JPH055056A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having excellent heat- resistance, mechanical properties, etc., small linear expansion coefficient and warpage and excellent dimensional stability by compounding a polyphenylene ether, a polyamide, etc. CONSTITUTION:The objective composition can be produced by compounding (A) 50-90wt.% (preferably 30-55wt.%) of a polyphenylene ether resin, (B) 0.5-20wt.% (preferably 2-10wt.%) of an amorphous or low-crystalline polyamide having a glass transition temperature of-250 deg.C and (C) 5-90wt.% (preferably 25-60wt.%) of a crystalline polyamide resin at a B/C weight ratio of <=0.2 (preferably <=0.15) and compounding 100 pts.wt. of the obtained mixture with (D) 0-40 pts.wt. (preferably 5-20 pts.wt.) of a rubbery material (e.g. ethylene-propylene rubber), (E) 2-100 pts.wt. (preferably 5-80 pts.wt.) of an inorganic filler and/or glass fiber and (F) 0.01-15 pts.wt. (preferably 0.1-5 pts.wt.) of a compatibilizing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel thermoplastic resin composition which can be used as a molded product, a sheet or the like by injection molding or extrusion molding. More specifically, polyphenylene ether, polyamide and inorganic filler and / or glass having excellent heat resistance, mechanical properties, molding processability, solvent resistance, etc., having a small linear expansion coefficient and warpage, and excellent dimensional stability. The present invention relates to a novel thermoplastic resin composition composed of fibers.

[0002]

2. Description of the Related Art Polyphenylene ether resin is a thermoplastic resin excellent in various properties such as mechanical properties, heat resistance, cold resistance and dimensional stability. However, impact resistance and solvent resistance are remarkably poor when the polyphenylene ether resin is used alone, and molding processability is poor due to its high melt viscosity. Polyamide resin, on the other hand, is a thermoplastic resin that has excellent mechanical strength, solvent resistance, and processability, but it has poor impact resistance and heat resistance, and its water absorption is large, resulting in significantly poor dimensional stability. .. In order to make use of the characteristics of these resins to make up for the drawbacks, it has been proposed to blend both. However, depending on the application field of the molded product, the dimensional stability, rigidity, and heat resistance may not be sufficient with only a blend of the two, improving the dimensional stability, heat resistance, rigidity, etc. of the polyphenyl ether / polyamide composition. Attempts have been made to add fillers in order to achieve this.

[0003]

Problems to be Solved by the Invention JP-A-63-1014
No. 52 discloses a composition to which wollastonite containing calcium silicate as a main component and / or glass fiber is added, and Japanese Patent Laid-Open No. 61-204263 discloses an aromatic polyphenylene ether resin, styrene. Compounds,
A composition comprising a composition composed of an α, β-unsaturated carboxylic acid anhydride and a high melting point polyamide and a fibrous, flake or powdery reinforcing agent is disclosed, but all of them have dimensional stability. However, if the amount of the reinforcing agent is increased in order to improve heat resistance, rigidity, etc., there is a drawback that the appearance is deteriorated.

JP-A-2-163158 discloses that a polyphenylene ether / polyamide composition is filled with a specific amount of a specific inorganic filler and / or glass fiber while maintaining the impact resistance, moldability and appearance of the composition. Although it is described that the dimensional stability, heat resistance, and bending rigidity of a product are improved, the type, shape, and filling amount of the filler and / or glass are limited, and the appearance, dimensional stability, and heat resistance are limited. The flexibility and rigidity were still insufficient.

The present invention provides dimensional stability, rigidity, heat resistance,
A filler-containing polyphenylene ether / polyamide composition obtained by filling a polyphenylene ether / polyamide composition with an inorganic filler and / or glass fiber (hereinafter referred to as a filler composition), which is a composition having excellent impact resistance and moldability.
It was made to obtain.

[0006]

[Means for Solving the Problems] That is, according to the present invention, in order to develop a technique effective for improving a filler composition comprising a polyphenylene ether, a polyamide, a rubber-like substance, a compatibilizing agent and a filler, a wide and precise method is developed. As a result of searching and research, blending an inorganic filler of a polyphenylene ether / crystalline polyamide composition and / or a glass fiber filler with a non-crystalline or low-crystalline polyamide resin in a fixed ratio with respect to the crystalline polyamide resin. Thus, the dimensional stability, heat resistance, and bending rigidity of the filler-containing polyphenylene ether / polyamide composition are improved while maintaining the impact resistance, moldability, and appearance.

That is, the gist of the present invention is: (a) polyphenylene ether resin; 5 to 90% by weight; (b) amorphous or low crystalline polyamide resin having a glass transition temperature of 90 to 250 ° C .; 0.5 ˜20 parts by weight, (c) crystalline polyamide resin; 90 to 5% by weight, and the weight ratio of (b) to (c) is (b) / (c) ≦
2 to 10 parts by weight of (d) a rubber-like substance; 0 to 40 parts by weight, based on 100 parts by weight of a resin mixture of 0.2;
0% by weight (f) one or more compatibilizers that improve the compatibility of the polyphenylene ether resin and the polyamide resin;
It exists in the thermoplastic resin composition characterized by mix | blending 01-15 weight part.

The present invention will be described in detail below. The polyphenylene ether used in the present invention has the general formula

[0009]

[Chemical 1]

In the formula, one unit of the ether oxygen atom is connected to the benzene nucleus of the next adjacent unit, n is at least 30, and Q is independently. Hydrogen, halogen, a hydrocarbon group containing no tertiary α-carbon atom, a halohydrocarbon group having at least two carbon atoms between a halogen atom and a phenyl nucleus, a hydrocarbon oxy group, a halogen atom and a phenyl nucleus And a monovalent substituent selected from the group consisting of halohydrocarbonoxy groups having at least 2 carbon atoms between
May be the same as or different from each other.

Further, 2,6-dimethylphenol and 2,
3,6-trimethylphenol copolymer, 2,6-dimethylphenol and 2,3,5,6-tetramethylphenol copolymer, 2,6-diethylphenol and 2,
A copolymer such as a copolymer of 3,6-trimethylphenol may be mentioned. Further, the polyphenylene ether used in the present invention is a modified polyphenylene ether obtained by grafting a styrenic monomer (for example, styrene, p-methylstyrene, α-methylstyrene, etc.) onto the polyphenylene ether defined by the above general formula. Also includes ether.

A method for producing a polyphenylene ether corresponding to the above is known, for example, US Pat. No. 3,30687.
4, No. 3306875, No. 3257357 and No. 3257358, and Japanese Patent Publication No. 52
-17880 and JP-A-50-51197. A preferred group of polyphenylene ethers for the purposes of the present invention is 2 per ether oxygen atom.
Having an alkyl substituent at one ortho position and 2,
It is a copolymer of 2,3,6-trialkylphenol of 6-dialkylphenol.

The polyphenylene ether resin of the present invention has a temperature of 25 g in a chloroform solution having a concentration of 0.6 g / dl.
It is preferable that the specific viscosity ηsp at 0 ° C is 0.05 to 1. The non-crystalline or low-crystalline polyamide resin (b) used in the present invention means an amide bond (--CO
-NH-) bond, and is non-crystalline or low-crystalline and has a glass transition temperature of 90 ° C or higher and 250 ° C or lower, more preferably 90 ° C or higher and 210 ° C or lower, and further preferably 100 ° C. It is in the range of 180 ° C or lower. The non-crystalline and low crystallinity generally means that there is no clear melting point or measurable heat of fusion, but in the present invention, it includes those which show some crystallinity when slowly cooled, Further, it also includes those exhibiting crystallinity within a range that does not significantly impair the effects of the present invention.

The glass transition temperature, melting point and heat of fusion can be measured using a differential scanning calorimeter commonly used for crystalline polyamides. PE as an example
There is DSC-II manufactured by RKIN-ELMER. Using this device, the heat of fusion can be measured at a rate of temperature rise of 10 ° C. per minute, for example. The sample is heated to a temperature above the expected melting point, then the sample is cooled at a rate of 10 ° C per minute, cooled to 30 ° C, allowed to stand for about 1 minute and then heated at a rate of 10 ° C per minute. It can be measured by As the heat of fusion, the one that has a constant value within the experimental error range even if it is measured in any of the heating and cooling cycles after the beginning is adopted.

The non-crystalline or low-crystalline polyamide in the present invention has a heat of fusion measured by the above-mentioned method,
It can also be defined as not exceeding 1 cal / g. According to this method, the heat of fusion of commercial nylon-6 is about 16
cal / g. In the polyamide resin (b) of the present invention, preferably, the amide bond constitutional unit is mainly composed of the following (I) to
It is composed of a compound selected from the structural formula (VI), and is constituted so as to satisfy the above glass transition temperature and the non-crystalline or low crystalline property. (I) -HN-W-NH- (W is at least one selected from a linear or branched aliphatic group having 2 to 12 carbon atoms) (II) -HN-X-NH- (X is a metaxylylene group. Or at least one selected from aliphatic groups having 5 to 22 carbon atoms and containing at least one alicyclic hydrocarbon skeleton) (III)

[0016]

[Chemical 2]

(R independently represents hydrogen or carbon number 1
Is at least one selected from aliphatic groups in the range of to 6 and each R may be the same or different) (IV)

[0018]

[Chemical 3]

(R independently represents hydrogen or carbon number 1
Is a group selected from aliphatic groups in the range of to 6 and each R may be the same or different. (V) -CO-Y-CO- (Y is a range of 2 to 22 carbon atoms) Of at least one selected from the group consisting of an aliphatic group and an alicyclic hydrocarbon group-containing aliphatic group) (VI) -CO-Z-NH- (Z is an aliphatic group or aromatic group having 4 to 14 carbon atoms) At least one selected from)

Relative viscosity of polyamide resin (b) (98%
Concentrated sulfuric acid in 1g / dl, measurement temperature 25 ℃) is 1.0 ~
5.0 dl / g, more preferably 1.4-3.5 dl / g,
More preferably, it is in the range of 1.6 to 3.0 dl / g.
Methods for producing these non-crystalline or low-crystalline polyamide resins are known, for example, JP-A-58-38751.
JP-A-60-217237 and JP-A-60-219.
Those disclosed in Japanese Patent No. 227, etc. can be applied.

Specific examples of W in the structural unit (I) include butylene group, hexylene group, octylene group,
Decanylene group, 2,2,4-trimethylhexylene group,
A 2,4,4-trimethylhexylene group, a 3-methylhexylene group, a pentylene group can be mentioned, and more preferably a butylene group, a hexylene group, a 2,4,4-trimethylhexylene group, 2,2,4- It is a trimethylhexylene group.

Specific examples of X in the above structural unit (II) include a metaxylylene group (Xa), a 4,4'-methylenedicyclohexane-1,1'-diyl group (Xb),
2,2'-dimethyl-4,4'-methylenedicyclohexane-1,1'-diyl group (Xc), 1,5,5-trimethylcyclohexylene-1-methylene group (Xd), cyclohexylene-1, 4-dimethylene group (Xe), 4-
Methylenecyclohexylene group (Xf), 3-methylenecyclohexylene group (Xg), cyclohexylene-1,3
-A dimethylene group (Xh) and the like. Structural formulas of specific examples of each X are shown below.

[0023]

[Chemical 4]

Specific examples of R in the structural units (III) and (IV) include a hydrogen atom, a methyl group, a tertiary butyl group, an isopropyl group and an ethyl group, more preferably a hydrogen atom, a methyl group, and It is preferably a hydrogen atom. Specific examples of Y in the structural unit (V) include ethylene group, propylene group, butylene group, hexylene group, octylene group, decanylene group, 1,4-cyclohexylene group, 1,3-cyclohexylene group, structural unit ( (Xa), (Xb), (Xc), (X
d), (Xe), (Xf), (Xg), (Xh) and the like, and more preferably ethylene group, propylene group, butylene group, octylene group, 1,4-cyclohexylene group, 1,3-. It is a cyclohexylene group, more preferably an ethylene group, a propylene group or a butylene group.

Specific examples of Z in the structural unit (VI) include a butylene group, a pentylene group, a hexylene group, a decanylene group, an undecanylene group and a paraphenylene group, and more preferably a pentylene group, a hexylene group and an undecanylene group. And more preferably a pentylene group. Specific preferred examples of the polyamide resin (b) are shown below.

[0026]

[Chemical 5]

The crystalline polyamide resin (c) used in the present invention has an amide bond in the polymer main chain, can be melted by heating, and has a definite melting point having a measurable heat of fusion. It is a thing. The melting point and the heat of fusion can be measured using a differential scanning calorimeter. Examples include the apparatus and measuring method used for the above-mentioned amorphous or low crystalline polyamide resin (b). The crystalline polyamide resin in the present invention can also be defined as one having a heat of fusion of more than 1 cal / g measured by this method.

As a typical example, nylon-
4, nylon-6, nylon-12, nylon-6,
6, Nylon-4,6, Nylon-6,10, Nylon-6,12 and Nylon-6, T (polyamide consisting of hexamethylenediamine and terephthalic acid), Nylon-MXD, 6 (meta-xylylenediamine and adipic acid) Polyamide), nylon-6 and nylon-6,6
And a copolymer of hexamethylenediamine, adipic acid and caprolactam. Among these, nylon-6,6 and nylon- are more preferable.
It is 6.

The relative viscosity of the crystalline polyamide resin (c) of the present invention (in 98% concentrated sulfuric acid, concentration 1 g / dl, measurement temperature 25)
C.) is preferably 1 to 6 dl / g. The rubber-like substance (d) used in the present invention may be an elastomer, a polyolefin resin having a low flexural modulus, or a modified product thereof (modified rubber-like substance). Such a rubber-like substance usually has an elastic modulus of 10,000 kg / cm ² or less,
It is preferably 8,000 kg / cm ² or less.

Specifically, ethylene-propylene rubber,
Ethylene-propylene-non-conjugated diene rubber, ethylene-
Buden rubber, propylene-budene rubber, isoprene-butylene rubber, polyisoprene, polybutadiene, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, partially hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, partially hydrogenated styrene-isoprene block Copolymer, thiochol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (for example, polypropylene oxide, etc.), epichlorohydrin rubber, polyester elastomer, polyamide elastomer, linear low density polyethylene, etc., or a mixture thereof is used.

The modified rubber-like substance is obtained by modifying the rubber-like substance with a "compatibilizer". For example, maleic anhydride grafted ethylene-propylene rubber, maleic anhydride grafted ethylene-butadiene-styrene block copolymer, maleic anhydride grafted partially hydrogenated styrene-
Butadiene block copolymer, maleic anhydride grafted partially hydrogenated styrene-isoprene block copolymer, glycidyl methacrylate grafted ethylene-propylene rubber and the like can be used.

Further, ethylene-acrylic acid ester-maleic anhydride copolymer obtained by polymerizing a compatibilizer, ethylene-
Acrylic ester-glycidyl methacrylate copolymers, ethylene-vinyl acetate-glycidyl methacrylate copolymers or blends thereof are also used as rubber-like substances. Among them, ethylene-propylene rubber, ethylene-butene rubber, styrene-butadiene block copolymer, partially hydrogenated styrene-butadiene block copolymer, styrene-butadiene-styrene-block copolymer (SBS), styrene-ethylene-butylene-
Styrene block polymer (SEBS), styrene-isoprene block copolymer, partially hydrogenated styrene-isoprene block copolymer, density 0.885-0.
935, preferably linear low density polyethylene in the range of 0.885 to 0.925, ethylene-methyl acrylate-maleic anhydride copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, Ethylene-methyl acrylate-glycidyl methacrylate copolymers or mixtures thereof are preferred.

Among the components (e) used in the present invention, the inorganic filler may be any one used for polyamide resins and polyphenylene ether resins, and the average particle diameter and shape are not particularly limited. Specifically, carbon black, mica, silica, TiO ₂ , clay, zinc oxide, talc,
Examples thereof include calcium carbonate, magnesium sulfate, wollastonite, whiskers, alumina and asbestos. The inorganic filler may be used without any treatment, but various silane coupling agents, titanium cups and titanium cups are used for the purpose of improving the interfacial adhesion with the polyphenylene ether resin and / or the nylon resin and improving the dispersibility. It is possible to use those whose surface is treated with a ring agent, higher fatty acid, higher fatty acid ester, higher fatty acid amide, higher fatty acid salt or other surfactant.

The glass fiber used in the present invention may be used in combination with an inorganic filler or may be used alone. From the viewpoint of dimensional stability, heat resistance, rigidity and appearance, it is preferable to use it together with an inorganic filler. As the glass fiber, a chopped strand having a diameter of 15 μm or less and a length of 6 mm or less is used. When it exceeds 15 μ, the degree of improvement in mechanical strength becomes small and the amount of warping becomes large, which is not preferable. Glass fibers having a diameter of 13 μm or less and a length of 3 mm or less are preferably used.

The glass fiber may be used in combination with various coupling agents in order to improve the interfacial adhesion and dispersibility with the polyphenylene ether resin / or the polyamide resin. The coupling agent usually includes a silane-based or titanium-based coupling agent. Among them, epoxy silanes such as γ-glycidoxypropyltrimethoxysilane,
It is preferable to include a silane coupling agent such as vinylsilane such as vinyltrichlorosilane and aminosilane such as γ-aminopropyltriethoxysilane.

The compatibilizer (f) used in the present invention is specifically selected from the following groups (A) to (E):
A compound of one or more species. (A); in the molecule, (a) a carbon-carbon double bond or a carbon-carbon triple bond, and (b) a carboxyl group, an acid anhydride, an amino group, an acid amide group, an imide group, an epoxy group,
A compound having a carboxylic acid ester group, an isocyanate group, a methylol group or a hydroxyl group at the same time.

Specific examples include maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide, and reaction products of maleic anhydride and diamine, for example,

[0038]

[Chemical 6]

(Wherein R represents an aliphatic or aromatic group) and the like, methylnadic acid anhydride, dichloromaleic anhydride, maleic acid amide, soybean oil, tung oil, castor oil, flaxseed Oil, hemp oil, cottonseed oil, rubber oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconut oil,
Natural fats and oils such as sardine oil, epoxidized natural fats and oils such as epoxidized soybean oil, acrylic acid, butenoic acid, crotonic acid, vinylacetic acid, methacrylic acid, pentenoic acid, angelic acid, tibric acid, 2-pentenoic acid, 3 -Pentenoic acid,
α-ethyl acrylic acid, β-methyl crotonic acid, 4-pentenoic acid, 2-hexenoic acid, 2-methyl-2-pentenoic acid, α-ethyl crotonic acid, 2,2-dimethyl-3-butene acid, 2- Heptenoic acid, 2-octenoic acid, 4-decenoic acid, 9-undecenoic acid, 10-undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4-tetradecenoic acid, 9-tetradecenoic acid, 9-hexadecenoic acid, 2- Octadecenoic acid, 9-octadecenoic acid, eicosenoic acid, docosenoic acid,
Erucic acid, tetracosenoic acid, mycolic acid, 2,4-
Pentadienoic acid, 2,4-hexadienoic acid, diallylacetic acid, geranium acid, 2,4-decadienoic acid, 2,4-dodecadienoic acid, 9,12-hexadienoic acid, 9,12-
Octadecadienoic acid, hexadecatrienoic acid, linoleic acid, linolenic acid, octadecatrienoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, eicosapentaenoic acid, Unsaturated carboxylic acids such as erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid, octacosenoic acid, and traacontenoic acid, or esters and acids of these unsaturated carboxylic acids. Amide, anhydride, or allyl alcohol, crotyl alcohol, methyl vinyl carbinol, methyl propenyl carbinol, 4-penten-1-ol,
10-undecen-1-ol, propargyl alcohol, 1,4-pentadiene-3-ol, 1,4-hexadiene-3-ol, 3,5-hexadiene-2-ol, 2,4-hexadiene-1-ol , General formula, H
_{2n-5 OH, C n H} 2n-7 OH, C n H 2n-9 OH, ( provided that
n is a positive integer), 3-butene-
1,2-diol, 2,5-dimethyl-3-hexane-
An unsaturated alcohol such as 2,5-diol, 1,5-hexadiene-3,4-diol, or 2,6-octadiene-4,5-diol, or an OH group of such an unsaturated alcohol is an NH ₂ group. Of the unsaturated amine,
Alternatively, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc. may be mentioned.
Among them, maleic anhydride, maleic acid, fumaric acid, itaconic acid, anhydrous-hymic acid, glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether are preferable.

(B); Formula (R ^I O) _m R (COOR ^II ) _n (CONR ^III R ^IV ) _S {wherein R is a linear or branched saturated aliphatic hydrocarbon having 2 to 20 carbon atoms. R ^I is hydrogen or C 1-10 selected from the group consisting of alkyl, aryl, acyl or carbonyldioxy groups: each R ^II is hydrogen or C 1-20 alkyl. Independently selected from the group consisting of groups or aryl groups: each R ^II and R ^III and R ^IV is independently selected from the group consisting of hydrogen or alkyl or aryl groups having 1 to 10 carbon atoms; Equal to 1 and (n + s) is greater than or equal to 2 and n and s are greater than or equal to 0 respectively; (OR ^I ) is at α or β to the carbonyl group and is at least 2 2 to 6 carbonyl groups Aliphatic polycarboxylic acids or their reaction products or consists derivatives represented by} are separated by carbon atoms.
Specifically, it is citric acid, malic acid, or their calcium and potassium salts.

(C); in the molecular structure, (a) at least one silicon atom having a carbon atom bonded through an oxygen bridge, and (b) at least an ethylenic carbon-carbon double bond or carbon-carbon. A silane compound having both a triple bond and / or a functional group selected from an amino group and a mercapto group, wherein the functional group is not directly bonded to a silicon atom. Specifically, γ (gamma) -aminopropyltriethoxysilane; vinyl-tris (2-methoxyethoxy)
Silane: 5 (bicycloheptenyl) triethoxysilane and γ-mercaptopropyltrimethoxysilane.

(D): In the molecule, (a) mercapto group, (b) carboxyl group, acid anhydride group, acid amide group,
A compound having at least one functional group selected from the group consisting of an imide group, a carboxylic acid ester group, an epoxy group, an amino group and a hydroxyl group at the same time, represented by the following general formula (HS) _m —R—X _n (formula Where m and n are positive integers, R is an aliphatic group or an aromatic group, X is a carboxyl group, an acid anhydride group, an acid amide group, an amide group, a carboxylic acid ester group, an epoxy group, an amino group. And at least one functional group selected from the group consisting of hydroxyl groups, provided that when n is 2 or more, X does not have to be the same. Specifically, mercaptopolycarboxylic acids such as thiomalic acid and thiocitric acid, and the carboxyl groups of these mercaptopolycarboxylic acids are acid anhydride groups, N, N'-dialkylamide groups, N-alkylimide groups, N-aryl. A compound converted into an imide group or an alkyl ester group,
1,2-epoxy-3-mercaptopropane, epoxy compounds such as 4-di (2,3-epoxypropyl) aminothiophenol, amines such as 1-amino-2-mercaptoethane and 4-aminothiophenol, 2 Examples include mercapto group-containing alcohols such as mercaptoethanol and 3-mercapto-1,2-propanediol, and mercaptophenols. Especially thiomalic acid,
Mercaptopolycarboxylic acids such as thiocitric acid are preferred.

(E); a copolymer having a vinyl aromatic compound unit and an α, β-unsaturated dicarboxylic acid or dicarboxylic anhydride unit, or a vinyl aromatic compound unit and an α, β-unsaturated dicarboxylic acid unit. It is a copolymer having a unit of an acid imide compound. Specifically, styrene-
Maleic anhydride copolymer, styrene-maleic anhydride-
Methacrylate terpolymers, styrene-maleic anhydride-acrylate terpolymers, and rubber modified modifications of these compounds.

In the present invention, the blending ratios of the components (a) to (c) are as follows with respect to the total weight of (a), (b) and (c). Component (a): 5-90% by weight, preferably 20-65% by weight, more preferably 30-55% by weight. If it is less than 5% by weight, the physical properties are significantly deteriorated due to water absorption, and 90% by weight
Excessive amounts are not preferable because they cause problems in fluidity and resistance to organic solvents. Component (b): 0.5 to 20% by weight, preferably 1 to 15
%, More preferably 2 to 10% by weight. 0.5
If the amount is less than 1% by weight, the effect intended by the present invention cannot be obtained, and 2
If it exceeds 0% by weight, the organic solvent resistance tends to be difficult, which is not preferable. Component (c): 5-90% by weight, preferably 20-65% by weight, more preferably 25-60% by weight. If it is less than 5% by weight, the organic solvent resistance becomes difficult, and if it exceeds 90% by weight, the physical properties are significantly deteriorated due to water absorption, which is not preferable.

The component ratio (weight ratio) of (b) and (c) is (b) / (c) ≦ 0.2, preferably (b) /
(C) ≦ 0.15. When (b) / (c)> 0.2, the releasability of the thermoplastic resin composition of the present invention is remarkably inferior, resulting in deformation of the product due to an increase in releasability and extension of the molding cycle, and moldability and dimensional stability Is reduced. Also (d),
The mixing ratio of the components (e) and (f) is (a) + (b) +.
(C) When the total amount is 100 parts by weight, it is as follows. Component (d): 0 to 40 parts by weight, preferably 2 to 30 parts by weight, more preferably 5 to 20 parts by weight. When the component (d) is not contained, the impact resistance is poor, but the heat resistance, rigidity and dimensional stability are improved. Therefore, it is preferable that the component (d) is blended as necessary in consideration of the application and the like. 40
If it exceeds the weight part, the heat resistance rigidity level becomes unsatisfactory, which is not preferable.

Component (e): 2 to 100 parts by weight, preferably 5 to 80 parts by weight. If it is less than 2 parts by weight, the rigidity is insufficient, and if it exceeds 100 parts by weight, the appearance is deteriorated.
When the inorganic filler and the glass fiber are used together, the ratio of the inorganic filler and the glass fiber is 90 to 10 parts by weight of the glass fiber to 10 to 90 parts by weight of the inorganic filler. Component (f): 0.01 to 15 parts by weight, preferably 0.0
It is 5 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight. If it is less than 0.01 part by weight, the effect intended by the present invention cannot be obtained, and if it exceeds 15 parts by weight, heat resistance becomes difficult, which is not preferable.

The composition according to the present invention contains a thermoplastic or thermosetting resin other than the above polymer component, a rubber component, an antioxidant, a weather resistance improver, if necessary, within a range not impairing the object of the present invention. Ingredients such as a nucleating agent, a slip agent, a flame retardant, various colorants, an antistatic agent, and a release agent can also be added. In the present invention, polyphenylene ether resin (a), amorphous or low crystalline polyamide resin (b), crystalline polyamide resin (c), rubber-like substance (d), inorganic filler and / or glass fiber (e) The mixing method of the compatibilizing agent (f) and the compounding agent (f) is not particularly limited, and a known melt-kneading method can be used. An extruder, a kneader, a roll or the like can be used as the melt-kneading device.

In a special case, all components may be directly supplied to various molding machines and kneaded by the molding machine to perform molding.
In addition, a filler or other components are kneaded to a high concentration in advance (with various additives as necessary) to form a masterbatch, which is then separately blended with another polymer or the like for blend compounding or molding. However, there is no particular limitation on the order of addition of the components during melt kneading.

That is, the components (a), (b), (c),
(D), (e) and (f) are added all at once and melt kneaded at the same time; components (a) and (f) are melt kneaded in advance in the presence or absence of a radical initiator, and then the components Method of performing melt kneading with additional addition of (b), (c), (d) and (e); components (a), (d) and (f) in the presence or absence of a radical initiator Melt kneading in advance,
Then, the components (b), (c) and (e) are additionally added and melt-kneaded; the components (a), (d), (f) and (e) are added in the presence or absence of a radical initiator. Melt kneading in advance, and then melt kneading by additionally adding components (b) and (c); components (a), (d) and (f) in advance in the presence or absence of a radical initiator. Melt kneading,
Then, (b) and (c) are additionally kneaded, and further (e) is additionally added and melt kneaded; components (a), (d) and (f) are added in the presence or absence of a radical initiator. Any method such as melt kneading in advance under the following conditions, then (k) is additionally kneaded, component (e) is additionally kneaded, and further component (c) is additionally added and melt kneading is possible. ..

The kneaded resin composition is molded by various molding methods such as injection molding and is used as various injection molded products, extrusion molded products, sheets, tubes, films, fibers, laminates and coating materials. The molded product obtained from the thermoplastic resin composition of the present invention is suitably used for automobile parts, electric / electronic parts and the like.

Examples of molded articles for automobile parts include bumpers,
Fenders, aprons, hood panels, fascias, loker panels, rocker panels, reinforcements, floor panels, rear quarter panels, door panels, door supports, roof tops, trunk lids, fuel lids, etc., instrument panels, console boxes, glove boxes , Shift knob, pillar garnish, door trim, handle, armrest, wind louver, headrest, seat belt, interior parts such as seat, distributor cap, air cleaner,
Examples include engine room parts such as a radiator tank, a battery case, a radiator shroud, a washer tank, a cooling fan, and a heater case, a miller body, a wheel cover, a trunk mat, a gasoline tank, and the like.

Further, it is used as a motorcycle component such as a cowling material, a muffler cover, and a leg shield.
Further, as electric and electronic parts, it is used for housings, chassis, connectors, printed circuit boards, pulleys, and other parts required to have strength and heat resistance.

[0053]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto. The test method in the examples was carried out by the following method. (1) Deflection temperature under load (HDT): ASTMD64
8 was carried out. (2) Izod impact strength: carried out according to ASTM D256. However, the test piece had a thickness of 3.2 mm and was notched. (3) Flexural modulus: According to ASTDM790. (4) Appearance: The surface roughness of the injection-molded product was measured with a SE-3FK surface roughness tester of Kosaka Laboratory. Surface irregularities of 3 μm or less …… ○ Surface irregularities of 3 μm or more …… × (5) Formability: 8 cm × 8 cm lattice type die with protruding pins (lattice size is 1 cm × 1 cm) Then, the releasability of the molded product was evaluated. Molded product demolds without deformation 〇 〇 Molded product deforms and does not demold …… × Polyphenylene ether used in the examples and comparative examples,
Polyamide, rubber substance, inorganic filler and glass fiber are commercially available.

Example 1 General polyphenylene ether resin. 44 parts by weight of poly (2,6-dimethylphenol) having a specific viscosity ηsp of 0.28 at a temperature of 25 ° C. of a chloroform solution of 0.6 g / dl concentration manufactured by Electric Co., 0.9 parts by weight of malic acid, styrene-butadiene -Styrene block copolymer (SBS: manufactured by Shell Chemical Co., trade name;
TR1101) 5 parts by weight, styrene-ethylene-butylene-styrene block polymer (SEBS: manufactured by Shell Chemical Co., trade name; G1651) 5 parts by weight of a continuous twin-screw extruder (TEM-35B, manufactured by Toshiba Machine Co., Ltd.). Amorphous polyamide (manufactured by Mitsubishi Kasei Co., Ltd., trade name: Novamid X21.S07, Novamid is a registered trademark; charged from the first hopper and further from the second hopper provided between the first hopper and the vent hole) The melting point of this product was slowly measured by DSC, but a clear melting point did not appear.) 6 parts by weight, crystalline polyamide (nylon 6 resin: Mitsubishi Kasei Co., Novamid 1015J) 50 parts by weight were used with a quantitative feeder. I put it in. Cylinder temperature is 270 ℃
Was set, and the mixture was pelletized by melt-kneading at a screw rotation speed of 250 rpm. Then, 37 parts by weight of talc (manufactured by Hayashi Kasei Co., Ltd., trade name: Micron White 5000A) was melt-kneaded together with 110.9 parts by weight of the pellets by a 40 mm single-screw extruder (Isuzu Kakoki Co., Ltd.) , Pelletized into granules.

An injection molding machine (made by Japan Steel Works, J10
0SA) Cylinder temperature 280 ℃ Mold temperature 100 ℃
After molding the test piece under the conditions described above, physical properties and appearance were measured. The results are shown in Table 1. Further, under the same molding conditions, moldability was evaluated using a mold for studying mold release.

Comparative Example 1 In Example 1, 50 parts by weight of the crystalline polyamide and 6 parts by weight of the amorphous polyamide were used together, but only 56 parts by weight of the crystalline polyamide was used, and 37 parts by weight of talc was 28 parts by weight. The same procedure as in Example 1 was carried out except that the parts were changed.

Comparative Example 2 The same procedure as in Example 1 was carried out except that 50 parts by weight of the crystalline polyamide and 6 parts by weight of the non-crystalline polyamide were used together in Example 1, but only 56 parts by weight of the crystalline polyamide was used. ..

Example 2 Example 1 was repeated except that 37 parts by weight of talc was changed to 28 parts by weight of mica [manufactured by Yamaguchi Mica Industry Co., Ltd., trade name: A21PE].

Comparative Example 3 The same procedure as in Example 2 was repeated except that the crystalline polyamide of 50 parts by weight and the non-crystalline polyamide of 6 parts by weight were used in combination in Example 2, but only the crystalline polyamide was changed to 56 parts by weight. did.

Example 3 37 parts by weight of talc in Example 1 was mixed with milled fiber (Asahi Fiber Glass Co., Ltd., trade name: FA-A) 2
Example 1 was repeated except that the amount was changed to 8 parts by weight.

Comparative Example 4 The procedure of Example 3 was repeated, except that the combination of 50 parts by weight of crystalline polyamide and 6 parts by weight of amorphous polyamide was changed to 56 parts by weight of crystalline polyamide only.

Example 4 In Example 1, 37 parts by weight of talc was used as wollastonite (Hayashi Kasei Co., Ltd., trade name: CHD-62N10) 37.
The same procedure as in Example 1 was repeated except that the amount was changed to parts by weight.

Comparative Example 5 The procedure of Example 4 was repeated, except that 50 parts by weight of the crystalline polyamide and 6 parts by weight of the non-crystalline polyamide in Example 4 were changed to 56 parts by weight of the crystalline polyamide.

Example 5 37 parts by weight of talc in Example 1 was mixed with glass fiber (made by Asahi Fiber Glass Co., Ltd., trade name: CS-03-MA4).
11) The procedure of Example 1 was repeated, except that the amount was changed to 12 parts by weight.

Comparative Example 6 The procedure of Example 5 was repeated, except that 50 parts by weight of the crystalline polyamide and 6 parts by weight of the amorphous polyamide were replaced by 56 parts by weight of the crystalline polyamide.

Example 6 Example 6 was repeated except that 5 parts by weight of SBS and 5 parts by weight of SEBS were changed to 5 parts by weight of SBS.

Comparative Example 7 The same as Example 5 except that 6 parts by weight of the non-crystalline polyamide and 50 parts by weight of the crystalline polyamide were replaced by 16 parts by weight of the non-crystalline polyamide and 40 parts by weight of the crystalline polyamide. It carried out similarly.

As shown in Example 1 and Comparative Example 1, in order to maintain a good appearance without using the non-crystalline polyamide, the amount of talc must be reduced, which causes a decrease in flexural modulus. The rigidity level is lowered. But,
When the amount of talc added is increased to increase the rigidity level, as shown in Comparative Examples 1 and 2, the crystalline polyamide alone gives a poor appearance. Therefore, when a crystalline polyamide and an amorphous polyamide are used together, Example 1 and Comparative Example 2
As shown in, the appearance becomes good.

As shown in Example 2 and Comparative Example 3, Example 3 and Comparative Example 4, and Example 4 and Comparative Example 5, crystalline polyamide and amorphous polyamide were used regardless of the type and shape of the filler. It can be seen that the combined use has the effect of improving the appearance. As shown in Example 5 and Comparative Example 6, it can be seen that also in the glass fiber, the combined use of the crystalline polyamide and the amorphous polyamide has the effect of improving the appearance.

As shown in Example 6, SEBS and SBS
It can be seen that the combined use of the crystalline polyamide and the non-crystalline polyamide has the effect of improving the appearance even without the use of. As shown in Example 5 and Comparative Example 7, unless the weight ratio (b) / (c) of the (b) non-crystalline polyamide and the (c) crystalline polyamide is 0.2 or less, the formability is remarkably reduced. I understand.

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[Table 1]

[0072]

As described above, according to the present invention, the dimensional stability, heat resistance, rigidity and impact strength of the polyphenylene ether-polyamide resin composition are maintained while maintaining the moldability and appearance of the composition. It is possible to provide a filler-containing polyphenylene ether-polyamide resin composition having an excellent balance.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 53/02 LLZ 7142-4J 77/00 LQS 9286-4J LQV 9286-4J

Claims (1)

Claims (a) Polyphenylene ether resin; 5
To 90% by weight, (b) a non-crystalline to low crystalline polyamide resin having a glass transition temperature of 90 to 250 ° C .; 0.5 to 20 parts by weight, and (c) a crystalline polyamide resin; 90 to 5 %, And the weight ratio of (b) and (c) is (b) / (c) ≦
(D) rubber-like substance 0-40 parts by weight (e) inorganic filler and / or glass fiber 2-100 with respect to 100 parts by weight of the resin mixture which is 0.2
Parts by weight, (f) one or more compatibilizers that improve the compatibility of the polyphenylene ether resin and the polyamide resin;
The thermoplastic resin composition is characterized by being blended in an amount of 01 to 15 parts by weight.