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    • 专利摘要:
    FLAME-RETARDANT POLYAMIDE RESIN COMPOSITIONS.The present invention relates to a flame retardant polyamide resin composition comprising: a polyamide (A) which contains a diamine unit including 70 mol% or more of a dicarboxylic acid unit including 70 mol% or more than one linear aliphatic dicarboxylic acid unit having 6 to 18 carbon atoms, an organic halogen compound (B) that serves as a flame retardant; an inorganic compound (C) that serves as a flame-retardant aid; an inorganic compound (C) that serves as a flame retardant aid; and an inorganic filler (D) in which a flame retardant aid; and an inorganic filler (D) wherein the polyamide (A) comprises a polyamide having a phosphorus atom concentration of 50 to 1000 ppm and a YI value of 10 or less in a color difference test in accordance with JIS K-7105, and an inorganic compound content (C) and an inorganic filler content (D) are to 1 to 100 parts by weight, 0.5 to 50 parts by weight, and 0 to 100 parts by weight, respectively, with respect to 100 parts by weight of polyamide (A).
    公开号:BR112012005734A2
    申请号:R112012005734-0
    申请日:2010-09-14
    公开日:2021-07-27
    发明作者:Kentaro Ishii；Hisayuki Kuwahara；Shun Ogawa；Shinichi Ayuba；Takahiko Sumino
    申请人:Mitsubishi Gas Chemical Company；
    IPC主号:
    专利说明:

    [1] [1] A flame retardant polyamide resin composition comprising: a polyamide (A) containing a diamine unit including 70% by mol or more of a p-xylylenediamine unit and a dicarboxylic acid unit including 70% in mol or more of a linear aliphatic dicarboxylic acid unit having from 6 to 18 carbon atoms, an organic halogen compound (B) which serves as a flame retardant; an inorganic compound (C) which serves as a flame-retardant aid; and an inorganic filler (D) wherein the polyamide (A) comprises a polyamide having a phosphorus atom concentration of 50 to 1000 ppm and a YI value of 10 or less in a color difference test of according to JIS K-7105, and an organic halogen compound content (B), an inorganic compound content (C) and an inorganic filler content (D) are 1 to 100 parts by weight, 0.5 to 50 parts by weight, and 0 to 100 parts by weight, respectively, with respect to 100 parts by weight of polyamide (A).
    [2] [2] A molded article comprising the flame retardant polyamide resin composition according to item [1].
    Advantageous Effects of the Invention The flame retardant polyamide resin composition of the present invention is excellent not only in flame retardancy but also in a variety of physical properties such as moldability, mechanical properties, heat resistance, and low ca. water absorption capacity, and can be used properly in a wide range of applications and conditions as a molding material for a variety of industries and industrial and household products such as electrical or electronic parts, automotive parts, and mechanical parts that are required to have a flame retardancy.
    Description of Modalities A flame retardant polyamide resin composition of the present invention includes, as mentioned below a polyamide (A) containing a diamine unit and a dicarboxylic acid unit, an organic halogen compound (B) which serves as a flame retardant, and an inorganic compound (C) which serves as a flame retardant aid, and as required, also includes an inorganic filler (D) which serves as a reinforcement.
    In this context, the diamine unit refers to a constituent unit derived from a raw material diamine component, and the dicarboxylic acid unit refers to a constituent unit derived from a raw material dicarboxylic acid. <polyamide A> Polyamide (A) contains the diamine unit which includes 70% by mol or more of a p-xylidenediamine unit and the dicarboxylic acid unit which includes 70% by mol or more of a linear aliphatic dicarboxylic acid having to 6 to 18 carbon atoms.
    The p-xylidenediamine unit is contained in a concentration of preferably 80 mol% or more, more preferably 90 mol% or more, most preferably 100 mol%.
    The linear aliphatic dicarboxylic acid unit having from 6 to 18 carbon atoms in the dicarboxylic acid unit is contained in a concentration preferably of
    80% by mol or more, more preferably 90% by mol or more, more preferably 100% by mol.
    Polyamide (A) can be obtained by polycondensing a diamine component comprising 70 mol% or more of p-xylidenediamine and a dicarboxylic acid component comprising 70 mol% or more of a linear aliphatic dicarboxylic acid having 6 up to 18 carbon atoms.
    The diamine component as the raw material for polyamide (A) includes p-xylidenediamine in a concentration of 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more. more specifically preferably 100% by mol.
    When the concentration of p-xylidenediamine in the diamine component is adjusted to 70% mol or more, a polyamide to be obtained exhibits a high melting point and a high crystallinity and can be used for a variety of applications. as a polyamide being excellent in heat resistance, chemical resistance and the like and having a low water absorption capacity.
    If the concentration of p-xylidenediamine in the diamine component used as a raw material is less than 70% by mol, the polyamide to be obtained has a decreased heat resistance and chemical resistance and an increased water absorption capacity. .
    Raw material of diamine component other than p-xylidenediamine can be exemplified by, but not limited to, an aliphatic diamine such as 1,4-butanediamine, diamine such as 1,4-butanediamine, 1,6- hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4, 4-trimethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine, or 5-methyl-1,9-nonanediamine, an alicyclic diamine such as 1,3-bis(aminomethyl) cyclohexane , 1,4-bis(aminomethyl)cyclohexane, cyclohexanediamine, methylcyclohexanediamine, or isophoronediamine, an arithmetic diamine such as am-xylenediamine, or a mixture thereof.
    The dicarboxylic acid component as a raw material of polyamide (A) includes linear aliphatic dicarboxylic acid having 6 to
    V 6/41 z 18 carbon atoms in a concentration of 70 mol% or more, of . preferably 80 mol% or more, more preferably 90 mol% or more, specifically preferably 100 mol%. When the concentration of linear aliphatic dicarboxylic acid having 6 to 18 carbon atoms is adjusted to 70% mol or more, a polyamide to be obtained exhibits melt processing fluidity, high crystallinity, and low water absorption and it can be used suitably for a variety of applications such as an excellent polyamide in heat resistance, chemical resistance, melt processability and dimensional stability if the linear aliphatic dicarboxylic acid concentration has 6 : up to 18 carbon atoms in the dicarboxylic acid component used as a raw material is less than 70% by mol, the polyamide to be obtained has its heat resistance, chemical resistance and processability of molding decreased.
    Examples of the linear aliphatic dicarboxylic acid having 6 to 18 carbon atoms may include adipic acid, pimelic acid, suberic acid, azelaic acid, sebaceous acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pen- tadecanedioic acid, and hexadecanedioic acid. Among these, there is preferably at least one selected from the group consisting of azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid, and most preferably are sebacic acid and/or azelaic acid. In the case where an aliphatic dicarboxylic acid having 5 or less carbon atoms is used, the dicarboxylic acid has a low melting point and a low boiling point, and for that reason it is distilled off from the reaction system during polycondensation reactions to change a molar ratio of reaction between diamine and dicarboxylic acid that results in low mechanical properties and thermal stability of a polyamide to be obtained. However, in the case where a dicarboxylic acid having 19 or more carbon atoms is used the heat resistance cannot be obtained because the melting point of the polyamide is significantly lowered.
    . 7/41 : A crude dicarboxylic acid material other than the linear aliphatic dicarboxylic acid having 6 to 18 carbon atoms can: be exemplified but not limited by malonic acid, succinic acid, acid 2-methyladipic, trimethyladipic acid, 2,2-dimethyl glutaric acid, 2,4-dimethyl glutaric acid, 3,3-dimethyl glutaric acid, 3,3-diethyl glutaric acid, 3,3-diethyl succinic acid, 1 acid, 3-cyclopentane dicarboxylic acid, 1,3-cyclohexane, dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, acid 1 ,4-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, or a mixture thereof.
    A lactam such as e-caprolactam or laurolactam, or an aliphatic aminocarboxylic acid such as aminocaproic acid can also be used as a component of the copolymerization for making - the polyamide (A) as well as the components of the diamine and the dicarboxylic acid components, provided that an effect of the present invention is not impaired.
    A small amount of a monofunctional compound having reactivity with an amino terminal group or a carboxyl terminal group of the polyamide can be added as a molecular weight modifier at the time of polycondensation of the polyamide (A). Examples of compounds that can be used can include, but are not limited to, aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid and pivalic acid, aromatic monocarboxylic acids such as benzoic acid, toluic acid, and naphthalene carboxylic acid, aliphatic monoamines such as butylamine, amylamine, isoamylamine, hexylamine, heptylamine and octylamine, monoamines aromatic — aliphatic, such as benzylamine and methyl benzylamine and mixtures thereof.
    In the case where a molecular weight modifier is used in the polycondensation of polyamide (A), a suitable amount of the molecular weight modifier used varies depending on, for example, the reactivation.
    : 8/41 : ity and boiling point of used molecular weight modifier and das . reaction conditions, and is usually from about 0.1 to 10% by weight | with respect to the total of the diamine component and the ]dicarboxylic acid component used as the base materials.
    A compound containing a phosphorus atom can be added to a polyamide (A) polycondensation system as an antioxidant to prevent polyamide coloration due to a catalyst for the polycondensation reaction and the oxygen present in the polycondensation system - ration.
    Examples of compounds containing a phosphorus atom include alkaline earth metal salts of hypophosphorous acids, alkali metal salts of phosphorous acid, alkaline earth metal salts of phosphorous acid, alkali metal salts of acid phosphoric acid, alkaline earth metal salts of phosphoric acid, alkali metal salts of pyrophosphoric acid, alkaline earth metal salts of pyrophosphoric acid, alkali metal salts of metaphosphoric acid and alkaline earth metal salts of metaphosphoric acid.
    Specific examples thereof may include calcium hypophosphite, magnesium hypophosphite, sodium phosphite, sodium hydrogen phosphite, potassium phosphite, potassium hydrogen phosphite, lithium phosphite, lithium hydrogen phosphite, magnesium phosphite, sodium phosphite magnesium hydrogen, calcium phosphite, calcium hydrogen phosphite, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, magnesium phosphate , dimagnesium hydrogen phosphate, magnesium dihydrogen phosphate, calcium phosphate, dicalcium hydrogen phosphate, calcium dihydrogen phosphate, lithium phosphate, dilithium hydrogen phosphate, lithium dihydrogen phosphate, sodium pyrophosphate, pyrophosphate , potassium, magnesium pyrophosphate, calcium pyrophosphate, lithium pyrophosphate, sodium metaphosphate, potassium metaphosphate, magnesium metaphosphate, calcium metaphosphate, meta- lithium phosphate, and mixtures thereof. Among these are preferably calcium hypophosphite, magnesium hypophosphite, calcium phosphite, calcium hydrogen phosphite and calcium phosphate dihydrogen and most preferably
    . 9/41 : is calcium hypophosphite. It should be noted that each of these compounds which contains a phosphorus atom can be a hydrate.
    The amount of the phosphorus-containing compound added to the polyamide polycondensation system (A) is from 50 to 1000 ppm, preferably from 50 to 400 ppm, more preferably from 60 to 350 ppm, preferably specifies 70 to 300 ppm in terms of a concentration of phosphorus atoms in the polyamide (A). In the case where the phosphorus concentration in the polyamide (A) is less than 50 ppm, the effect of the compound as an antioxidant is not sufficiently exerted, and the composition of the polyamide resin is colorable. However, : in the case where the concentration of the phosphorus atom in the polyamide (A) is -. more than 1,000 ppm, a gelling reaction of the resin - polyamide composition is promoted, and foreign material probably due to the - compound containing the phosphorus atom can get mixed into a molded article, which is prone to deterioration of the appearance of the molded article.
    The concentration of phosphorus atoms in polyamide (A) is preferably derived from at least one type of compound which contains a phosphorus atom selected from the group consisting of an alkaline earth metal salt of hypophosphorous acid, an alkali metal salt of phosphoric acid, an alkaline earth metal salt of phosphoric acid, an alkali metal salt of pyrophosphoric acid, an alkaline earth metal salt of pyrophosphoric acid, an alkali metal salt of metaphosphoric acid, an alkaline earth metal salt of metaphosphoric acid, most preferably derived from a type of compound containing a phosphorus atom selected from the group consisting of calcium hypophosphite, magnesium hypophosphite, calcium phosphite and calcium phosphate dihydrogen.
    Also a polymerization rate modifier is preferably added to the polyamide (A) polycondensation system in combination with the compound containing a phosphorus atom. In order to prevent coloring of the polyamide during polycondensation, there needs to be a sufficient amount of compound containing the phosphorus atom. However, the compound can cause the poly-gelation to gel.
    V 10/41 amide and for that reason, for the purpose of controlling as well a rate. of amidation reaction, the polymerization rate modifier is used from | preferably together with the compound. yY Examples of polymerization rate modifiers include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal acetates and alkaline earth metal acetates.
    Among these, alkali metal hydroxides and alkali metal acetates are preferred.
    Examples of the polymerization rate modifier include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide. strontium, barium hydroxide, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, acetate. magnesium, calcium acetate, strontium acetate, barium acetate and . mixtures thereof.
    Among these are preferably sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium acetate and potassium acetate, and more preferably are sodium hydroxide, sodium acetate. sodium and potassium acetate.
    In the case where the polymerization rate modifier is added to the polycondensation system, from the point of view of a balance between promotion and suppression of the amidation reaction, the molar ratio of a phosphorus atom in the compound containing the phosphorus atom and the polymerization rate modifier (=[mole number of polymerization rate modifier//[mole number of phosphorus atom in compound containing phosphorus atom]) is preferably of 0.3 to 1.0, more preferably 0.4 to 0.95, and particularly preferably 0.5 to 0.9. A polymerization method for polyamide (A) may be an arbitrary method such as: (a) melt-state polycondensation; (b) so-called solid phase polymerization involving the production of a low molecular weight polyamide by polycondensation in a melt state and heat treatment of the resulting polyamide in a solid phase state; or (c) extrusion polymerization involving the production of
    : 11/41 : a low molecular weight polyamide by polycondensing in a melt state and increasing the molecular weight in a melt state : using a kneading extruder. The method for polycondensation in a molten state is not specifically limited, and examples of it may include: a method which involves conducting polycondensation in a molten state while removing water and water from the condensation through heating an aqueous solution of a nylon salt of a diamine component and a dicarboxylic acid component under increased pressure; and a method that involves carrying out polycondensation in an ordinary pressure or in an atmosphere of pressurized water vapor -. by directly adding a diamine component to a dicarboxylic acid in a molten state. In the case where the polymerization is carried out * through the direct addition of a diamine to a dicarboxylic acid in a molten state, the polycondensation is carried out while controlling the reaction temperature in such a way that the temperature does not go lower than the melting points of an oligoamide and a polyamide to be generated by continuously adding the diamine component in a molten dicarboxylic acid phase to maintain the reaction system in a uniform liquid state. In the case where, in the production of a product by the above-mentioned polycondensation method, the inner part of the device is washed, due to, for example, a change in the type of product, triethylene glycol, ethylene glycol, m -xylylenediamine, or the like can be used.
    The polyamide obtained through polycondensation in the molten state is taken first, pelletized and then dried before use. Polyamide can be produced through solid phase polymerization to further increase a degree of polymerization. As a heating device to be used for drying or for solid phase polymerization, a continuous heating drying device, a rotating drum device called a swirl dryer, a conical dryer or a rotary dryer and a heating device shaped like
    : 12/41 s cone equipped with a blade in its internal part called nauta. mixer are used properly. However the device does not | is limited thereto, and a known method and device may be used. Specifically, in the case of carrying out the solid phase polymerization of the polyamide. Among the aforementioned devices, a rotating drum heating device is preferably used, as the system can be sealed to facilitate polycondensation in a state in which the oxygen, which causes the coloring, is removed.
    Polyamide (A) is less colored and less gelatinized. Furthermore, polyamide (A) has a YI value of 10 or less, more preferably 5 or less, even more preferably 1 or less in a color difference test according to JIS K 7105 A molded article obtained from a resin composition containing a polyamide (A) having a . YI value of more than 10 is not preferred because the article has a yellowish color and therefore has a low ability to be commodified.
    Although there are some indices for the degree of polymerization of a polyamide, a relative viscosity is generally used. The relative viscosity of polyamide (A) is preferably from 1.8 to 4.2, more preferably from 1.9 to 3.5, even more preferably from 2.0 to 3.0 from the standpoint of appearance and processing capacity in molding the molded article. It should be noted that the relative viscosity in the form used herein in this patent application is a proportion of a decay time (t) which is measured with respect to a solution obtained by dissolving 1 g of a polyamide in 100 ml of sulfuric acid to 96% at 25°C using a Cannon-Fenske viscometer, up to a decay time (t0), which is measured by 96% sulfuric acid itself in the same way as above, and is represented by the following equation (1 ).
    Relative viscosity = t/tO... (1) The number average molecular weight (Mn) of polyamide (A), which is determined by measurement by gel permeation chromatography (GPC), falls within the preferred range from from 10,000 to 50,000, from
    - 13/41: more preferably from 12,000 to 40,000, even more preferably from 14,000 to 30,000. When Mn is adjusted to the range, the mechanical strength of the molded article obtained from the polyamide is stabilized, and the polyamide has a necessary melt viscosity — for a satisfactory processing condition in terms of capacity. of molding.
    However, the dispersivity (weight average molecular weight/number average molecular weight = Mw/Mn) falls within the preferred range from 1.5 to 5.0, more preferably from 1.5 up to 3.5. When the dispersivity is adjusted to the range, the melt fluidity and the viscosity stability of the molten material are increased, resulting in ".a satisfactory processability in mash molding or melt molding."
    Furthermore, polyamide is satisfactory in . toughness as well as some of the physical properties such as resistance to water absorption, chemical resistance and resistance to aging by heat. <Organic halogen compound (B)> Examples of organic halogen compound (B) that serve as a flame retardant include brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, an epoxy-based polymer of the type brominated bisphenol, a brominated styrene maleic anhydride polymer, a brominated epoxy resin, a brominated phenoxy resin, decabromodiphenyl ether, a brominated crosslinked aromatic polymer, and perchlorocyclopentadecane.
    Among these, a bromine-based compound is preferably brominated polystyrene and brominated polyphenylene ether are preferably specific from the viewpoints of flame retardancy and resistance to thermal degradation.
    The compounds can be used singly or in combination of two or more types thereof.
    A content of halogen atoms in the organic halogen compound (B) is preferably from 15 to 87% by weight, more preferably from 20 to 60% by weight, from the viewpoints of flame retardancy and resistance to thermal degradation.
    - 14/41 : The content of the organic halogen compound (B) is from 1 to . 100 parts by weight, preferably from 10 to 60 parts by weight with respect to 100 parts by weight of polyamide (A). If the content of the organic halogen compound (B) is less than 1 part by weight with respect to 100 parts by weight of the polyamide (A), a flame retardant effect is not obtained, whereas if the content exceeds at 100 parts by weight with respect to 100 parts by weight of polyamide (A), the mechanical properties are significantly reduced.
    <Inorganic Compound (C)> Examples of inorganic compounds (C) that serve as: a flame retardant auxiliary may include antimony trioxide, ..antimony pentoxide, sodium antimonate, tin oxide, iron oxide , zinc oxide, zinc borate, magnesium hydroxide, calcium hydroxide, calcium carbonate and kaolin clay. Among these, antimony trioxide, antimony pentoxide and sodium antimonate are preferred from the standpoints of flame retardancy and resistance to thermal decomposition. The compounds can be treated with, for example, a silane coupler or a titanium coupler, and can be used singly or in combination of two or more types thereof.
    The content of the inorganic compound (C) is from 0.5 to 50 parts by weight, preferably from 1 to 30 parts by weight, based on 100 parts by weight of the polyamide (A). If the content of the inorganic compound (C) is less than 0.5 part by weight with respect to 100 parts by weight of the polyamide (A), the flame retardancy effect is low, whereas if if it exceeds 50 parts by weight with respect to 100 parts by weight of the polyamide (A) the mechanical properties are lowered, or the surface condition of the molded article is deteriorated. <Inorganic filler (D)> The flame-retardant polyamide resin composition of the present invention preferably contains the inorganic filler (D) which serves as a reinforcement, from the viewpoints of mechanical properties and moldability . Examples of inorganic filling
    : co (D) may include fiberglass, glass beads, a carbon fiber, . a boron fiber, talc, mica, silica, silica alumina, alumina, graphite, kaolin, : titanium dioxide and molybdenum disulfide. Among these, a glass fiber and a carbon fiber are preferred from the viewpoints of mechanical strength and moldability. Fillers can be used singly or in combination of two or more types of fillers. The content of the inorganic filler (D) is preferably from 0 to 100 parts by weight, more preferably from 10 to 100 parts by weight, specifically preferably from 50 to 100 parts by weight with respect to 100: parts by weight of the polyamide (A), from the point of view of a balance = between mechanical properties and moldability. - The flame-retardant polyamide resin composition of the present invention may contain, as another component In addition to the above-mentioned components, an antioxidant based on impaired phenol, an antioxidant based on impaired amine, an antioxidant with thio base, a dye, an ultraviolet absorber, a light stabilizer, an anti-static agent, a plasticizer, a lubricant and a nucleating agent, if necessary.
    Furthermore, in the flame retardant polyamide resin composition of the present invention, a heat resistant resin can be combined, as long as the effect of the present invention is not impaired. Examples of heat resistant resins that can be combined include heat resistant thermoplastic resins such as polyphenylene ether (PPE), polyphenylene sulfite, modified polyolefin, polyether sulfone (PES), polyether imide (PEI) and a molten liquid crystal polymer, and modified resin products. In the case where the polyamide resin composition of the present invention is a resin composition for a sliding part, from the viewpoints of slip properties and mechanical properties of a molded article, the composition preferably contains such thermoplastic resin that has a high melting point.
    , 16/41. (Polyphenylene Sulfide). The polyphenylene sulfide which can be combined in the composition of the polyamide resin of the present invention is a polymer having a structural unit represented by the following general formula (1) at a concentration of 70% by mol or more, preferably 90% mol or more in total structure units.
    A d—— i . Examples of polyphenylene sulfides which can be combined. ted in the polyamide resin composition of the present invention include a polymer which has only the unit of structure represented by * 10 of the general formula (1) as well as polymers which have units of structure 7 represented by the following general formulas (II) through (VI), and the polymer can include one type or two or more types of units. s— (11) g— AADAÁD + A DA ã A IA dai Polyphenylene sulfide may further include a trifunctional structural unit, represented by the following general formula (VII) in a
    . 17/41 : concentration of 10% mol or less in total structure units. VS : AS (VII) — The constituent units represented by the general formulas (1) through (VII) may each have a substituent such as an alkyl group, a nitro group, a phenyl group, or an alkoxy group therein. aromatic ring.
    The viscosity of polyphenylene sulfide that can be combined. in the composition of the polyamide resin of the present invention, which is determined. nothing with the use of a flow tester under a load of 20 kg in -. a temperature of 300°C, preferably within the range of preferably: 10 from 100 to 10,000 poise, more preferably from 200 to 5,000 | poise, even more preferably from 300 to 3,000 poise.
    Polyphenylene sulfide can be prepared by an arbitrary method.
    The polyamide resin composition of the present invention from the viewpoint of heat resistance, a weight ratio between polyamide (A) and polyphenylene sulfide is preferably from 5:95 to 99.9:0 , , even more preferably from 10:80 to 80:20. (Modified Polyolefin) As the modified polyolefin, a product obtained by modifying a polyolefin with an unsaturated «,B carboxylic acid or an ester or a metal salt derivative through copolymerization, or through introduction by grafting, for example, a carboxylic acid or an acid anhydride onto a polyolefin.
    Specific examples may include, but are not limited to, ethylene/propylene copolymer, an ethylene/1-butene copolymer, an ethylene/4-methyl-1-pentene copolymer, an ethylene/1-hexene copolymer, a ethylene/1-octene copolymer, an ethylene/1-decene copolymer, a propylene/ethylene copolymer, a propylene/1-butene copolymer, a propylene/4-methyl-1-pentene copolymer, a propylene/1-hexene copolymer, a propylene/1-octene copolymer, a propylene/1-decene copolymer, a copolymer
    : 18/41: of propylene/1-dodecene, an ethylene/propylene/1,4-hexadiene copolymer, . an ethylene/propylene/dicyclopentadiene copolymer, an ethylene/1-butene/1,4hexadiene copolymer, and an ethylene/1-butene/5-ethylidene-2-norbonene copolymer.
    In the polyamide resin composition of the present invention, from the viewpoints of mechanical strength, impact strength, heat resistance and the like to the combined amount of modified polyolefin, preferably 0.5 to 50 parts by weight, more p-reference from 1 to 45 parts by weight, even more preferably from 5 to 40 parts by weight, with respect to 100 parts by weight of the polyamide (A). (Fused Liquid Crystal Polymer) "" It is preferable that the molten liquid crystal polymer has - the property of forming a liquid crystal in a molten phase (ie - which exhibits an optical anisotropy) has an intrinsic viscosity [n ] which is determined in pentafluorophenol at 60°C, from 0.1 to 5 di/g.
    Typical examples of the molten liquid crystal polymer may include, but are not limited to, a polyester that is substantially formed from an aromatic hydroxy carboxylic acid unit, an aromatic dicarboxylic acid unit, and an aromatic diol unit, a polymer that is substantially formed from a moisture of an aromatic hydroxy carboxylic acid, a moisture of an aromatic dicarboxylic acid, and a moiety of an aliphatic diol; a polyester amide which is substantially formed by an aromatic hydroxycarboxylic acid unit, an aromatic aminocarboxylic acid unit, an amide polyester which is substantially formed by an aromatic hydroxycarboxylic acid unit, an aromatic acid unit aromatic dicarboxylic acid, and an aromatic diamine unit; an amide polyester which is substantially formed of an aromatic hydroxycarboxylic acid, an aromatic aminocarboxylic acid unit, an aromatic dicarboxylic acid unit and an aromatic diol unit; and an amide polyester which is substantially formed of an aromatic hydroxycarboxylic acid unit, an amino carboxylic acid unit.
    y 19/41 . aromatic xyllic, a unit of an aromatic dicarboxylic acid in a . unit of an aliphatic diol. : Examples of aromatic hydroxycarboxylic acid unit for constructing the molten liquid crystal polymer may include units derived from p-hydroxybenzoic acid, m-hydroxybenzoic acid; 6-hydroxy-2-naphthoic acid, 7-hydroxy-2-naphthoic acid and the like.
    Examples of aromatic dicarboxylic acid unit include units derived from terephthalic acid, isophthalic acid, chlorobenzoic acid, 4,4'-biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4.41-oxydibenzoic acid, diphenylmethane-4,41-dicarboxylic acid, diphenylsulfone-4,41-dicarboxylic acid and the like.
    - Examples of the aromatic diol acid unit may include . units derived from hydroquinone, resorcinol, methyl hydroquinone, — chlorohydroquinone, phrenyl hydroquinone, 4,41-dihydroxybiphenyl, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-di -hydroxybiphenyl, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl ether, 4,4'-dihydroxybiphenylmethane, 4,4'-dihydroxybiphenyl sulfone, and the like.
    Examples of the aliphatic acid diol unit may include units derived from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1.8 -octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and the like.
    Examples of aminocarboxylic acid units may include units derived from p-aminobenzoic acid, m-aminobenzoic acid, 6-amino-2-naphthoic acid, 7-amino-2-naphthoic acid and the like.
    Examples of aromatic diamine unit may include units derived from p-phenylenediamine, m-phenylenediamine, 4,4"-diaminobiphenyl, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, and the like.
    Preferable examples of the molten liquid crystal polymer may include: a polyester which is formed from a p-hydroxybenzoic acid unit and a 6-hydroxy-2-naphthoic acid unit; a polye-
    - 20/41, having that it is formed by a unit of p-hydroxybenzoic acid a uni-. 4,4'-dihydroxybiphenyl, a terephthalic acid moiety; a polyester which is formed by a p-hydroxybenzoic acid unit, an ethylene glycol unit, and a terephthalic acid unit and a polyester amide which is formed by a p-hydroxybenzoic acid unit, a terephthalic acid unit. 6-hydroxy-2-naphthoic acid and a p-aminobenzoic acid moiety. In the thermoplastic resin composition of the present invention, from the viewpoints of molding processability, dimensional stability and chemical resistance of a molded article and the like, the amount of the combined molten liquid crystal polymer is "i preferably of 0.1 to 200 parts by weight, more preferably from 0.5 - to 150 parts by weight, even more preferably from 1 to 100 parts by weight with respect to 100 parts by weight of the polyamide (A).
    A production method for the polyamide resin composition for a molding material of the present invention is not specifically limited, and the composition can be produced by combining predetermined amounts of the polyamide (A) of the compound. organic halogen (B), inorganic compound (C) and if required, inorganic filler (D), another additive and another resin; kneading the mixture into melt. Melting kneading can be carried out using a conventionally known method. For example, melt kneading can be accomplished by feeding all materials using a single-screw or twin-screw extruder, a Bam-bury mixer, or other similar device from the base of the extruder into a stage; or a method that involves first feeding the resin components; and kneading the melted components together with a side feed of fibrous reinforcements can be carried out to produce pellets. Furthermore the method may be one which involves pelletizing different types of composite products and blending the resulting pellets, or one which involves separately blending part of a powdered component or a liquid component.
    - 21/41, <Molding Article>: The flame retardant polyamide resin composition of the present invention is excellent not only in flame retardancy but also in a variety of physical properties such as moldability, mechanical properties, heat resistance, chemical resistance, and low water absorption, and can be used properly in a wide range of applications and conditions as a molding material for electrical and electronic parts, and other products that require a time delay. flame.
    The flame-retardant polyamide resin composition of the present invention can be used to produce a molded product having a desired shape by a method of known molding such as injection molding, injection molding. flation, extrusion molding, compression molding, molding by . stretching or vacuum.
    Examples Hereinafter, in this patent application, the present invention is described in more detail by way of Examples and Comparative Examples, but it is not limited to the examples.
    It should be noted that measurement against a variety of items in the examples was carried out using the following methods. (1) Relative Viscosity of Polyamide 1 g of a polyamide was carefully weighed and dissolved in 100 ml of 98% sulfuric acid with stirring at 20 to 30°C.
    After the polyamide was completely dissolved, 5 ml of the solution was imme- diately taken in a Canon-Fenske viscometer and left to rest in a thermostat bath at 25ºC for 10 minutes and then a fall time (t) was measured.
    Meanwhile, a fall time of sulfuric acid itself (t0) to 96% was measured in the same way as above.
    A relative viscosity was calculated from the values of t and tO using the following equation (1): Relative viscosity = to ... (1)
    . 22/41 . (2) Y value! of Polyamide. : According to JIS K 7105, a YI value was measured by 'a reflection method.
    A polyamide having a higher YI value is evaluated to be more colored in yellow.
    As a device for measuring the value of Yl, a color difference measuring device manufactured by Nippon Denshoku Industries Co., Ltd. (type: Z-=80 Color Measuring System) was used. (3) Concentration of the Phosphorus Atom.
    A phosphorus atom concentration was measured by a fluorescent X-ray analysis.
    How the measuring device was used the ZSX primis (trademark) manufactured by Rigaku Corporation, À | the analysis was performed under conditions of: vacuum tube Rh 4 kW; atmosphere; - vacuum; analysis window, 5 µm polyester film; measurement mode: . EZ scan; and measuring diameter: 30 mmg.
    The calculation was performed using the SOX calculation using software manufactured by Rigaku Corporation. (4) Molecular Weight A molecular weight was measured by gel permeation chromatography (GPC). As the measuring device a GPC device HLC-8320GPC (trade name manufactured by TOSOH CORPORATION) was used to which two TSK gel Super HM-H columns (trade name) manufactured by TOSOH CORPORATION were connected as the measurement.
    As the solvent, hexafluorisopropanol (HFIP) was used, and 10 mg of a polyamide used as a sample were dissolved in 10 g of HFIPe used in the measurement.
    The measurement was performed under conditions of: column temperature: 40°C; and solvent flow rate: 0.3 ml/minute and methyl methacrylate was used as a standard sample for the determination of a number average molecular weight (Mn) and an average molecular weight (Mw) . (5)Flammability.
    A burn test was performed in accordance with a UL94V standard shown below.
    A test piece with a size of
    - 23/41 and 125X13X6 mm was fixed vertically using a staple and dry absorbent BR cotton was placed on the lower side of the test piece. " A predetermined flame was brought into contact with the lower end of the test piece, held for 10 seconds in that state and then withdrawn from the test piece and a burning time (first contact with the flame) was measured.
    After the fire had gone out, a flame was brought into contact with the lower end of the test piece again for 10 seconds and a burning time (second contact with flame) was measured.
    For five test pieces, measurement was performed to evaluate the test piece to be V-O, V-1 or V-2, selected from the | classification that follows. " Table 1: Judgment criteria test lo less — jou minus or minus 250 sec-1250 sec. test lo less nos Second contact with flame or less — joumenos Joumenos ee LITE eee out ee = | Outgoing per droplet emitting flame. yes (6) Mechanical Properties of Molded Article.
    The mechanical properties of a molded article were measured under the following conditions.
    . 24/41 . Table 2 7 À Part dimension . Item under test Test method under test : ISO3167 part type) Tensile strength According to ISO527 dumbbell. . The same as a-| Elastic traction module | The same as above. above; Resistance to bending | According to ISO178 | 80x10x4 mm -. Elastic module of do-| Same as above 80x10x4 mm - braze Impact resistance According to ISO179 | 80x10x4 mm sharp Folding module e-| According to IS0178, high temperatu-| 80x10x4 mm measured at 140°C ra Deflection temperature) According to ISO75 |80x10x4 mm is under load (7) Water Absorption Balance The absolute dry mass of a disk-shaped test piece (diameter 50 mm x thickness 3 mm) was weighed and then the test piece was immersed in boiling water at atmospheric pressure.
    Weight changes were measured with time and water absorption when no change in mass was observed was determined as an equilibrium in water absorption.
    Synthesis Example 1. 8.950 g (44.25 moles) of sebacic acid manufactured by ITOH OIL CHEMICALS CO., LTD (trade name: Sebacic Ácido TA), 12.54 9g (0.073)
    25/41 mol) of calcium hypophosphite (manufactured by KANTO CHEMICAL CO,, INC.), and to 6.45 g (0.073 mol) of sodium acetate (KANTO CHEMICAL CO,, INC.) were carefully prepared. weighed and fed to a reaction vessel which had an internal volume of 50 liters and equipped with an agitator, a deflagrator, a chiller, a thermometer, a pouring device, a nitrogen inlet tube, and a filament mold ( a mole ratio of a phosphorus atom in calcium hypophosphite and sodium acetate was 0.5). The air in the reaction vessel was sufficiently replaced with nitrogen and the vessel was pressurized with nitrogen to 0.3 MPa and heated with stirring to 160°C to uniformly melt the sebacic acid. Then 06.026 g (44.25 moles) of p-xylylenediamine (i. manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.) was added dropwise with stirring over 170 minutes. During this proce- . Afterwards, the internal temperature of the reaction vessel was continuously raised to 281°C. In the drip step, the pressure was controlled to 0.5 MPa, and the water generated was removed from the system through the deflagrator and the cooler. The deflagrator temperature was controlled in such a way to fall within the range from 145 to 147°C. After the p-xylylenediamine drop was completed, the pressure was reduced at a rate of 0.4MPa/h to common pressure for 60 minutes. During this procedure, the internal temperature was raised to 300ºC. Thereafter, the pressure was reduced at a rate of 0.002 MPa/min to 0.08 MPa for 20 minutes. Then the reaction was continued at 0.08 MPa until the torque of the stirring device reached a predetermined value. After that the system was pressurized with nitrogen and a polymer was taken from the filament mold and pelletized, to thereby obtain 13 kg of a polyamide (PAI). Table 3 shows the physical property values of the resulting polyamide (PAI). Polyamide (PAI) was found to have a phosphorus atom concentration of 315 ppm, a YI value of -6.5, a relative viscosity of 2.47, a number average molecular weight (Mn) of
    21,000 and a Mn/Mw of 2.6.
    . 26/41 Pr Synthesis Example 2.
    . Melt polycondensation was performed in the same manner as in Synthetic Example 1, except that the type and amount of dicarboxylic acid blending was changed to 8.329 g (44.25 moles) of azelaic acid (manufactured by Cognis, with the trade name of EMEROX 1144), to thereby obtain a polyamide (PA2).
    Table 3 shows the physical property values of the resulting polyamide (PAI). Polyamide (PA2) was found to have a phosphorus atom concentration of 302 ppm, a YI value of -1.0, a relative viscosity of 2.22, a number average molecular weight Mn of : 17,500 and a Mw/Mn of 2.5.
    i Synthesis Example 3.
    - Melt polycondensation was carried out in the same way. as in Synthesis Example 1, except that the diamine component was changed to 5.453 g (39.82 mol) of p-xylylenediamine (manufactured by MIT-SUBISHI GAS CHEMICAL COMPANY, INC.) and 603 g (4.43 mol.) ) of m-xylylenediamine (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.) (p-xylylenediamine and m-xylylenediamine accounted for 90% mol and 10% mol of the diamine component, respectively) to — however A polyamide (PA3) is obtained.
    Table 3 shows the physical property values of the resulting polyamide (PAI). Polyamide (PA3) was found to have a phosphorus atom concentration of 300 ppm, a YI value of -2.0, a relative viscosity of 2.11, a number average molecular weight Mn of
    17,200eumaMw/Mn of 2.7. Synthesis Example 4.
    Melt polycondensation was performed in the same manner as in Synthetic Example 1, except that the combined amount of calcium hypophosphite was changed to 1.19 g (0.007 mol), and the combined amount of sodium acetate was changed to 0 .57 g (0.007 mol) a molar ratio between a phosphorus atom and calcium hypophosphite and sodium acetate was 0.5, to thereby obtain a polyamide (PA4).
    . 27/41 . Table 3 shows the physical property values of the resulting polyamide E: amide (PA4). Polyamide (PA4) was found to have a phosphorus atom concentration of 28 ppm, a YI value of 25.0, a relative viscosity of 2.23. a number average molecular weight Mn of
    18,000eumaMw/Mn of 2.6. Synthesis Example 5.
    Melt polycondensation was performed in the same manner as in Synthesis Example 1, except that the combined amount of calcium hypophosphite was changed to 49.25 g (0.292 mol), and the combined amount of sodium acetate was changed to 23 .95 g (0.292 mol) (a molar ratio between a phosphorus atom and calcium hypophosphite and sodium acetate was 0.5). In this case, the molecular weight increased rapidly during the melt polymerization and the control of the molecular weight was difficult.
    . Table 3 shows the physical property values of the resulting polyamide (PAS). Polyamide (PAS) was found to have a phosphorus atom concentration of 1,210 ppm, a YI value of 0.5, a relative viscosity of 2.42, a number average molecular weight Mn of
    40,000 and a Mw/Mn of 2.7.
    . 28/41 sc , z o o Di Fa Dx z o o a a eo
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    : Example 1 . 30 parts by weight of brominated polystyrene (manufactured by Nissan-Ferro Organic Chemical Company, Ltd., trade name: PyroChek 68PB, halogen atom content 66% by weight) and 10 parts by weight of antimony trioxide (manufactured by Nihon Seiko Co., LTD., trade name: Padox C) were dry blended with 100 parts by weight of the polyamide (PA1) which had been dried under reduced pressure at 150°C for 7 hours.
    The mixture was fed into a base hopper of a twin screw extruder (manufactured by TOSHIBA MACHINE CO,, LTD., trade name: TEM37BS) at a rate of 8 kg/h, and extruded at a barrel temperature of 280 to 300°C and at a screw rotation speed of Í: 150 rpm, and with the side-feed of 100 parts by weight of a fiberglass (manufactured by Nippon Electrico Glass Co., Ltd., trade name: 03T- 296GH) with respect to 100 parts by weight of the polyamide (PA1) was carried out, to thereby prepare the resin pellets of the composition.
    The pellets resulting from the resin composition were submitted to injection molding, using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name: SE130DU-HP) at a cylinder temperature of 300ºC and a mold temperature of 120°C, to thereby obtain a test piece for evaluation.
    With respect to the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Example 2 A test piece for evaluation was obtained in the same manner as in Example 1, except that polyamide (PA1) was changed to polyamide (PA2). With respect to the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Example 3 A test piece for evaluation was obtained in the same manner as in Example 1, except that polyamide (PA1) was changed to polyamide (PA3). With respect to the resulting test piece, the
    . 30/41' physical properties of the molded article.
    Table 4 shows the results of the assessment.
    Example 4 A test piece for evaluation was obtained in the same manner as in Example 1, except that 30 parts by weight of brominated polystyrene was exchanged for 80 parts by weight of brominated polyphenylene ether (manufactured by ALBERMALE JAPAN CORPORATION, trade name of SAYTEX102E, halogen atom content 83% by weight). - — With respect to the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Example 5 l A test piece for evaluation was obtained in the same way. as in Example 1, except that the amount of polyphenylene ether . Combined brominated was changed from 80 parts by weight to 4 parts by weight.
    For the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Example 6 A test piece for evaluation was obtained in the same manner as in Example 1, except that 10 parts by weight of antimony trioxide was exchanged for 1 part by weight of antimony pentoxide (manufactured by NISSAN CHEMICAL INDUSTRIES, LTD., trade name: NA-1030). For the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Example 7 A test piece for evaluation was obtained in the same manner as in Example 1, except that 1 part by weight of antimony trioxide was exchanged for parts by weight of sodium antimonate.
    For the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Example 8 A test piece for evaluation was obtained in the same way as in Example 1, except that the amount of fiberglass combined.
    - 31/41. nothing was changed from 100 parts by weight to 50 parts by weight.
    For the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Example 9 A test piece for evaluation was obtained in the same manner as in Example 8, except that the fiberglass was changed to a chopped carbon fiber based on PAN.
    For the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Example 10 A test piece for evaluation was obtained in the same manner B as in Example 1, except that the fiberglass was not combined. - For the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Example 11 A test piece for evaluation was obtained in the same manner as in Example 1, except that the amount of combined brominated polyphenylene was changed from 30 parts by weight to 10 parts by weight and the amount of trioxide. Combined antimony was changed from 10 parts by weight to 4 parts by weight.
    For the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Comparative Example 1 30 parts by weight of brominated polystyrene (manufactured by Nissan-Ferro Organic Chemical Company, Ltd., trade name: PyroChek 68PB,) and 10 parts by weight of antimony trioxide (manufactured by Nihon Seiko Co., LTD. ., trade name: Padox C) were dry blended into 100 parts by weight of polyamide 6 T (polyhexamethylene terephthalamide manufactured by Solvay, trade name: Amodel). The mixture was fed into a base hopper of a twin screw extruder (manufactured by TOSHIBA MACHINE CO,, LTD., trade name: TEM37BS) at a rate of 8 kg/h, and extruded at a barrel temperature of 300 to 340°C and at a speed
    . 32/41 b screw rotation speed of 150 rpm, and with the side feed of 100 parts by weight of a fiberglass (manufactured by Nippon Electrico Glass Co., Ltd., trade name: 03T-296GH) with respect to 100 parts of resin was executed, to thereby prepare the resin composition pellets. The resulting pellets from the resin composition were subjected to injection molding, using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name: SE130DU-HP) at a cylinder temperature of 300ºC and a mold temperature of 120°C, to thereby obtain a test piece for evaluation. For the resulting test piece, the physical properties of the molded article were measured. Table 4 shows the results of the assessment.
    | Comparative Example 2.
    - 30 parts by weight of brominated polystyrene (manufactured by Nis-l - san-Ferro Organic Chemical Company, Ltd., trade name: PyroChek 68PB,) and 10 parts by weight of antimony trioxide (manufactured by Nihon Seiko Co., LTD. ., trade name: Padox C) were dry blended in 100 parts by weight of a polyamide 46 (polytetramethylene adipamide, manufactured by DSM, trade name: Stanyl). The mixture was fed into a base hopper of a twin screw extruder (manufactured by TOSHIBA MACHINE CO,, LTD., trade name: TEM37BS) at a rate of 8 kg/h, and extruded at a barrel temperature of 290 to 310°C and at a screw rotation speed of 150 rpm, and with the side feed of 100 parts by weight of a fiberglass (manufactured by Nippon Electrico Glass Co., Ltd., trade name: 03T-296GH) with relation to 100 parts of resin was carried out, to thereby prepare the resin composition pellets. The resulting pellets from the resin composition were subjected to injection molding, using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name: SE130DU-HP) at a cylinder temperature of 310ºC and a mold temperature of 120°C, to thereby obtain a test piece for evaluation. For the resulting test piece, the physical properties of the molded article were measured. Table 4 shows the results of the assessment.
    ' 33/41 y Comparative Example 3 A test piece for evaluation was obtained in the same manner as that of Example 1, except that the polyamide (PA1) was changed to polyamide (PA4). With respect to the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Comparative Example 4 A test piece for evaluation was obtained in the same manner as in Example 1, except that polyamide (PA1) was changed to polyamide (PAS). For the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the evaluation. dog. - Comparative Example 5 . A test piece for evaluation was obtained in the same manner as in Example 1, except that the brominated polystyrene was not combined.
    For the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Comparative Example 6 A test piece for evaluation was obtained in the same manner as in Example 1, except that the brominated polystyrene and antimony trioxide were not combined.
    For the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Comparative Example 7 A test piece for evaluation was obtained in the same manner as in Example 1, except that the amount of the brominated polyphenylene was changed from 30 parts by weight to 150 parts by weight.
    For the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Comparative Example 8. A test piece for evaluation was obtained in the same manner as in Example 1, except that the antimony trioxide was not combined.
    '34/41 swim.
    For the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Comparative Example 9 A test piece for evaluation was obtained in the same manner as in Example 1, except that the amount of antimony trioxide was changed from 10 parts by weight to 70 parts by weight.
    For the resulting test piece, the physical properties of the molded article were measured.
    Table 4 shows the results of the assessment.
    Comparative Example 10 An attempt to prepare pellets of a resin composition was made in the same manner as in Example 1, except that . the amount of combined fiberglass was changed from 100 parts by weight to 250 parts by weight.
    However, it was not possible to prepare the resin composition pellets because dull filaments were formed.
    '35/41
    Polyamide (A) are the pores ii ne” [100 | 100 | 100 | 100 [100 | Organic halogen compound Brominated polystyrene st Es co (B) (parts by weight) Brominated polyphenylene ether E E 1 fed. |
    Antimony trioxide [16 for ro bio ro |
    . Inorganic compound (C) Antimony pentoxide 7 (parts by weight)
    Inorganic filler (D) Fiberglass [100 109 [100 [100 100 | Facts and Fo NES carbon fiber Flame retardancy Physical properties of molded article Tensile strength (MPa) Elastic tensile modulus (GPa) [176 [ara 176 | 152 140 | Bending strength (MPa) [204 [336 [31 [a21 |x2 | Elastic bending modulus (GPa) Acute impact resistance (Im Elastic bending modulus at high temperature (GPa) [04 91 las [oz Jos | Deflection temperature under load (*C) Balance in water absorption (% by weight ) [16 146 114 [15 das |
    Table 4 (continued
    ENESFSFPSEPSPA Pean (weight pairs) FSFPSEAPSPADA halogen co Polyphenylene ether (B) brominated parts by weight; Compound — inorganic — Antimonic pentoxide (C) 1 Inium a (parts by weight) Sodium antimonate 40 magnesium (D) Carbon fiber parts by weight. Physical properties of the molded article Feed strength (MPa) [226 105 [146 faso 170 [ao | Elastic bending module at high temperature ANNSSS 94 perature (GPa; Detent temperature under load (O) Balance in water absorption (% by weight 14 1.8 2.8 sec)
    - 37/41 Table 4 (continued: Í E penpooment — Comparison of da | ls | parts by weight, a and dA parts by weight) brominated with (C) (parts in | Antmount pentoxide 1-1 | 1 | : weight) |sodium antimonate 1 1 1 | | | - Jenehimento inorga- | Injury due — [100 [100 Iron [400 tax | Eme CIT. Weight, carbon fiber | Moguro siastco feed (GPa) — >> 1165 [sign dae |as | | Bending strength ia) — — > |ro 201 [352 [wing [360 | | Elastic folding module(GPay — — [144 [12 |ass (454 1asa | Eme ee 7.2 81 9.3 9.2 raturation (GPa; | Equiforium in water absorption (Mempese)) [aa [36 l15 Jas los | PA6T: Polyhexanomethylene terephthalamide PAA46: Polytetramethylene adipamide
    ' 38/41 Table 4 (continued: ' Comparative Example le | de le lo | Polyamide (A) (parts by weight) 100 100 100 100 100 Halogen compound | Brominated polystyrene | B) (part | Polyphenylene ether by weight) UV brominated Inorganic compound | Anti-ENSSSEN 7 pentoxide (C) (parts by weight) monium Anmensto de sado |- 1 | | | | Inorganic filler | Fiberglass FESPSPSPNPAA (0) (weight pairs) Jrmadecameno 1 1 | Physical properties of the molded article Tensile strength (MPa) Not possible Elastic modulus to tension (GPa) possible Resistance to bending (MPa) to preparation Elastic modulus of bending (GPa) 16.2 | 11.9 [152 | 125 LRessenca a mpace agueo amo — [rs Jaz [ssa ra | h Ns 2 Acute impact resistance (KkJ/m") 19 6.2 15.1 |71 pellets Elastic modulus of high tempera-
    32 97 38 due to ture (GPa filament- Deflection temperature under load (°C) in-
    Balance in absorption and water (% by weight) lo2 aa 16 115 | Blurred It should be noted that in Examples 8 to 10 the elastic moduli of high temperature resistance were not measured.
    - 39/41 As becomes clear from Table 4, each of the molded articles of Comparative Examples 1 and 2 using polyamide 6T or polyamide 46 were found to have low mechanical strength and a low elastic modulus and had a balance in the high water absorption. A nylon 46 resin, which has been conventionally studied as a resin for an electronic part, is a resin obtained from tetramethylenediamine and adipic acid, and is excellent in heat resistance and mechanical properties. However the resin contains an amide group in a higher proportion when compared to usual polyamide resins such as nylon 6 resin and a nylon 66 resin, and for that reason it has the disadvantage of a high water absorption . For that | For this reason, although nylon 46 resin has excellent resistance to ca- . i lor and excellent mechanical properties in a dry state, in real use, the - resin has a higher water absorption when compared to usual polyamide resins and therefore shows a greater reduction in heat resistance and mechanical properties when compared to the usual resins, Furthermore, the high water absorption consequently leads to a large change in dimension, and therefore the dimensional accuracy is insufficient in some cases. For that reason, it is difficult to use the resin in parts that are required to have a high precision. Furthermore, due to the state of water absorption, when mounting on a substrate in a surface mounting system, so-called bubble damage appears on the surface of a part, which results in a significantly lowered performance. and on the reliability of the part.
    Polyamide (PA4) which has a phosphorus atom concentration of 50 ppm or less has a large YI value, and therefore the molded article obtained from the polyamide has a yellowish color and has a low commercial value (Example comparative 3).
    However, in the case of polyamide (PA5) which has a phosphorus atom concentration of 1,000 ppm or more, the molecular weight significantly increased during melt polymerization, and weight control was impossible. molecular (Comparative Example 4).
    Furthermore, each of the molded articles of Comparative Examples 5 and 6, in which no organic halogen compound (B) serving as a flame retardant was mixed, was found to have low flame retardancy. In addition, the molded article of Comparative Example 27, which has an excessive amount of organic halogen compound (B) serving as a flame retardant, was added, and the molded article of Comparative Example 9, for which an excessive amount of Inorganic compounds (C) which serve as a flame-retardant aid were added, were considered to be poor in mechanical properties.
    The molded article of Comparative Example 8, to which no organic compound (C) which serves as a flame retardant auxiliary was added, was found to be poor in flame retardancy when compared to the molded article from Example 1.
    Also, in the case of the resin composition to which an excessive amount of inorganic filler (D) was added, blurred filaments were produced in the pelletizing, and for this reason it was not possible to produce pellets (Comparative Example 10 ).
    However, in the case of each of the polyamides (PA1) through (PA3) used in Examples 1 to 11, the molecular weight was able to be controlled in the melt polymerization. Furthermore, the resulting resin was almost uncolored, and the molded article formed was found to have an excellent appearance. Furthermore, each of the molded articles of Examples 1 to 11 obtained using the polyamide resins were found to have low water absorption and to be excellent in flame retardancy, mechanical properties and heat resistance. .
    Industrial Applicability The flame retardant polyamide resin composition of the present invention excels not only in flame retardancy but also in a variety of physical properties such as moldability, mechanical properties, heat resistance and low ca.
    - 41/41 water absorption capacity and can be used suitably in ' a wide range of applications and conditions as a molding material for a variety of industries and in industrial and household products such as electrical parts and electronics, automotive parts, and mechanical parts—required to have flame retardancy.
    权利要求:
    Claims (15)
    [1]
    - 113
    A flame retardant polyamide resin composition comprising: a polyamide (A) which contains a diamine unit including 70% by mol or more of a p-xylidenediamine unit and a dicarboxylic acid unit which includes 70% in mol or more of a unit of linear aliphatic dicarboxylic acid having 6 to 18 carbon atoms, an organic halogen compound (B) which serves as a flame retardant; an inorganic compound (C) that serves as a flame-retardant aid; and an inorganic filler (D) wherein the polyamide (A) comprises a polyamide having a concentration of phosphorus atoms of 50 to 1000 ppm and a Y| of 10 or less in a color difference test in accordance with JIS K-7105, and a compound content of : organic halogen (B), an inorganic compound content (C) and a content of the inorganic filler (D) are from 1 to 100 parts by weight, 0.5 to 50 parts by weight, and 0 to 100 parts by weight, respectively, with respect to 100 parts by weight of the polyamide (A).
    [2]
    A flame retardant polyamide resin composition according to claim 1, wherein the linear aliphatic dicarboxylic acid unit comprises at least one selected from the group consisting of an azelaic acid unit, an acid unit sebacic, one unit of undecanedioic acid, and one unit of dodecanedioic acid.
    [3]
    The flame retardant polyamide resin composition of claim 1, wherein the linear aliphatic dicarboxylic acid unit comprises the sebacic acid unit and/or the azelaic acid unit.
    [4]
    A flame retardant polyamide resin composition as claimed in any one of claims 1 to 3, in which the polyamide (A) comprises a polyamide which contains a diamine unit including 90% mol or more of the powder unit. -xylylenediamine and a dicarboxylic acid unit including 90% by mol or more of the sebacic acid unit and/or azelaic acid unit.
    « 213 «
    [5]
    A flame retardant polyamide resin composition as claimed in any one of claims 1 to 4, in which the polyamide (A) has a relative viscosity within a range from 1.8 to 4.2.
    [6]
    A flame retardant polyamide resin composition according to any one of claims 1 to 5, in which the polyamide (A) has a number average molecular weight (Mn) within a range from 10,000 to 50,000 in chromatography of gel permeation and a dispersivity (weight average molecular weight/number average molecular weight = Mw/Mn) within a range from 1.5 to 5.0.
    [7]
    A flame retardant polyamide resin composition according to any one of claims 1 to 6, in which the organic halogen compound (B) comprises at least one selected from "Ô from the group consisting of brominated polystyrene, ether of brominated polyphenylene, brominated polycarbonate, a brominated bisphenol type epoxy-based polymer, a brominated styrene maleic anhydride polymer, a brominated epoxy resin, a brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl , a brominated cross-linked aromatic polymer, and a perchlorocyclopentadecane.
    [8]
    A flame retardant polyamide resin composition as claimed in any one of claims 1 to 7, in which the organic halogen compound (B) comprises brominated polystyrene and/or brominated polyphenylene ether.
    [9]
    A flame retardant polyamide resin composition according to any one of claims 1 to 8, in which the organic halogen compound (B) has a halogen atom content of 15 to 87% by weight.
    [10]
    A flame retardant polyamide resin composition according to any one of claims 1 to 9, in which the inorganic compound (C) comprises at least one selected from the group consisting of antimony trioxide, antimony pentoxide, antimonate of sodium, tin oxide, iron oxide, zinc oxide, zinc borate, magnesium hydroxide, calcium hydroxide, calcium carbonate and kaolin clay.
    » 3/3
    [11]
    A flame retardant polyamide resin composition according to any one of claims 1 to 10, in which the inorganic compound (C) comprises at least one selected from the group consisting of antimony trioxide, pentoxide of antimony and anti-sodium monate.
    [12]
    A flame-retardant polyamide resin composition according to any one of claims 1 to 11, in which the inorganic filler (D) comprises at least one selected from the group consisting of a fiberglass, fiberglass beads. glass, a carbon fiber, a boron fiber, talc, mica, silica, silica alumina, alumina, graphite, kaolin, titanium dioxide and molybdenum disulphide.
    [13]
    * A flame-retardant polyamide resin composition E: according to any one of claims 1 to 12, in which the inorganic filler (D) comprises glass fiber and/or carbon fiber.
    [14]
    A molded article, comprising the polyamide resin composition as defined in any one of claims 1 to 13.
    [15]
    A molded article according to claim 14, which is an electrical part or an electronic part.
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    同族专利:
    公开号 | 公开日
    JP5857742B2|2016-02-10|
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    CN102575100A|2012-07-11|
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    JPWO2011030911A1|2013-02-07|
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    法律状态:
    2021-08-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2021-08-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-11-30| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|
    优先权:
    申请号 | 申请日 | 专利标题
    JP2009-211834|2009-09-14|
    JP2009211834|2009-09-14|
    PCT/JP2010/065879|WO2011030911A1|2009-09-14|2010-09-14|Flame-retardant polyamide resin composition|
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