西班牙专利ES2641954T9 Molded products

专利PDF首页>>西班牙专利

专利附录

专利说明

权利要求

类似技术

同族专利

引用文献

法律状态

优先权

专利摘要:

公开号:ES2641954T9
申请号:ES12858493.5T
申请日:2012-11-22
公开日:2018-09-28
发明作者:Hatsuki Oguro；Jun Mitadera
申请人:Mitsubishi Gas Chemical Co Inc；
IPC主号:

专利说明:

5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
DESCRIPTION
Molded products Technical field
The present invention relates to molded products formed by molding polyamide resin compositions. Specifically, it refers to molded products that have high chemical resistance, low water absorption rate and high dimensional stability. It also refers to processes for preparing said molded products.
Prior art
Polyamide resins generally show excellent mechanical properties such as strength, impact resistance and abrasion resistance, as well as high heat resistance and also show good impact resistance, so that they are widely used in the fields of parts of electrical / electronic equipment, auto parts, office equipment parts, various machinery parts, construction equipment / housing equipment parts. Among others, aliphatic polyamide resins such as polyamide 6 and polyamide 66 are widely used as versatile engineering plastics due to their excellent properties and ease of molding.
However, molded products formed by molding aliphatic polyamide resins have the disadvantages that they show high water absorption (hygroscopy) and low chemical resistance. Specifically, it is known that some of the molded products formed by molding of aliphatic polyamide resins absorb approximately 5% by mass of water based on the total mass. In molded products formed from polyamide 66, the modulus of elasticity possibly causes a decrease of approximately 3 GPa to less than 1 GPa after water absorption. In addition, most importantly, molded products of aliphatic polyamide resins have the disadvantage that they show a low chemical resistance and especially suffer a significant weight loss resulting in a significant loss of strength and modulus of elasticity in the presence of an acid or an alkali. In addition, molded products obtained by molding aliphatic polyamide resins also have the disadvantage that they show low dimensional stability. Especially, aliphatic polyamide resins are crystalline resins so that the resulting molded products undergo considerable dimensional changes or deformations, which can impair assembly or splicing with other parts, especially in molded products that are becoming thinner and smaller. such as the chassis. The molded products thus obtained also had the disadvantage of having poor dimensional stability for use as precision parts since they swelled or deformed when they absorbed moisture.
To compensate for the disadvantages of molded products using said crystalline aliphatic polyamide resins, proposals have been made for use in combination with semi-crystalline polyamide resins.
For example, patent document 1 proposes to use a polyamide resin composition comprising (A) a polycaproamide resin or a polyhexamethylene adipamide resin, (B) a semi-aromatic polyamide resin derived from an aliphatic diamine with acid isophthalic and terephthalic acid, (C) an inorganic filler and (D) a saturated aliphatic carboxylic acid. In addition, patent document 2 proposes to use a polyamide resin composition comprising (A) an aliphatic polyamide resin, (B) a semi-aromatic polyamide resin, (C) an inorganic filler and (D) an oxanilide stabilizer and He mentions specific examples of the semi-aromatic polyamide resin which include polyamide resins derived from m- or p-xylylenediamine with adipic acid and polyamide resins derived from hexamethylenediamine with iso and terephthalic acids.
However, the compositions of the polyamide resins proposed in these documents improved in water absorption, but their chemical resistance and dimensional stability during molding were not always sufficient and needed additional improvements.
In addition, it has been found that biaxially oriented films are made of a resin composition comprising an aliphatic polyamide resin and a polyamide resin synthesized from m-xylylenediamine and a dicarboxylic acid such as sebacic acid (patent document 3) . However, the films are different from the molded products used as pieces of machinery since they have a thickness of up to 0.25 mm or less.
On the other hand, a resin composition comprising a polyamide resin synthesized from m-xylylenediamine and sebacic acid has been discovered as well as a small amount of an aliphatic polyamide resin (patent document 4). This composition was excellent in water absorption and chemical resistance, but sometimes of poor crystallinity.
WO, A, 2012 110511 according to article 54 (3) EPC) discloses a polyamide composition.
EP, A, 0 458 470 discloses a polyamide resin, GB, A, 1 490 453 discloses a polyamide resin composition and JP, A S62 223262 discloses a resin composition.
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
References
Patent documents
Patent document 1: JP-A H3-269056;
Patent document 2: JP-A2010-189467;
Patent document 3: JP-A S48-54176;
Patent document 4: JP-A S63-137955:
Summary of the invention
Problems to be solved by the invention
An objective of the present invention is to solve the problems of the prior art described above and to provide molded products that show low water absorption, high chemical resistance, high crystallinity index and high dimensional stability while preserving the excellent intrinsic mechanical properties. to aliphatic polyamide resins. Another objective is to prepare molded products of aliphatic polyamide resins that show low water absorption, high chemical resistance and high crystallinity index with high dimensional stability.
Means to solve the problems
As a result of careful studies to achieve the above objectives, the inventors surprisingly discovered that molded products showing a markedly reduced water absorption, high chemical resistance can be obtained, for example, a reduced weight loss and therefore a markedly reduced loss. of resistance and an elastic modulus in the presence of an acid or an alkali, as well as a high crystallinity index, while retaining the excellent mechanical and similar properties intrinsic to aliphatic polyamides when formed using a resin composition of polyamide comprising (A) an aliphatic polyamide resin and a specific proportion in the range of 1 to 50% by mass of (B) a polyamide resin derived from a diamine that includes 70 mol% xylylenediamine and a dicarboxylic acid which includes 50 mol% or more of sebacic acid.
Specifically, the problems described above were resolved by the means shown below in
[1], preferably [2] to [9]. [1] A molded product formed from a polyamide resin composition containing 50 to 99 parts by mass of (A) an aliphatic polyamide resin and 50 to 1 parts by mass of (B) a polyamide resin which includes 70 mol% or more of a structural unit of diamine derived from xylylenediamine and 50% mol or more of a structural unit of dicarboxylic acid derived from sebacic acid, provided that the total of (A) and (B) be 100 parts by mass, in which the xylylenediamine is composed of 50 to 100 mol% of m-xylylenediamine and 0 to 50 mol% of p-xylylenediamine.
[2] The molded product according to [1], wherein the aliphatic polyamide resin (A) is polyamide 6 or polyamide 66.
[3] The molded product according to [1] or [2], wherein the xylylenediamine is m-xylylenediamine, p-xylylenediamine or a mixture thereof.
[4] The molded product according to any one of [1] to [3], in which the polyamide resin (B) is a poly (m-xylylene sebacamide) resin, a poly (p-xylylene) resin sebacamide) or a poly (m- / p-xylylene sebacamide) resin.
[5] The molded product according to any one of [1] to [4], in which the polyamide resin composition further contains 1 to 230 parts by mass of (C) a load per 100 parts by mass of the Total polyamide resin (A) and polyamide resin (B).
[6] The molded product according to any one of [1] to [5], which has the thinnest part having a thickness of 0.5 mm or more.
[7] The molded product according to any one of [1] to [6], wherein the amount of the polyamide resin (B) contained in the polyamide resin composition is 20 to 50 parts by mass per 100 parts by mass of the total of (A) and (B).
[8] The molded product according to any one of [1] to [7], which is formed by any one of injection molding, compression molding, vacuum molding, pressure molding and direct blow molding.
[9] A method of preparing a molded product, which comprises molding a polyamide resin composition containing 50 to 99 parts by mass of (A) an aliphatic polyamide resin and 50 to 1 parts by mass of (B) a polyamide resin that includes 70 mol% or more of a diamine structural unit derived from xylylenediamine and 50 mol% or more of a dicarboxylic acid structural unit derived from sebacic acid (provided that the total of (A) and (B) is 100 parts by mass) in which the xylylenediamine is composed of 50 to 100 mol% of m-xylylenediamine and 0 to 50 mol% of p-xylylenediamine by any one of injection molding, compression molding, vacuum molding, pressure molding and direct blow molding.
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
Advantages of the invention
The present invention allowed to provide molded products that have high chemical resistance, low water absorption, high crystallinity index and high dimensional stability.
The most preferred embodiments of the invention
The present invention will be explained in detail below. As used herein, the term "a" between two values means that it includes the values indicated before and after as lower and upper limits, unless otherwise specified.
[Summary of the invention]
Molded products formed by molding polyamide resin compositions according to the present invention (hereinafter referred to as "molded products of the present invention") are obtained by molding a polyamide resin composition comprising 50 to 99 parts by mass of (A) an aliphatic polyamide resin and 50 to 1 parts by mass of (B) a polyamide resin that includes a mole% or more of a diamine structural unit derived from xylylenediamine and a 50 Mole% or more of a structural unit of dicarboxylic acid derived from sebacic acid, provided that the total of (A) and (B) is 100 parts by mass.
[(A) Aliphatic polyamide resin]
The aliphatic polyamide resin (A) used in the present invention is an aliphatic polyamide resin obtained by polycondensation of a lactam containing three or more ring members, a polymerizable w-amino acid or an aliphatic diamine aliphatic dicarboxylic acid. As used herein, the term "aliphatic" means that it also includes alicyclic compounds.
Such lactams include, for example, amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid; £ -caprolactam and w-laurolactam. The w-amino acids include £ -aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
In addition, aliphatic dicarboxylic acids include, for example, aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, subic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid. Brazilian, tetradecanoic diacid, pentadecanoic diacid and octadecanoic diacid and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.
In addition, aliphatic diamines include, for example, aliphatic diamines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane (pentamethylenediamine), 1,6-diaminohexane, 1,7-diaminoheptane, 1 , 8-diaminooctane, 1,9-diaminononano, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16 - diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosan and 2-methyl-1,5-diaminopentane and alicyclic diamines such as cyclohexanediamine.
Specifically, the aliphatic polyamide resins (A) preferably include polyamide 4, polyamide 6, polyamide 46, polyamide 7, polyamide 8, polyamide 11, polyamide 12, polyamide 66, polyamide 69, polyamide 610, polyamide 611, polyamide 612, polyamide 6 / 66 and polyamide 6/12. These can be used in combination. Among others, especially preferred aliphatic polyamide resins (A) include polyamide 6, polyamide 66 and polyamide 6/66.
The aliphatic polyamide resin (A) preferably has a number average molecular weight (Mn) of 5,000 to 50,000. If the average molecular weight is too low, the mechanical strength of the resulting resin composition tends to be insufficient, but if it is too high, its moldability tends to decrease. More preferably, those having a number average molecular weight of 10,000 to 35,000 are used, most preferably 20,000 to 29,000.
[(B) Polyamide Resin]
The polyamide resin (B) used in the present invention is a polyamide resin composed of a structural unit of diamine (a structural unit derived from a diamine) and a structural unit of dicarboxylic acid (a structural unit derived from a dicarboxylic acid) wherein 70 mol% or more of the diamine structural unit is derived from xylylenediamine and 50 mol% or more of the dicarboxylic acid structural unit is derived from sebacic acid.
The polyamide resin (B) is obtained by polycondensation of a diamine component that includes 70% in
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
moles or more, preferably 80 mol% or more of xylylenediamine with a dicarboxylic acid component that includes 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more of sebacic acid.
If the xylylenediamine herein is less than 70 mol%, the composition of the polyamide resin finally obtained will be insufficient in the barrier properties, while if the sebacic acid is less than
50 mol%, the composition of the polyamide resin that forms the molded products of the present invention will be hard so that the moldability decreases.
The xylylenediamine used is composed of 50 to 100 mol% of m-xylylenediamine and 0 to 50 mol% of p-xylylenediamine if more importance is added to the moldability.
Examples of diamines other than xylylenediamine may include aliphatic diamines such as tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-methylenediamine, 2,2,4-methylmethylamine; Alicyclic diamines such as 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis ( 4-aminocyclohexyl) propane, bis (aminomethyl) decalin (including its structural isomers) and bis (aminomethyl) tricyclodecane (including its structural isomers); diamines having an aromatic ring such as bis (4-aminophenyl) ether, p-phenylenediamine and bis (aminomethyl) naphthalene (including its structural isomers) and can be used alone or as a mixture of two or more of them.
When a diamine other than xylylenediamine is used as the diamine component, it should be used in a proportion of less than 30 mol%, preferably 1 to 25 mol%, especially preferably 5-20 mol% of the structural unit of diamine
Sebacic acid is used in a proportion of 50 mol or more, preferably 70 mol or more, more preferably 80 mol or more of the structural unit of dicarboxylic acid. The proportion of the sebacic acid component is preferably greater since compatibility with the aliphatic polyamide resin (A) tends to increase.
Components of dicarboxylic acid other than sebacic acid that may be used preferably include straight chain aliphatic α, w-dicarboxylic acids containing 4 to 20 carbon atoms excluding sebacic acid, examples of which include, for example, aliphatic dicarboxylic acids such as adipic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, undecanoic diacid and dodecanoic diacid and can be used alone or as a mixture of two or more of them.
51 a straight chain aliphatic α, w-dicarboxylic acid excluding sebacic acid is used, it is preferably adipic acid or succinic acid, especially adipic acid.
Aromatic dicarboxylic acids can also be used as dicarboxylic acid components other than sebacic acid, and examples include phthalic acid compounds such as isophthalic acid, terephthalic acid and orthophthalic acid; Isomeric naphthalenedicarboxylic acids such as 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-
naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-
Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid and can be used alone or as a mixture of two or more of them. In addition, they can also be used in combination with monocarboxylic acids such as benzoic acid, propionic acid and butyric acid; polycarboxylic acids such as trimellitic acid and pyromellitic acid; carboxylic anhydrides such as trimellitic anhydride and pyromellitic anhydride. If a dicarboxylic acid other than straight chain aliphatic α, w-dicarboxylic acids containing 4 to 20 carbon atoms is to be used as a dicarboxylic acid component other than sebacic acid, it is preferably isophthalic acid due to moldability and the barrier properties. The proportion of isophthalic acid is preferably less than 30 mol%, more preferably in the range of 1 to 25 mol%, especially preferably 5 to 20 mol% of the structural unit of the dicarboxylic acid.
Especially preferred polyamide (B) resins are poly (m-xylylene sebacamide) resins derived from m-xylylenediamine with sebacic acid, poly (p-xylylene sebacamide) resins derived from p-xylylenediamine with sebacic acid and poly ( m- / p- xylylene sebacamide) derived from m-xylylenediamine and p-xylylenediamine with sebacic acid.
The melting point of the polyamide resin (B) is preferably in the range of 150 to 310 ° C, more preferably 160 to 300 ° C, even more preferably 170 to 290 ° C. The melting point is preferably in the previous intervals since its processability tends to improve. The glass transition point of the polyamide resin (B) is preferably in the range of 50 to 130 ° C. The glass transition point is preferably in the previous range since its barrier properties tend to improve.
As used herein, the melting point and the glass transition point of the aliphatic polyamide resin (A) and the polyamide resin (B) refer to the melting point and the glass transition point that can be determined by differential scanning calorimetry (DSC) by melting a sample by heating it once to eliminate the influence of thermal history on crystallinity and then heating it again. Specifically, a
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
test sample is melted, for example, by heating from 30 ° C to a temperature equal to or greater than an expected melting point at a rate of 10 ° C / min, then maintained at that temperature for 2 minutes and then cooled to 30 ° C at a speed of 20 ° C / min. The sample is then heated to a temperature equal to or greater than the melting point at a rate of 10 ° C / min, whereby the melting point and the glass transition point can be determined.
The polyamide resin (B) also preferably has a concentration of amino terminal groups of less than 100 peq / g, more preferably 5 to 75 peq / g, even more preferably 10 to 50 peq / g and preferably has a group concentration terminal carboxyl of less than 100 peq / g, more preferably 10 to 90 peq / g, even more preferably 10 to 50 peq / g.
The polyamide resin (B) also preferably has a relative viscosity of 1.7 to 4, more preferably 1.9 to 3.8 determined at a resin concentration of 1 g / 100 cc in 96% sulfuric acid at a temperature of 25 ° C.
In addition, the number average molecular weight of the polyamide resin (B) is preferably 6,000 to 50,000, more preferably 10,000 to 43,000. When it is in the previous intervals, its mechanical resistance and its moldability improve.
The polyamide resin (B) is composed of a diamine component that includes 70 mol% or more of xylylenediamine and a dicarboxylic acid component that includes 50 mol% or more of sebacic acid and is prepared using any of the procedures and previously known polymerization conditions including, but not limited to, atmospheric pressure melt polymerization, high pressure melt polymerization and the like.
For example, it is prepared by heating a polyamide salt composed of xylylenediamine and sebacic acid in the presence of pressurized water to polymerize it in the molten state while removing the added water and condensed water. It can also be prepared by directly adding xylethylenediamine to the molten sebacic acid to condense it at atmospheric pressure. In the latter case, the polycondensation proceeds by continuously adding xylylenediamine while the reaction system is heated to a reaction temperature equal to or greater than the melting points of the oligoamide and polyamide produced to prevent the reaction system from solidifying.
When the polyamide resin (B) is to be obtained by polycondensation, the polycondensation reaction system can be supplied with lactams such as £ -caprolactam, w-laurolactam and w-enantholactam; amino acids such as 6-aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 9-aminononanoic acid and p-aminomethylbenzoic acid as long as the yield is not affected.
Polyamide resin (B) can also be used after being heat treated further to increase the viscosity of the melt. Heat treatment processes include, for example, gently heating in the presence of water in an atmosphere of inert gas or reduced pressure using a discontinuous heater such as a rotary drum to induce crystallization while preventing melting, and then heating additional; or heating in an inert gas atmosphere using a slot stirrer / heater to induce crystallization and then heating in an inert gas atmosphere using a hopper-shaped heater; or use a stirrer / slot heater to induce crystallization, and then heat with a discontinuous heater such as a rotating drum.
Among others, the process using a discontinuous heater for crystallization and heat treatments is preferred. The preferred conditions for the crystallization treatment are as follows: heating a polyamide resin obtained by melt polymerization from 70 to 120 ° C for 0.5 to 4 hours in the presence of 1 to 30% by mass of water to crystallize it, then heat the crystallized resin to a temperature in the range of [the melting point of the polyamide resin obtained by melt polymerization minus 50 ° C] to [the melting point of the polyamide resin obtained by polymerization in molten state minus 10 ° C] for 1 to 12 hours in an inert gas atmosphere or at reduced pressure.
[Combination of (A) an aliphatic polyamide resin and (B) a polyamide resin]
The polyamide resin compositions that form the molded products of the present invention comprise 50 to 99 parts by mass of (A) an aliphatic polyamide resin and 50 to 1 parts by mass of (B) a polyamide resin per 100 parts in mass of the total of the resin (A) of aliphatic polyamide and the polyamide resin (B), and said intervals allow to reduce water absorption and improve chemical resistance and dimensional stability. If the polyamide resin (B) exceeds 50 parts by mass, the flexibility decreases. The maximum amount of the polyamide resin (B) should preferably be less than 50 parts by mass, more preferably 45 parts by mass or less, even more preferably 40 parts by mass or less, especially 35 parts by mass or less, while the minimum amount should preferably be 3 parts by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, especially 20 parts by mass or more. In addition, the difference between the melting points of the aliphatic polyamide resin (A) and the polyamide resin (B) is preferably more than 50 ° C. Although the underlying mechanism has been until now
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
unknown, there is a tendency that molding contraction can be reduced by selecting an associated polyamide resin (B) so that the difference in melting point can be 50 ° C or more even if the same resin is used (A ) of aliphatic polyamide. In the present invention, the difference between the melting points of the aliphatic polyamide resin (A) and the polyamide resin (B) is more preferably more than 50 ° C and 80 ° C or less.
[(C) Load]
The polyamide resin compositions that form the molded products of the present invention preferably contain (C) a filler, and the filler (C) is not specifically limiting as long as it is one of those conventionally used in this type of compositions and can be preferably use inorganic fillers in the form of powders, fibers, granules and platelets, as well as resin fillers or natural fillers.
The fillers in the form of powders and granules that can be used preferably have a particle size of 100 pm or less, more preferably 80 pm or less, and include kaolinite, silica; carbonates such as calcium carbonate and magnesium carbonate; sulfates such as calcium sulfate and magnesium sulfate; alumina, glass beads, carbon black, sulfides and metal oxides. Loads in the form of fibers that can be used include glass fibers, mustaches of potassium titanate or calcium sulfate, wollastonite, carbon fibers, mineral fibers and alumina fibers. Loads in the form of platelets include glass flakes, mica, talc, clay, graphite and sericite. Resin fillers include crystalline liquid aromatic polyester resins, entirely aromatic polyamide resins, acrylic fibers and poly (benzimidazole) fibers. Natural loads include kenaf, pasta, hemp paste and wood pulp. Among them, glass fibers and carbon fibers are preferred, especially glass fibers.
The content of the filler (C) is preferably 1 to 230 parts by mass per 100 parts by mass of the total polyamide resin (A) and the polyamide resin (B). Polyamide resin compositions containing the filler (C) in such range greatly improve in stiffness, strength and heat resistance. If it exceeds 230 parts by mass, the fluidity of the polyamide resin composition decreases to cause difficulty in kneading and casting in the molten state. More preferably, The content of the filler (C) is 180 parts by mass or less, even more preferably 100 parts by mass or less, while the content is more preferably at least 10 parts by mass or more, even more preferably 20 parts by mass or more, especially 30 parts by mass or more.
[(D) Carbodiimide Compound]
The polyamide resin compositions that form the molded products of the present invention also preferably contain (D) a carbodiimide compound. Said carbodiimide compounds (D) preferably include aromatic, aliphatic or alicyclic polycarbodiimide compounds prepared by various methods. Among them, aliphatic or alicyclic polycarbodiimide compounds are preferred due to the ability to knead in the molten state during extrusion, and alicyclic polycarbodiimide compounds are more preferably used.
These carbodiimide compounds (D) can be prepared by decarboxylation condensation of organic polyisocyanates. For example, they can be synthesized by decarboxylation condensation of various organic polyisocyanates at a temperature of about 70 ° C or more in an inert solvent or without using a solvent in the presence of a carbodiimidation catalyst. The isocyanate content is preferably 0.1 to 5% by mass, more preferably 1 to 3% by mass. The content of the above ranges tends to promote the reaction with polyamide resins (A) and (B), thereby improving hydrolysis resistance.
Organic polyisocyanates that can be used as starting materials for the synthesis of carbodiimide compounds (D) include, for example, various organic diisocyanates such as aromatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates and mixtures thereof.
Examples of organic diisocyanates specifically include 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,4-phenylene diisocyanate 2,4-Toluylene, 2,6-toluylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tetramethyl hexamethylene diisocyanate diisocyanate, diisocyanate , 2,6-diisopropylphenyl isocyanate, 1,3,5-triisopropylbenzene 2,4-diisocyanate and methylenebis (4,1-cyclohexylene) diisocyanate and two or more of them can be used in combination. Among them, 4,4'-dicyclohexylmethane diisocyanate and methylenebis (4,1-cyclohexylene) diisocyanate are preferred.
To cover the ends of the carbodiimide compounds (D) to control their degree of polymerization, terminal blocking agents such as monoisocyanates are also preferably used. Monoisocyanates include, for example, phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate and naphthyl isocyanate and the like, and two or more of them can be used in combination.
The terminal blocking agents are not limited to the monoisocyanates mentioned above, but can be any active hydrogen compound that can react with isocyanates. Examples of said
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
Active hydrogen compounds may include aliphatic, aromatic or alicyclic compounds having an OH group such as methanol, ethanol, phenol, cyclohexanol, N-methylene ethanolamine, polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether; secondary amines such as diethylamine and dicyclohexylamine; primary amines such as butylamine and cyclohexylamine; carboxylic acids such as succinic acid, benzoic acid and cyclohexanecarboxylic acid; thiols such as ethyl mercaptan, allyl mercaptan and thiophenol and compounds having an epoxy group and two or more of them can be used in combination.
Carbodiimidation catalysts that can be used include, for example, phospholene oxides such as 1- phenyl-2-phospholene-1-oxide, 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl- 2-phospholene -1-oxide, 3-methyl-2-phospholene-1-oxide and 3-phospholene isomers thereof; metal catalysts such as tetrabutyl titanate; Among which 3- methyl-1-phenyl-2-phospholene-1-oxide is preferred due to reactivity. Two or more carbodiimidation catalysts can be used in combination.
The content of the carbodiimide compound (D) is preferably 0.1 to 2 parts by mass, more preferably 0.2 to 1.5 parts by mass, still more preferably 0.3 to 1.5 parts by mass per 100 parts by mass of the total polyamide resins (A) and (B). If it is less than 0.1 parts by mass, the resulting resin composition will have insufficient resistance to hydrolysis, so that an irregular distribution is more likely to occur during kneading in the molten state such as extrusion, resulting in result in insufficient kneading in molten state. However, if it exceeds 2 parts by mass, the viscosity of the resin composition during kneading in the molten state tends to increase significantly, which may impair the ability to knead and moldability in the molten state.
[(E) Stabilizer]
The polyamide resin compositions that form the molded products of the present invention also preferably contain (E) a stabilizer. Such stabilizers preferably include, for example, organic stabilizers such as phosphorus stabilizers, hindered phenol stabilizers, hindered amine stabilizers, organic sulfur stabilizers, oxanilide stabilizers and aromatic secondary amine stabilizers and inorganic stabilizers such as copper and halide compounds . Phosphorus stabilizers preferably include phosphite compounds and phosphonite compounds.
Phosphite compounds include, for example, distearyl pentaerythritol diphosphite, dinonylphenyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl diphosphite) ) pentaerythritol, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-isopropylphenyl) pentaerythritol diphosphite, bis (2,4) diphosphite , 6-tri-t-butylphenyl) pentaerythritol, bis (2,6-di-t-butyl-4-sec-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-t diphosphite -octylphenyl) pentaerythritol and bis (2,4-dicumylphenyl) pentaerythritol diphosphite, among which bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,4-dicumylphenyl) diphosphite Pentaerythritol are especially preferred.
Phosphonite compounds include, for example, tetrakis diphosphonite (2,4-di-t-butylphenyl) -4,4'-biphenylene, tetrakis diphosphonite (2,5-di-t-butylphenyl) -4,4 ' -biphenylene, tetrakis diphosphonite (2,3,4-trimethylphenyl) -4,4'-biphenylene, tetrakis diphosphonite (2,3-dimethyl-5-ethylphenyl) -4,4'-biphenylene, tetrakis diphosphonite (2 , 6-di-t-butyl-5-ethylphenyl) -4,4'-biphenylene, tetrakis diphosphonite (2,3,4-tributylphenyl) -4,4'-biphenylene, tetrakis diphosphonite (2,4,6 -tri-t-butylphenyl) -4,4'-biphenylene and the like, among which tetrakis diphosphonite (2,4-di-t-butylphenyl) -4,4'-biphenylene is especially preferred.
The hindered phenol stabilizers include, for example, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate,
1.6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] of
pentaerythritol, 3,9-bis [1,1-dimethyl-2- {p-3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-
tetraoxaspiro [5,5] undecano, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1, 3,5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,2-thiodyethylene bis [3- (3,5-di-t-butyl-4 -hydroxyphenyl) propionate], tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate and N, N'-hexamethylene bis (3,5-di-t-butyl-4-hydroxyhydrocinamide). Among them, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) propionate], tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] of pentaerythritol, 3,9-bis [1,1-dimethyl-2- {p-3-t-butyl -4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and N, N'-hexamethylene bis (3,5-di-t-butyl-4- hydroxyhydrocinamide) are preferred.
The hindered amine stabilizers include, for example, the well-known hindered amine compounds having a 2,2,6,6-tetramethylpiperidine skeleton. Specific examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-phenylacetoxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-
2.2.6.6- tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-
benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4-ethylcarbamoyloxy-2,2,6,6-
tetramethylpiperidine, 4-cyclohexylcarbamoyloxy-2,2,6,6-tetramethylpiperidine, 4-phenylcarbamoyloxy-2,2,6,6-
tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6,6-tetramethyl- 4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) adipate, bis (2,2,6, 6-tetramethyl-4-piperidyl) terephthalate, 1,2-bis (2,2,6,6-tetramethyl-4-piperidyloxy) ethane, a, a'-bis (2,2,6,6-tetramethyl-4 - piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidylthylene) -2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
piperidyl) hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4- piperidyl) benzene-1,3,4-tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5- di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, the condensation product of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6- pentamethyl-4-piperidinol and p, p, p ', p'-tetramethyl-3,9- [2,4,8,10-
tetraoxaspiro (5,5) undecano] dietanol, the product of the polycondensation of dimethyl succinate and 1 - (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine and 1,3-benzenedicarboxamide-N, N'-bis (2,2,6,6-tetramethyl-4 piperidyl).
Commercially available hindered amine compounds include "ADK STAB LA-52, LA-57, LA-62, LA-67, LA- 63P, LA-68LD, LA-77, LA-82, LA-87" of ADEKA CORPORATION (all these designations included in quotes above and below represent brand names (registered trademarks)); "TINUVIN 622, 944, 119, 770, 144" from Ciba Specialty Chemicals Inc .; "SUMISoRb 577" from Sumitomo Chemical Company; "CYASORB UV- 3346, 3529, 3853" by American Cyanamid Company and "Nylostab S-EED" by Clariant (Japan) KK, etc.
Organic sulfur stabilizers include, for example, organic thio acid compounds such as didodecyl thiodipropionate, ditetradecyl thiodipropionate, dioctadecyl thiodipropionate, tetrakis (3- dodecylthiopropionate) of pentaerythritol and thio-bis (N-phenylamine); mercaptobenzimidazole compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole and metal salts of 2- mercaptobenzimidazole; dithiocarbamate compounds such as metal salts of diethyldithiocarbamic acid and metal salts of dibutyldithiocarbamic acid and thiourea compounds such as 1,3-bis (dimethylaminopropyl) -2-thiourea and tributylthiourea as well as tetramethylthiuram monosulfide, tetramethylthiuram disulphide, dithiocarbodium dibutyl dithiocarbamide , isopropyl nickel xanthate and trilauryl trithiophosphite.
Among them, mercaptobenzimidazole compounds, dithiocarbamate compounds, thiourea compounds and organic thio acid compounds are preferred, among which mercaptobenzimidazole compounds and organic thio acid compounds are more preferred. Especially, thioether compounds having a thioether structure can be conveniently used as they accept oxygen from oxidized materials to reduce it. Specifically, 2-mercaptobenzimidazole, 2-mercaptometilbencimidazol thiodipropionate, ditetradecyl thiodipropionate, dioctadecyl and tetrakis (3-dodecylthiopropionate), pentaerythritol are preferred, including thiodipropionate ditetradecyl, tetrakis (3-dodecylthiopropionate), pentaerythritol and 2 - Mercaptomethylbenzimidazole are even more preferred and tetrakis (3-dodecylthiopropionate) of pentaerythritol is especially preferred.
The organic sulfur compounds normally have a molecular weight of 200 or more, preferably 500 or more, and usually up to 3,000.
Oxanilide stabilizers preferably include 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxyanilide, 2,2'-didodecyloxy-5,5'- di-tert-butoxyanilide, 2-ethoxy-2'-ethylxanilide, N, N'-bis (3- dimethylaminopropyl) oxanilide, 2-ethoxy-5-tert-butyl-2'-ethoxyanilide and mixtures thereof with 2-ethoxy- 2'-ethyl-5,4'-di-tert-butoxyanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
Aromatic secondary amine stabilizers preferably include compounds that have a diphenylamine backbone, compounds that have a phenylnaphthylamine backbone and compounds that have a dinaphthylamine backbone, more preferably compounds that have a diphenylamine backbone and compounds that have a phenylnaphthylamine backbone. Specifically, compounds having a diphenylamine backbone include p, p'-dialkyl diphenylamine (in which the alkyl group contains 8 to 14 carbon atoms), octylated diphenylamine, 4,4'-bis (a, a-dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamide) diphenylamine, N, N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N '- (1,3-dimethylbutyl) - p-phenylenediamine and N-phenyl-N '- (3- methacryloxy-2-hydroxypropyl) -p-phenylenediamine; Compounds that have a phenylnaphthylamine skeleton include N-phenyl-1-naphthylamine and N, N'-di-2-naphthyl-p-phenylenediamine and compounds that have a dynaphthylamine skeleton include 2,2'-dynaphthylamine, 1, 2'-dynaphylamine and 1,1'-dynaphylamine. Among them, 4,4'-bis (a, a-dimethylbenzyl) diphenylamine, N, N'-di-2-naphthyl-p-phenylenediamine and N, N'-diphenyl-p-phenylenediamine are more preferred, among that N, N'-di-2-naphthyl-p-phenylenediamine and 4,4'-bis (a, a-dimethylbenzyl) diphenylamine are especially preferred.
When organic sulfur stabilizers or aromatic secondary amine stabilizers mentioned above are to be used, they should preferably be used in combination. Polyamide resin compositions that contain them in combination tend to improve heat aging resistance compared to those in which either is used.
More specific preferred combinations of organic sulfur stabilizers and aromatic secondary amine stabilizers include combinations of at least one organic sulfur stabilizer selected from ditetradecyl thiodipropionate, 2-mercaptomethylbenzimidazole and tetrakis (3-dodecylthiopropionate) of pentaerythritol and at least one stabilizer of aromatic secondary amine selected from 4,4'-bis (a, a-dimethylbenzyl) diphenylamine and N, N'-di-2-naphthyl-p-phenylenediamine. A combination of an organic sulfur stabilizer consisting of pentaerythritol tetrakis (3-dodecylthiopropionate) and an aromatic secondary amine stabilizer consisting of N, N'-di-2-naphthyl-p-phenylenediamine is more preferred.
When organic sulfur stabilizers and aromatic secondary amine stabilizers mentioned
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
previously to be used in combination, the ratio (mass ratio) of the amounts of the aromatic secondary amine stabilizers / organic sulfur stabilizers contained in the polyamide resin composition is preferably 0.05 to 15, more preferably from 0.1 to 5, even more preferably from 0.2 to 2. By selecting said content ratio, heat aging resistance can be efficiently improved while maintaining barrier properties.
Inorganic stabilizers preferably include copper and halide compounds.
Copper compounds are copper salts of various inorganic or organic acids excluding the halides mentioned below. Copper can be cuprous or cupric, and specific examples of copper salts include copper chloride, copper bromide, copper iodide, copper phosphate, copper stearate, as well as natural minerals, such as hydrotalcite, steatite and pyrolite.
Halides used as inorganic stabilizers include, for example, alkali metal or alkaline earth metal halides; ammonium halides and quaternary ammonium halides of organic compounds and organic halides, such as alkyl halides and allyl halides, the specific examples of which include ammonium iodide, triethyl stearyl ammonium bromide and triethyl benzyl ammonium iodide. Among them, alkali metal halide salts such as potassium chloride, sodium chloride, potassium bromide, potassium iodide and sodium iodide are preferred.
The copper compounds are preferably used in combination with the halides, especially with the halide salts of the alkali metal since excellent effects are provided on the aspects of heat induced discoloration resistance and weathering alterability resistance (resistance to the light). For example, when a copper compound alone is used, the molded product may be discolored in reddish brown by copper, which is not preferred for use in some applications. However, reddish-brown discoloration can be avoided by combining the copper compound with a halide.
In the present invention, organic sulfur stabilizers, aromatic secondary amine stabilizers and inorganic stabilizers are especially preferred among the stabilizers described above due to the processing stability during molten state molding, heat aging resistance, the appearance of Molded products and fading prevention.
The content of the stabilizer (E) is usually 0.01 to 1 part by mass, preferably 0.01 to 0.8 parts by mass per 100 parts by mass of the total polyamide resins (A) and (B) . The resistance to heat discoloration and weather / light alterability can be sufficiently improved by selecting the content in 0.01 parts by mass or more, while the loss of mechanical properties can be reduced by selecting the content in 1 part by mass or less.
The polyamide resin compositions that form the molded products of the present invention may also contain other resins than the polyamide resin (A) and the polyamide resin (B) as long as the benefits of the present invention are not affected. The other resins preferably include, for example, polyamide resins other than polyamide resin (A) and polyamide resin (B), polyester resins, polycarbonate resins, polyimide resins, polyurethane resins, acrylic resins, polyacrylonitrile , ionomers, ethylene vinyl acetate copolymers, fluorine resins, vinyl alcohol copolymers such as ethylene vinyl alcohol and biodegradable resins, and these can be used alone or as a mixture of two or more of them.
[Other additives]
The polyamide resin compositions that form the molded products of the present invention may also contain additives other than those described above, such as lubricants, matting agents, time stabilizers, UV absorbers, nucleating agents, plasticizers, strength improvers. to shock, flame retardants, conductive agents, antistatic agents, discoloration inhibitors, anti-gelling agents, pigments, dyes, dispersing agents and the like, or a mixture of various materials without limitation to the above list, as long as the Benefits of the present invention are not affected.
Nucleating agents normally include inorganic nucleating agents, such as fine talcum powder and boron nitride, but organic nucleating agents can also be added. The amount of the nucleating agents added is preferably 0.01 to 6 parts by mass, more preferably 0.03 to 1 parts by mass in the case of organic nucleating agents and boron nitride per 100 parts in mass of resin components.
[Procedures for preparing resin compositions]
The methods of preparing the compositions of the polyamide resins used in the present invention are not specifically limited, but can be prepared by mixing a polyamide resin (A) and a polyamide resin (B) and optionally other components in any order for Form a dry mixture. They can also be prepared by kneading the dried mixture further.
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
Among others, they are preferably prepared by kneading in a molten state using one or more conventional extruders, such as a single screw or double screw extruder, especially preferably a double screw extruder due to productivity and versatility. In this case, the kneading in the molten state is preferably performed under controlled conditions at a temperature of 200 to 300 ° C for a residence time of 10 min or less using a screw having at least one or more, preferably two or more elements. of reverse propeller screw and / or kneading discs in which the mixture remains partially. Insufficient extrusion kneading or resin decomposition tends to be less likely to occur by controlling the melting temperature in the molten state in the previous range.
Alternatively, compositions having a predetermined component ratio can be prepared by preliminary kneading polyamide resins with additives in high concentrations to prepare a masterbatch and then dilute it with polyamide resins.
If fibrous materials such as glass fibers and carbon fibers are used, they are preferably supplied from a side feeder mounted midway along the extruder cylinder.
[Preparation procedures for molded products]
The polyamide resin compositions that form the molded products of the present invention can be shaped into molded products in various ways by conventionally known molding procedures. Examples of molding processes may include, but are not limited to, injection molding, blow molding, extrusion molding, compression molding, vacuum molding, pressure molding, direct blow molding, rotational molding, sandwich molding, and molding two colors, for example, more preferably injection molding, compression molding, vacuum molding, pressure molding and direct blow molding. Especially preferred are injection molding, compression molding, vacuum molding, pressure molding and direct blow molding, among which injection molding is more preferred because the resulting molded products show very good dimensional stability and high chemical resistance.
The molded products obtained from the polyamide resin compositions described above can be conveniently used as various molded articles that are required to have low water absorption, high chemical resistance and high crystallinity index, including various parts such as, for example, auto parts (connectors), machinery parts and electrical / electronic equipment parts. In addition, the molded products of the present invention can also be in sheet or tube form so that they can be conveniently used as industrial, engineering and household goods. As used herein, the term "sheet" means those having a thickness of, for example, more than 0.25 mm.
The molded products of the present invention are especially useful when they have the thinnest thickness of 0.5 mm or more (preferably 1 to 2.5 mm), for example.
According to the methods of preparing the molded products of the present invention, various molded products that required to have low water absorption, high chemical resistance and high crystallinity index can be prepared with high dimensional stability.
Examples
The following Examples further illustrate the present invention, but the present invention should not be construed as limiting these Examples / Comparative Examples.
[Used materials]
The materials used in the Examples and in the Comparative Examples are the following:
<(A) Aliphatic polyamide resins>
The following commercially available products were used as resins (A) of aliphatic polyamide.
- Polyamide 6 (Ny6)
The product available from Ube Industries, Ltd. as 1024B grade having a molecular weight of 28,000, a melting point of 225 ° C and a glass transition point of 48 ° C.
- Polyamide 66 (Ny66)
The product available from Toray Industries, Inc. as grade CM3001N having a molecular weight of 25,000, a melting point of 265 ° C and a glass transition point of 50 ° C.
<(B) Polyamide resins>
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
The polyamide resins prepared in the following preparation examples 1 to 4 were used as polyamide resins (B).
<Preparation example 1 (synthesis of poly-m-xylylene sebacamide (MXD10)>
In a reaction vessel, sebacic acid (TA grade available from Itoh Oil Chemicals Co., Ltd.) was melted by heating to 170 ° C and then the temperature rose to 240 ° C while m-xylylenediamine (MXDA in Mitsubishi Gas Chemical Company, Inc.) was gradually added dropwise in a 1: 1 molar ratio to sebacic acid while stirring the contents. After completing the dropwise addition, the temperature rose to 260 ° C. After completing the reaction, the contents were collected in the form of strands and granulated in a granulator. The resulting microgranules were placed in a vessel and polymerized in solid phase under reduced pressure to give a polyamide resin having a controlled molecular weight.
The polyamide resin (MXD10) had a melting point of 191 ° C, a glass transition point of 60 ° C, a number average molecular weight of 30,000 and an oxygen transmission rate of 0.8 cc.mm/m2. day.atm determined by the procedures described below.
This polyamide resin is hereinafter referred to as "MXD10".
<Preparation example 2 (synthesis of poly (p-xylylene sebacamide) (PXD10)>
A reaction vessel equipped with a stirrer, a partial condenser, a total condenser, a thermometer, a drip device and a nitrogen inlet, as well as a strand die is loaded with heavy amounts with precision 8950 g (44 moles) of sebacic acid (TA grade available from Itoh Oil Chemicals Co., Ltd.), 13.7401 g of calcium hypophosphite (150 ppm expressed as the concentration of phosphorus atoms in the polyamide resin), and 10.6340 g of acetate of sodium. The molar ratio between calcium hypophosphite and sodium acetate is 1. The reaction vessel was thoroughly purged with nitrogen and then pressurized with nitrogen at 0.3 MPa and heated to 160 ° C with stirring to homogeneously melt the acid. sebaceous
Then, 6026 g (44 mol) of p-xylylenediamine (PXDA) was added dropwise with stirring for 170 min. At that time, the internal temperature rose continuously to 281 ° C. During the dropwise addition step, the pressure was controlled at 0.5 MPa and the water generated was removed out of the system through the partial condenser and the total condenser. The temperature in the partial condenser is controlled in the range of 145 to 147 ° C. After completing the dropwise addition of p-xylylenediamine, the pressure was reduced at a rate of 0.4 MPa / h at atmospheric pressure for 60 min. At that time, the internal temperature rose to 299 ° C. Then, the pressure was reduced at a rate of 0.002 MPa / min to 0.08 MPa for 20 min.
Then, the reaction was continued at 0.08 MPa until the stirrer torque reached a predetermined value. The reaction period at 0.08 MPa was 10 min. The interior of the system was then pressurized with nitrogen, and the polymer was collected from the strand die and granulated to give a polyamide resin. The resulting polyamide PXD10 resin had a melting point of 290 ° C and a glass transition point of 75 ° C. It had a number average molecular weight of 25,000 and an oxygen transmission rate of 2.5 cc.mm/m2.día.atm.
This polyamide resin is hereinafter referred to as "PXD10".
<Preparation example 3 (synthesis of poly (m- / p-xylylene sebacamide) (MPXD10-1)>
A polyamide resin was obtained in the same manner as in Preparation Example 1, except that m-xylylenediamine was substituted by a 3: 7 (molar ratio) mixture of m-xylylenediamine and p-xylylenediamine and the temperature rose to 260 ° C while the xylylenediamine mixture was gradually added dropwise in a 1: 1 molar ratio to sebacic acid and after completing the dropwise addition, the temperature rose to 280 ° C.
The polyamide resin (MPXD10-1) had a melting point of 258 ° C, a glass transition point of 70 ° C, a number average molecular weight of 20,000 and an oxygen transmission rate of 2 cc.mm/ m2.día.atm determined by the procedures described below.
This polyamide resin is hereinafter referred to as "MPXD10-1".
<Preparation of Example 4 (synthesis of poly (m- / p-xylylene sebacamide) (MPXD10-2)>
A polyamide resin was obtained in the same manner as in Preparation Example 1, except that m-xylylenediamine was substituted by a 7: 3 (molar ratio) mixture of m-xylylenediamine and p-xylylenediamine.
The polyamide resin (MPXD10-2) had a melting point of 215 ° C, a glass transition point of 63 ° C, a number average molecular weight of 28,000 and an oxygen transmission rate of 1.4 cc. mm / m2 day
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
determined by the procedures described below.
This polyamide resin is hereinafter referred to as "MPXD10-2".
The melting point and the glass transition point (expressed in ° C) of the polyamide resins described above was determined by the following procedure.
Melting point and glass transition point was determined by differential scanning calorimetry (DSC) using DSC-60 available from SHIMADZU CORPORATION under the following analytical conditions: a sample of approximately 5 mg was heated from 30 to 300 ° C at a speed of 10 ° C / min, maintained at 300 ° C for 2 min, then cooled to 30 ° C at a speed of 20 ° C / min, and then heated at a speed of 10 ° C / min, so that the melting point and the glass transition point were determined.
The number average molecular weight of each of the XD10 resins described above was determined as follows. The number average molecular weight was determined by GPC analysis and expressed as a PMMA equivalent using HLC-8320GPC available from Tosoh Corporation on TSKgel SuperHM-H columns eluting with hexafluoroisopropanol (HFIP) containing 10 mmol / l sodium trifluoroacetate at temperature of 40 ° C. A calibration curve was prepared by six PMMA standards dissolved in HFIP.
<Other additives>
- Fiberglass:
Cut threads available at Nippon Electric Glass Co., Ltd. under the brand “T-275H".
- Nucleating agent: fine-grained talc available from Hayashi-Kasei Co., Inc. under the "Micron White # 5000S" brand.
- Aromatic secondary amine stabilizer:
N, N'-di-2-naphthyl-p-phenylenediamine available from Ouchi Shinko Chemical Industrial Co., Ltd. under the trademark "NOCRAC white".
- Inorganic stabilizer: a 1: 5 (mass ratio) mixture of copper chloride / potassium iodide.
(Examples 1 to 7 and Comparative Examples 1 to 4)
The components described above were weighed in the amounts shown in Table 1 below (all expressed in mass parts), mixed in a vessel and introduced into a double screw extruder ("TEM26SS" available from Toshiba Machine Co., Ltd. ). The components were kneaded in the molten state under the conditions of a cylinder temperature of 300 ° C and a screw speed of 100 rpm and the melt was extruded and granulated and then dried under vacuum at 150 ° C for 5 hours to Prepare microgranules of polyamide resin compositions.
The resulting microgranules were used to perform various evaluations by the evaluation procedures described below.
The results of the evaluation are shown in Table 1.
[Evaluation Procedures]
In the Examples and Comparative Examples, the analysis / evaluation procedures are as follows.
(1) Evaluation of dimensional stability (molding contraction expressed in%)
The microgranules described above were injection molded into 60 mm x 60 mm x 2 mm test samples using the "model SE130DU-HP" injection molding machine available from Sumitomo Heavy Industries, Ltd. under the conditions of a cylinder temperature from 250 ° C to 300 ° C, a mold temperature of 30 ° C and a molding cycle time of 40 seconds. The lengths of the test samples in the MD and TD directions were measured and compared with the dimensions of the mold cavity to determine the molding contraction (expressed in%).
The average of the contractions of molding in machine direction (MD) and transverse direction (TD) was calculated and evaluated as follows.
A: less than 1 B: 1 or more and less than 1.5 C: 1.5 or more and less than 2 D: 2 or more.
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
(2) Evaluation of chemical resistance (elastic modulus retention rate and resistance retention rate)
The microgranules described above were injection molded into ISO test samples (having a thickness of 4 mm) using the injection molding machine "model SE130DU-HP" available in Sumitomo Heavy
Industries, Ltd. under the conditions of a cylinder temperature of 250 ° C to 300 ° C, a mold temperature of 30 ° C and a molding cycle time of 40 seconds. The resulting ISO test samples were annealed at 150 ° C for 1 hour. Its flexural strength (expressed in MPa) and the modulus of elasticity by flexion (expressed in GPa) were measured in accordance with ISO178 at a temperature of 23 ° C.
Then, the ISO test samples were immersed in aqueous solutions each containing 10% by mass of hydrochloric acid, NaOH or CaCl2 (at a temperature of 23 ° C), and after 7 days, the flexural strength (expressed in MPa) and the modulus of elasticity by flexion (expressed in GPa) of the test samples were measured and compared with the values measured before immersion to determine retention rates (expressed in%).
In addition, the average retention rates of the elastic modulus and the resistance after immersion in aqueous solutions each containing 10% by mass of hydrochloric acid, NaOH or CaCh (at a temperature of 23 ° C) was evaluated as follows.
A: average of 90% or more B: average of less than 90% and 60% or more C: average of less than 60% and 40% or more D: average of less than 40%.
(3) Evaluation of the water absorption rate determined as the weight change rate (expressed in%)
The ISO test samples described above were immersed in distilled water at 23 ° C, and after 110 days, the surface water was removed and then the weight and water absorption rate (the rate of change) weight expressed in%) was calculated from the difference between weights before and after immersion to observe changes in the rate of water absorption over time.
In addition, the water absorption rate was evaluated according to the following criteria:
A: less than 5%
B: 5% or more and less than 7%
C: 7% or more and less than 10%
D: 10% or more.
(4) Crystallinity Index
The microgranules described above were injection molded into test samples that are 4 mm thick using the "model SE130DU-HP" injection molding machine available from Sumitomo Heavy Industries, Ltd. under the conditions of a cylinder temperature of 250 ° C to 300 ° C, a mold temperature of 30 ° C and a molding cycle time of 40 seconds. The resulting molded products were analyzed by differential scanning calorimetry (DSC) using "DSC-60" available from SHIMADZU CORPORATION. The evaluation was done according to the crystallization maximums during heating as follows:
A: maximum crystallization during heating with 0 J / g or more and less than 3 J / g
B: maximum crystallization during heating with 3 J / g or more and less than 5 J / g
C: maximum crystallization during heating with 5 J / g or more and less than 7 J / g
D: crystallization maximums during heating with 7 J / g or more.
(5) Overall evaluation
Based on the results of (1) to (4) above, the total numbers of classifications A to D were counted.

权利要求:
Claims (8)
[1]
5
10
fifteen
twenty
25
30
35

1. A molded product formed from a polyamide resin composition containing 50 to 99 parts by mass of (A) an aliphatic polyamide resin and 50 to 1 parts by mass of (B) a composite polyamide resin by 70 mol% or more of a structural unit of diamine derived from xylylenediamine and by 50 mol% or more of a structural unit of dicarboxylic acid derived from sebacic acid, provided that the total of (A) and (B) It is 100 parts by mass in which xylylenediamine is composed of 50 to 100 mol% of m-xylylenediamine and 0 to 50 mol% of p-xylylenediamine.
[2]
2. The molded product according to claim 1, wherein the aliphatic polyamide resin (A) is polyamide 6 or polyamide 66.
[3]
3. The molded product according to any one of claims 1 to 2, wherein the polyamide resin (B) is a poly (m-xylylene sebacamide) resin or a poly (m- / p-xylylene) resin sebacamida).
[4]
4. The molded product according to any one of claims 1 to 3, wherein the polyamide resin composition contains in addition to 1 to 230 parts by mass of (C) a charge per 100 parts by mass of the total the polyamide resin (A) and the polyamide resin (B).
[5]
5. The molded product according to any one of claims 1 to 4, having the thinnest part having a thickness of 0.5 mm or more.
[6]
6. The molded product according to any one of claims 1 to 5, wherein the amount of the polyamide resin (B) contained in the polyamide resin composition is 20 to 50 parts by mass per 100 parts in mass of the total of (A) and (B).
[7]
7. The molded product according to any one of claims 1 to 6, which is formed by any one of injection molding, compression molding, vacuum molding, pressure molding and direct blow molding.
[8]
8. A process for preparing a molded product, which comprises molding a polyamide resin composition containing 50 to 99 parts by mass of (A) an aliphatic polyamide resin and 50 to 1 parts by mass of (B) a polyamide resin composed of 70 mol% or more of a structural unit of diamine derived from xylylenediamine and 50% mol or more of a structural unit of dicarboxylic acid derived from sebacic acid (provided that the total of (A ) and (B) is 100 parts by mass) wherein the xylylenediamine is composed of 50 to 100 mol% of m-xylylenediamine and 0 to 50 mol% of p-xylylenediamine, by any one of molding by injection, compression molding, vacuum molding, pressure molding and direct blow molding.

类似技术:

公开号 | 公开日 | 专利标题

ES2641954T3|2017-11-14|Molded products

US8603600B2|2013-12-10|Polyamide resin compositions

JP5168432B2|2013-03-21|Reactive polyamide resin and polyamide resin composition

US8841407B2|2014-09-23|Polyamide resins and processes for molding them

JP5673130B2|2015-02-18|Polyamide resin and method for producing the same

JP5212582B1|2013-06-19|Thin-walled molded product

JP6098058B2|2017-03-22|Flame retardant polyamide resin composition

同族专利:

公开号 | 公开日

JP6156150B2|2017-07-05|

EP2792714A4|2015-07-08|

CN103987782B|2018-02-06|

KR20190089225A|2019-07-30|

TW201331296A|2013-08-01|

ES2641954T3|2017-11-14|

NO2792714T3|2018-01-20|

KR20140107445A|2014-09-04|

EP2792714B1|2017-08-23|

MX345572B|2017-02-03|

US20140342145A1|2014-11-20|

HK1200477A1|2015-08-07|

EP2792714B9|2018-04-04|

EP2792714A1|2014-10-22|

TWI593751B|2017-08-01|

MX2014006923A|2014-09-11|

BR112014013991A2|2017-06-13|

ES2641954T5|2021-06-21|

CN103987782A|2014-08-13|

JPWO2013088932A1|2015-04-27|

EP2792714B2|2020-09-23|

WO2013088932A1|2013-06-20|

引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

NL103099C|1957-04-11|

DE1669543A1|1966-01-29|1971-07-22|Teijin Ltd|Polyamide compounds for molding, pressing and coating purposes|

JPS5129192B2|1971-11-08|1976-08-24|

US3939901A|1973-04-19|1976-02-24|White Motor Corporation|Method and apparatus for cooling and deaerating internal combustion engine coolant|

JPS5432458B2|1974-11-26|1979-10-15|

US3968071A|1975-11-20|1976-07-06|Mitsubishi Gas Chemical Company, Inc.|Polyamide resin molding composition|

CA1288885C|1986-12-01|1991-09-10|Kenichi Narita|Molding polyamide resin composition|

JPH0444658B2|1987-03-10|1992-07-22|Suzuki Sakan Tairukoten Jugen|

AU638120B2|1990-05-21|1993-06-17|Mitsubishi Gas Chemical Company, Inc.|Polyamide resin, and polyamide resin compositions|

US5147944A|1990-10-16|1992-09-15|Mitsubishi Gas Chemical Company, Inc.|Polyamide resin, and polyamide resin compositions|

US5994209A|1996-11-13|1999-11-30|Applied Materials, Inc.|Methods and apparatus for forming ultra-shallow doped regions using doped silicon oxide films|

US6855755B1|1999-08-04|2005-02-15|Mitsubishi Engineering-Plastics Corporation|Polyamide resin composition having improved weathering resistance and its molded products|

CN1322027C|2003-05-06|2007-06-20|三菱瓦斯化学株式会社|Fuel-barrier polyamide resin and multilayer shaped article|

JP4444723B2|2004-04-20|2010-03-31|豊田合成株式会社|Plastic molded product|

JP2006028327A|2004-07-15|2006-02-02|Unitika Ltd|Molding material for precision part|

FR2884518B1|2005-04-14|2007-09-21|Arkema Sa|BARRIER STRUCTURE BASED ON POLYAMIDE MXD.10|

WO2007138966A1|2006-05-25|2007-12-06|Mitsubishi Engineering-Plastics Corporation|Moldings of fiber-reinforced thermoplastic resin|

JP5200335B2|2006-05-31|2013-06-05|三菱瓦斯化学株式会社|Polyamide resin composition|

RU2441043C2|2006-05-31|2012-01-27|Мицубиси Гэс Кемикал Компани, Инк.|Polyamide resin composition|

US8927647B2|2008-09-18|2015-01-06|Mitsubishi Gas Chemical Company, Inc.|Polyamide resin|

JP5555432B2|2009-02-16|2014-07-23|三菱エンジニアリングプラスチックス株式会社|Polyamide resin composition|

CN102449028B|2009-05-28|2014-07-02|三菱瓦斯化学株式会社|Polyamide resin|

JP5407789B2†|2009-11-16|2014-02-05|三菱瓦斯化学株式会社|Thermoplastic resin composition having excellent hydrolysis resistance|

JP5120518B2|2010-07-27|2013-01-16|三菱瓦斯化学株式会社|Polyamide resin|

JP5621449B2|2010-09-17|2014-11-12|三菱瓦斯化学株式会社|Manufacturing method of polyamide resin composition pellets|

JP5625668B2|2010-09-17|2014-11-19|三菱瓦斯化学株式会社|Polyamide resin composition and molding method thereof|

US20140039134A1|2011-02-17|2014-02-06|Dsm Ip Assets B.V.|Polyamide composition|TWI485191B|2009-10-09|2015-05-21|Ube Industries|A colored polyimide molded article and a method for producing the same|

JP2016169291A|2015-03-12|2016-09-23|三菱瓦斯化学株式会社|Polyamide resin composition and method for producing the same, film, and multilayer film|

CN104830054B|2015-03-26|2018-05-18|金发科技股份有限公司|A kind of daiamid composition|

CN107531002B|2015-05-08|2019-10-01|三菱瓦斯化学株式会社|Honeycomb structure and sandwich structural body and honeycomb substrate for manufacturing them|

JP6703389B2|2015-10-20|2020-06-03|ダイセルポリマー株式会社|Molded article manufacturing method|

JP6691771B2|2015-12-25|2020-05-13|三菱エンジニアリングプラスチックス株式会社|Polyamide resin composition, kit, method for producing molded article, molded article and method for producing polyamide resin composition|

FR3057572A1|2016-10-19|2018-04-20|Arkema France|USE OF A SEMI-AROMATIC POLYAMIDE IN AN ALIPHATIC POLYAMIDE MIXTURE COMPRISING CIRCULAR SECTION GLASS FIBERS FOR LIMITING WEIGHT|

FR3057573A1|2016-10-19|2018-04-20|Arkema France|USE OF GLASS FIBERS WITH A CIRCULAR SECTION IN A MIXTURE COMPRISING A SEMI-AROMATIC POLYAMIDE AND AN ALIPHATIC POLYAMIDE FOR IMPROVING THE MECHANICAL PROPERTIES OF SAID MIXTURE|

JP6561217B2|2016-12-27|2019-08-21|住友理工株式会社|Refrigerant transport hose|

EP3663361B1|2017-07-31|2021-03-17|Mitsubishi Gas Chemical Company, Inc.|Easily-torn film, multilayer film, packaging material, and container|

CN107383365A|2017-08-09|2017-11-24|无锡殷达尼龙有限公司|A kind of Semi-aromatic polyamide resin and preparation method thereof|

EP3966283A1|2019-05-08|2022-03-16|Solvay Specialty Polymers USA, LLC.|Hot-water moldable polyamide molding compositions|

KR20210012103A|2019-07-23|2021-02-03|주식회사 엘지화학|Apparatus For Fire Detection of Vehicle Battery and Method Thereof|

WO2021187616A1|2020-03-19|2021-09-23|宇部興産株式会社|Polyamide resin composition|

法律状态:

优先权:

申请号 | 申请日 | 专利标题

JP2011275249|2011-12-16|

PCT/JP2012/080262|WO2013088932A1|2011-12-16|2012-11-22|Molded article|

[返回顶部]