvent, or the reaction mixture is The manufacturing method which is a mixture obtained by neutralization or washing with water.
[35" claim-type="Currently amended] The reaction mixture according to claim 31, wherein the slurry containing the swollen diacetal represented by the formula (1) is a reaction mixture obtained by condensation of a corresponding sorbitol or xylitol with a replaceable benzaldehyde in the presence of an acid catalyst in water, or A process for producing an aqueous slurry obtained by neutralizing or washing the reaction mixture.
[36" claim-type="Currently amended] The nucleating agent for polyolefin resin containing the granular or powdery diacetal composition of Claim 1.
[37" claim-type="Currently amended] The nucleating agent for polyolefin resin according to claim 36, wherein the diacetal composition further contains at least one member selected from the group consisting of an antistatic agent, a neutralizing agent or a stabilizer, and a lubricant.
[38" claim-type="Currently amended] (Iii) a polyolefin resin powder or flake and powder or granules of the nucleating agent according to claim 36 or 37 or (ii) a polyolefin resin powder or flake, powder or granules of the nucleating agent according to claim 36 or 37 and at least one A powdery polyolefin resin composition obtained by blending an additive for polyolefin resin.
[39" claim-type="Currently amended] (Iii) blending the polyolefin resin powder or flake and the nucleating agent according to claim 36 or 37, or (ii) the polyolefin resin powder or flake, the nucleating agent according to claim 36 or 37 and the additive for at least one polyolefin resin. The polyolefin resin composition obtained by melt-kneading the obtained powdery composition under heating, extruding, cooling the extruded strand, cutting | disconnecting and pelletizing the obtained strand.
[40" claim-type="Currently amended] (Iii) a polyolefin resin powder or flake and the nucleating agent according to claim 36 or 37, or (ii) a polyolefin resin powder or flake, a powder of the nucleating agent according to claim 36 or 37, and an additive for at least one polyolefin resin. And blending the obtained powdery composition to a temperature above or below the melting point of the diacetal composition to melt-kneading and extruding, cooling the extruded strand, and cutting the obtained strand.
[41" claim-type="Currently amended] A nucleating agent in a polyolefin resin composition comprising the step of molding the polyolefin resin composition according to claim 38 or 39 by an injection molding method, an injection blow molding method, a blow molding method, or an extrusion molding method, or pneumatically molding a sheet obtained by the extrusion molding method. The manufacturing method of the polyolefin resin molded object containing a microdispersion in the minimum amount.
[42" claim-type="Currently amended] The polyolefin obtainable by the method containing the process of shape | molding the polyolefin resin composition of Claim 38 or 39 by the injection molding method, the injection blow molding method, the blow molding method, the extrusion molding method, or the pneumatic molding of the sheet | seat obtained by this extrusion molding method. Resin molded body.
[43" claim-type="Currently amended] (a) R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms or a halogen atom, and a and b Represents an integer of 1 to 5, respectively, and c is composed of at least one diacetal represented by the general formula (1) of 0 or 1, and (b) a binder containing at least one organic acid as an essential component. The binder is a composition that is uniformly dispersed in the diacetal, the average value of the particle diameter is 3 to 500 ㎛ powdery diacetal composition, characterized in that.
[44" claim-type="Currently amended] The method of claim 43, wherein the binder is tartaric acid, lactic acid, malic acid, citric acid, gluconic acid, pantothenic acid, 12-hydroxystearic acid, mandelic acid, cholic acid, β-oxynaphthoic acid, ricinolic acid, quinic acid, shikimic acid, salicylic acid, proto Powdery diacetal composition which is at least 1 sort (s) chosen from the group which consists of a catekunic acid, a coumalic acid, and a gallic acid.

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同族专利:

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公开号 | 公开日

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CA2273301C|2006-08-29|

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CA2273301A1|1999-04-15|

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MY123194A|2006-05-31|

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KR100376241B1|2003-03-15|

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AU746895B2|2002-05-02|

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CN1111161C|2003-06-11|

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ES2206946T3|2004-05-16|

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AT251165T|2003-10-15|

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NO992670D0|1999-06-02|

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ID21523A|1999-06-24|

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WO1999018108A1|1999-04-15|

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BR9806259A|2000-01-25|

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RU2177479C2|2001-12-27|

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DE69818641D1|2003-11-06|

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EP0962459A1|1999-12-08|

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EP0962459B1|2003-10-01|

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NO992670L|1999-08-02|

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JP3458190B2|2003-10-20|

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AU7938498A|1999-04-27|

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EP0962459A4|2001-06-20|

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TW515807B|2003-01-01|

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CN1241190A|2000-01-12|

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DE69818641T2|2004-07-29|

---

US6245843B1|2001-06-12|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1997-10-03|Priority to JP28792497

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1997-10-03|Priority to JP97-287924

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1998-03-04|Priority to JP7136298

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1998-03-04|Priority to JP98-71362

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1998-04-02|Priority to JP9017398

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1998-04-02|Priority to JP98-90173

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1998-07-07|Application filed by 후지타 기요시, 신닛폰 리카 가부시키가이샤

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2000-11-25|Publication of KR20000069250A

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2003-03-15|Application granted

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2003-03-15|Publication of KR100376241B1

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2004-06-29|First worldwide family litigation filed

优先权:

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申请号 | 申请日 | 专利标题

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JP28792497|1997-10-03|

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JP97-287924|1997-10-03|

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JP7136298|1998-03-04|

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JP98-71362|1998-03-04|

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JP9017398|1998-04-02|

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JP98-90173|1998-04-02|