JPH0726135A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition useful as outside plate material of automobile, building material, etc., having excellent impact resistance, adhesiveness of coating film, heat stability and processability, comprising a polyphenylene ether and a polyamide as main components in a specific ratio. CONSTITUTION:(A) 1-60wt.% of a polyphenylene ether (preferably homopolymer of 2,6-dimethylphenol) and (B) 40-99wt.% of a polyamide (preferably nylon 46 or nylon 6) are mixed with (C) 1-50 pts.wt. of a hydogenated conjugated diene- alkenyl aromatic random copolymer (hydrogenated styrene-butadiene random copolymer having preferably 10-40wt.% styrene amount) having <=10,000kg/cm<2> modulus of elasticity at normal temperature based on 100 pts.wt. of the total of the components A and B and (D) a compatibilizing agent (preferably maleic anhydride, maleic acid, fumaric acid, etc.) in a sufficient amount to compatibilize the component A and the component B (preferably 0.05-25 pts.wt. based on 100 pts.wt. of the total of the components A and B) to give the objective composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition containing polyphenylene ether and polyamide as main components.

[0002]

2. Description of the Related Art Polyphenylene ether resin is a thermoplastic resin excellent in various properties such as mechanical properties, heat resistance stability and dimensional stability. However, the polyphenylene ether resin alone has a markedly poor impact resistance and solvent resistance, and its high melt viscosity results in poor processability. Polyamide resin, on the other hand, is a thermoplastic resin with excellent mechanical properties, solvent resistance, processability, etc., but it has poor impact resistance, heat stability, etc., and its dimensional stability due to its high water absorption. Is remarkably poor, and the mechanical properties are significantly deteriorated by water absorption.
In order to make up for the drawbacks of these resins, it has been proposed to use a blend of both resins. However, simply blending loses the good mechanical properties of both resins. Therefore, at the time of blending the polyphenylene ether resin and the polyamide resin, various compatibilizers are added to improve the dispersibility and mechanical properties are improved (for example, Japanese Patent Publication No. 60-11966, Japanese Patent Publication No. See JP-A-61-1494, JP-A-59-66452, and JP-A-56-49753.). The polyphenylene ether / polyamide resin composition thus obtained is used as a material having excellent mechanical properties, heat resistance stability, solvent resistance, processability, dimensional stability, and hygroscopicity, and is applied to the electric / electronic fields and automobile fields. Is being done. Further, in order to improve the impact resistance of these resin compositions, resin compositions using ethylene-propylene rubber, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-butadiene rubber, etc. are disclosed. ing. However, when ethylene-propylene rubber or hydrogenated styrene-butadiene block copolymer is used, coating adhesion is poor, and when styrene-butadiene block copolymer or styrene-butadiene rubber is used, heat stability is poor. sex,
It is still insufficient to maintain a good balance of coating film adhesion and heat stability.

[0003]

In view of the present situation, the problem to be solved by the present invention is to provide a thermoplastic resin composition containing polyphenylene ether and polyamide as main components, which has impact resistance, coating adhesion. The purpose of the present invention is to provide a thermoplastic resin composition which maintains a good balance between performance and heat stability and is excellent in processability.

[0004]

That is, the present invention comprises the following components (A) to (D), the content of the component (A) is 1 to 60% by weight, and the content of the component (B) is Is 40-9
9% by weight, the content of the component (C) is 1 to 50 parts by weight per 100 parts by weight of the total amount of the components (A) and (B), and the content of the component (D) is the component (A). And a thermoplastic resin composition in an amount sufficient to compatibilize the component (B). (A): Polyphenylene ether (B): Polyamide (C): Hydrogenated conjugated diene-alkenyl aromatic random copolymer having an elastic modulus at room temperature of 10,000 kg / cm ² or less (D): Compatibilizer

The details will be described below. The component (A) of the present invention is a polyphenylene ether, and is a polymer obtained by oxidatively polymerizing one or more phenol compounds represented by the following formula with oxygen or an oxygen-containing gas using an oxidation coupling catalyst. Is preferred.

[0006]

[Chemical 1]

(In the formula, R _{1 to} R ₅ are independently one kind selected from hydrogen, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, and at least one of them is a hydrogen atom). Specific examples of R _{1 to} R ₅ include hydrogen, chlorine, bromine, fluorine, iodine, methyl, ethyl, n- or iso-propyl, pri-, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, Benzyl, hydroxymethyl, carboxyethyl,
Methoxycarbonylethyl, cyanoethyl, phenyl,
Chlorophenyl, methylphenyl, dimethylphenyl,
Examples include ethylphenyl and allyl.

Specific examples of the compound represented by the above formula include phenol, o-, m-, or p-cresol, 2,6-, 2,5-, 2,4- or 3,5-dimethyl. Phenol, 2-methyl-6-phenylphenol,
2,6-diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, 2,3
Examples include 5-, 2,3,6- or 2,4,6-trimethylphenol, 3-methyl-6-t-butylphenol, thymol, 2-methyl-6-allylphenol and the like.

Further, as the component (A), a phenol compound other than the above-mentioned formula, for example, a polyvalent hydroxyaromatic compound such as bisphenol-A, tetrabromobisphenol-A, resorcin, hydroquinone and novolac resin is represented by the above formula. You may use the copolymer of the compound.

Preferred as the component (A) are:
Homopolymer of 2,6-dimethylphenol, homopolymer of 2,6-diphenylphenol, copolymer of a large amount of 2,6-xylenol and a small amount of 3-methyl-6-t-butylphenol, a large amount of 2,6-xylenol and a small amount of a 2,3,6-trimethylphenol copolymer.

The content of the component (A) in the thermoplastic resin of the present invention is 1 to 60% by weight, preferably 5 to 60% by weight. When the content is too small, the high temperature rigidity is lowered, while when the content is too large, the impact resistance and the fluidity are remarkably lowered.

The component (B) of the present invention is a polyamide,
The polyamide is at least one polyamide selected from crystalline aliphatic polyamides and aromatic polyamides.

The crystalline aliphatic polyamide used in the present invention is, for example, the one shown below.

These include equimolar amounts of 4 to 4 carbon atoms.
Saturated aliphatic dicarboxylic acids containing 12 and 2 to 1 carbon atoms
It can be produced by combining with an aliphatic diamine containing two diamines, and in that case, a diamine or the like can be used in the polyamide so that the amine end group is provided in excess from the carboxyl end group in the polyamide, if desired. Conversely, dibasic acids can be used to provide an excess of acidic groups. Similarly, these polyamides can be successfully prepared from acid-forming and amine-forming derivatives of the acids and amines such as esters, acid chlorides, amine salts and the like. Typical aliphatic dicarboxylic acids used to make this polyamide include adipic acid, pimelic acid, azelaic acid, suberic acid, sebacic acid and dodecanedioic acid, while typical aliphatic diamines are hexamethylene. Diamines and octamethylene diamines are included. In addition, these polyamides can be produced by the self-condensation of lactams.

Examples of polyamides are polyhexamethylene adipamide (nylon 66), polyhexamethylene azeramide (nylon 69), polyhexamethylene sebacamide (nylon 610), and polyhexamethylene dodecanoamide (nylon). 612), poly-bis- (p-aminocyclohexyl) methane dodecanoamide, polytetramethylene adipamide (nylon 46) or polyamides formed by ring opening of lactams; ie polycaprolactam (nylon 6), and polylauryllactam. included. It is also possible to use a polyamide produced by polymerization of at least two amines or acids used in producing the above polymer, for example, a polymer produced from adipic acid, sebacic acid, and hexamethylenediamine. . Blends of polyamides such as blends of nylon 66 and nylon 6 include copolymers such as nylon 66/6.

Of these crystalline polyamides, nylon 46, nylon 6, nylon 66, nylon 11 and nylon 12 are preferably used. More preferably, nylon 6, nylon 66, or a mixture of nylon 6 and nylon 66 in any ratio is used. The terminal functional groups of these polyamides are preferably those having a large number of amine terminals, those having a large number of carboxy terminals, those in which both are balanced, or a mixture thereof in any desired ratio.

The aromatic polyamide used in the present invention is a copolyamide containing an aromatic component such as polyhexamethylene isophthalamide (nylon 61). A thermoplastic copolyamide containing such an aromatic component can be melt-polymerized with an aromatic amino acid and / or an aromatic dicarboxylic acid, for example, para-aminomethylbenzoic acid, para-aminoethylbenzoic acid, terephthalic acid, isophthalic acid, etc. as main constituent components. Means a polyamide.

The diamines which are the other constituents of the polyamide are hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4.
4-trimethylhexamethylenediamine, metaxylylenediamine, paraxylylenediamine, bis (p-aminocyclohexyl) methane, bis (p-aminocyclohexyl) propane, bis (3-methyl, 4-aminocyclohexyl) methane, 1, 3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, etc. can be used. Isocyanates can be used instead of diamine. For example, 4,4 ′ diphenylmethane diisocyanate, tolylene diisocyanate and the like.

The copolymerization component used as necessary is not particularly limited, and may be lactam or ω-containing 4 to 12 carbon atoms.
A unit of amino acid, or a compound derived from an aliphatic dicarboxylic acid having 4 to 12 carbon atoms and an aliphatic diamine having 2 to 12 carbon atoms, for example, ε-caprolactam,
ω-laurolactam, 11-aminoundecanoic acid, 12
-A lactam such as aminododecanoic acid, or an amino acid, and a molar salt of the above-mentioned various diamines with adipic acid, azelaic acid, sebacic acid, or the like can be used.

Typical examples of the thermoplastic aromatic copolyamides containing these components are copolymerized polyamides of paraaminomethylbenzoic acid and ε-caprolactam (nylon AMBA / 6), 2,2,4- / 2,4. , 4-Trimethylhexamethylenediamine terephthalate-based polyamide (nylon TMDT, TMDT / 6
1), hexamethylenediamine, isophthalate and /
Alternatively, the main component is hexamethylenediamine terephthalate, and bis (paraaminocyclohexyl) methane isophthalate and / or terephthalate or bis (3
-Methyl, 4-aminocyclohexyl) methane isophthalate and / or terephthalate or bis (paraaminocyclohexyl) propane isophthalate and / or
Alternatively, polyamide containing bis (paraaminocyclohexyl) propane terephthalate as a copolymerization component (nylon 6I
/ PACM I, Nylon 6I / DMPACM I, Nylon 6I / PACP I, Nylon 6I / 6T
/ PACM I / PACMT, nylon 6I / 6T /
DMPACM I / DMPACM T, Nylon 6I /
6T / PACP I / PACP T), hexamethylenediamine / isophthalate or hexamethylenediamine / terephthalate as a main component, and ε-caprolactam, 12-aminododecanoic acid, hexamethylenediamine adipate, bis (paraamino) Polyamide (nylon 6I, 6I / 6T, 6I / containing 6% cyclohexyl) methane adipate, bis (3-methyl, 4-aminocyclohexyl) methane adipate as a copolymerization component
12, 6T / 6, 6T / 66, 6I / PACM 6,6
I / DMPACM 6), bis (paraaminocyclohexyl) methane isophthalate or bis (3-methyl,
4-aminocyclohexyl) methane, isophthalate as the main component, hexamethylenediamine dodecane diacid salt,
Polyamide containing 12-aminododecanoic acid as a copolymerization component (nylon PACM I / 612, nylon DMP
ACM I / 12) and the like.

Amorphous aromatic polyamides are preferably used in the aromatic polyamide group.

The content of the component (B) in the thermoplastic resin of the present invention is 40 to 99% by weight, preferably 40 to 85.
% By weight.

The component (C) of the present invention is a hydrogenated conjugated diene-alkenyl aromatic random copolymer having an elastic modulus at room temperature of 10,000 kg / cm ² or less. Examples of the conjugated diene include butadiene and isoprene. Examples of alkenyl aromatics include styrene. That is, as the conjugated diene-alkenyl aromatic random copolymer,
For example, styrene-butadiene random copolymer (SB
R), styrene-isoprene random copolymer and the like. The proportion of the alkenyl aromatic in the random copolymer is preferably 5 to 65% by weight, more preferably 7 to 45% by weight. If the proportion of the alkenyl aromatic is too small, the impact resistance may not be sufficiently improved, while if the proportion is too large, the impact resistance may not be sufficiently improved. The component (C) of the present invention is obtained by hydrogenating the double bond part derived from the conjugated diene of the conjugated diene-alkenyl aromatic random copolymer. The rate of hydrogenation (hydrogenation rate) is usually 90% or more, preferably 95% or more. If the hydrogenation rate is too small, the heat stability may be poor. Component (C) of the present invention has an elastic modulus at room temperature is 10000 kg / cm ² or less, preferably of 4000 kg / cm ² or less. When the elastic modulus is too large, the effect of improving impact resistance may be insufficient.
A preferable component (C) is a hydrogenated styrene-butadiene rubber having a styrene unit content of 5 to 65% by weight, more preferably 7 to 45% by weight. In addition,
The method for producing the component (C) is described in, for example, JP-B-42-870.
No. 4 and JP-A-59-133203. A commercially available product may be used as the component (C).

The content of the component (C) in the thermoplastic resin of the present invention is 1 to 50 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the total amount of the components (A) and (B). is there. If the content is too small, the effect of improving impact resistance is not sufficient, while if the content is too large, the thermoplastic resin composition is inferior in rigidity, impact resistance and coating adhesion. In the present invention, as described below, (A) to (D)
In addition to the component, an alkenyl aromatic resin may be used in combination. In this case, the content of the component (C) is (A) component,
The total amount of the components (B) and (C) is 1 to 50 parts by weight, preferably 1 to 30 parts by weight, per 100 parts by weight.

In the present invention, the component (D) is a compatibilizer, and specific examples thereof include the following (D1) to (D9).
Can be raised. (D1): Epoxy compound having no ethylenic or acetylenic unsaturated bond (D2): (i) At least one unsaturated group, that is, carbon-carbon double bond or carbon-carbon triple bond and (ii) in the same molecule. ) Compound having at least one polar group (D3): Oxidized polyolefin wax (D4): In the molecular structure, (i) a carbon atom through an oxygen bridge, and (ii) at least an ethylenic carbon-carbon double bond Alternatively, a silane compound having both a carbon-carbon triple bond and / or a functional group selected from an amino group and a mercapto group, the functional group not directly bonded to a silicon atom (D5): in the same molecule (i ) (OR) (wherein R is hydrogen or an alkyl, aryl, acyl or carbonyldioxy group) and (ii) a carboxylic acid, an acid halide, Compound having at least two identical or different functional groups selected from acid anhydride, acid halide anhydride, acid ester, acid amide, imide, imide, amino and salts thereof (D6): (i) in the same molecule ) Acid halide group and (ii)
Compound having at least one carboxylic acid, carboxylic acid anhydride, acid ester or acid amide group (D7): having a unit of vinyl aromatic compound and a unit of α, β-unsaturated dicarboxylic acid or dicarboxylic acid anhydride A unit of copolymer or vinyl aromatic compound and α,
Copolymer having unit of β-unsaturated dicarboxylic acid imide compound (D8): at least selected from the group consisting of (D1), (D2), (D4), (D5) and (D6) Polyphenylene ether functionalized with one compatibilizing agent (D9): Polyphenylene ether functionalized with at least one compatibilizing agent selected from the group consisting of (D1) to (D7) and a small amount Composition obtained by melt-kneading the above polyamide

The component (D) used in the present invention is (A)
Since polyphenylene ether as a component and polyamide as a component (B) originally have poor affinity, they are melt-kneaded at the same time and polyphenylene ether particles are dispersed only at a particle size of about 10 μm or more, resulting in extremely low mechanical properties. It is added to improve the drawback of not showing.

The compatibilizer of the (D1) group used in the present invention is (1) a condensate of polyhydric phenol (for example, bisphenol A, tetrabromobisphenol A, resorcin, etc.) and epichlorohydrin, and kohl, propylene glycol, Polyethylene glycol and the like) and a condensate of epicudorhydrin.

The (D2) group compatibilizing agent used in the present invention is an unsaturated group, that is, a carbon-carbon double bond or a carbon-carbon triple bond, and an amide bond contained in a polar group or polyamide resin. , A compound having a functional group showing affinity or chemical reactivity with a carboxyl group or an amino group existing at the chain end in the same molecule. Such functional groups include carboxylic acid groups, groups derived from carboxylic acids, that is, various salts or esters substituted with hydrogen atoms or hydroxyl groups of carboxyl groups, acid amides, acid anhydrides, imides,
Functional group such as acid azide, acid halide, or oxazoline, nitrile, epoxy group, amino group, hydroxyl group,
Or, isocyanic acid ester group or the like, a compound having both an unsaturated group and a polar group, that is, an unsaturated carboxylic acid, an unsaturated carboxylic acid derivative, an unsaturated epoxy compound,
Unsaturated alcohols, unsaturated amines, unsaturated isocyanates are used.

Specifically, maleic acid, maleic anhydride, fumaric acid, maleimide, maleic hydrazide,
Reaction product of maleic anhydride and diamine, for example:

[0030]

[Chemical 2]

(However, R represents an aliphatic or aromatic group.)
Those having a structure represented by, such as methyl nadic acid anhydride, dichloromaleic anhydride, maleic acid amide, itaconic acid, itaconic anhydride, soybean oil, tung oil, castor oil,
Natural oils and fats such as linseed oil, hemp oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconut oil, sardine oil, epoxidized natural oils and fats, acrylic acid, butenoic acid,
Crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid,
Angelic acid, tiglic acid, 2-pentenoic acid, 3-pentenoic acid, α-ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-hexene, 2-methyl-2-
Pentenoic acid, 3-methyl-2-pentenoic acid, α-ethylcrotonic acid, 2,2-dimethyl-3-butenoic 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-hexadienoic acid,
Diallylacetic acid, geranium acid, 2,4-decadienoic acid,
2,4-dodecadienoic acid, 9 / 12-hexadecadienoic acid, 9 / 12-octadecadienoic acid, hexadecatrienoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, ricinoleic acid, eleostearine acid,
Oleic acid, aicosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid,
Unsaturated carboxylic acids such as docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid, octacosenoic acid, traacontenoic acid, or esters of these unsaturated carboxylic acids, acid amides, anhydrides, or allyl alcohol, crotyl alcohol, Methyl vinyl carbinol, allyl 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 of the general formula C _n H _2n-5 O
H, C _n H _2n-7 OH, C _n H _2n-9 OH (where n is a positive integer), 3-butene-1,2-
Diol, 2,5-dimethyl-3-hexene-2,5-
Diol, 1.5-hexadiene-3,4-diol,
Unsaturated alcohols such as 2,6-octadiene-4,5-diol or O of such unsaturated alcohols
An unsaturated amine in which the H group is replaced with a —NH ₂ group, glycidyl (meth) acrylate, allyl glycidyl ether, etc. may be mentioned.

Further, low polymerization of butadiene, isoprene and the like (for example, those having an average molecular weight of about 500 to 10,000) or high molecular weight compounds (for example, an average molecular weight of 1)
Maleic anhydride and phenols are added to 0000 or more), those into which an amino group, a carboxylic acid group, a hydroxyl group, an epoxy group and the like are introduced, allyl isocyanate and the like.

The definition of a compound having both an unsaturated group and a polar group in the same molecule in the present invention includes a compound containing two or more unsaturated groups and two or more polar groups (same or different). Needless to say, it is also possible to use two or more specific compounds.

Of these, maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid and glycidyl (meth) acrylate are preferably used, and maleic anhydride and fumaric acid are more preferably used.

The compatibilizer of the (D3) group used in the present invention is usually adjusted by oxidation of a polyolefin wax in the air or in a suspension, and a polyethylene wax or the like is preferable.

The compatibilizer of the (D4) group used in the present invention comprises a) at least one silicon atom bonded to a carbon atom through a bridge of oxygen in the molecular structure, and a)
At least an ethylenic carbon-carbon double bond or carbon-carbon triple bond and / or having a functional group selected from an amino group and a mercapto group, the functional group is not bonded to a silicon atom, a silane compound There, gamma aminopropitriethoxysilane, 2- (3-cyclohexyl) ethyltrimethyloxysilane and the like can be used.

Phases of the (D5) group used in the present invention
Aliphatic polycarboxylic acid, acid ester
Or an acid amide having the general formula (R₁O)_mR (COOR
₂) _n(CONR₃R_Four)_l(Where R is: linear or
A branched saturated aliphatic hydrocarbon having 2 to 20
Having, preferably 2 to 10 carbon atoms
R₁Is hydrogen, an alkyl group, an aryl group, an acyl group,
Or a carbonyldioxy group, particularly preferably hydrogen.
R₂Is hydrogen, an alkyl group, or an aryl group and has carbon atoms
1-20, preferably 1-10, R₃And R_FourIs
Hydrogen, an alkyl group, or an aryl group having 1 to 10 carbon atoms,
Preferably 1-6, more preferably 1-4, m =
1 and n + 1 is an integer of 2 or more, preferably 2 or 3
And n is an integer of 0 or more, l is an integer of 0 or more
Yes, (R₁O) is located at the α-position or β-position of the carbonyl group
2 to 6 between at least two carbonyl groups
The carbon of is present. )
Saturated aliphatic polycarboxylic acid and its derivative compounds. (Ingredients
Physically, the ester compound of saturated aliphatic polycarboxylic acid
Compounds, amide compounds, anhydrides, hydrates, salts and the like.
As saturated aliphatic polycarboxylic acid, citric acid, apple
Acid, agaric acid and the like. Details of these compounds
Is disclosed in Published Patent Publication No. 61-502195.
There is. )

The compatibilizer of the (D6) group used in the present invention is represented by the general formula ((I) -Z- (II)) (wherein
(I) has at least the formula: (X-CO)-(wherein X is
F, Cl, B, I, OH, OR or -O-CO-R,
R is H, an alkyl group or an aryl group), (I
I) is at least a carboxylic acid, an acid anhydride group, an acid amide group, an imide group, a carboxylic acid ester group, an amino group or a hydroxyl group, and the groups (I) and (II) are divalent hydrocarbon bonds. Covalently bonded via Z. ] The compound represented by. (Specifically, it includes chloroformyl succinic anhydride, chloroethanoyl succinic anhydride, trimellitic anhydride acid chloride, trimellitic anhydride acetic anhydride, terephthalic acid chloride and the like.). It consists of one or more compounds selected from the group. However, the compatibility improver in the present invention is
The compound is not limited to those exemplified here, and any compound may be used as long as it is used for the purpose of improving the compatibility between PPE and nylon, and a single or a plurality of compatibilizing agents may be used at the same time. The amount of the compatibility improver is 0 to 30 parts by weight with respect to a total of 100 parts by weight of the polyphenylene ether resin and the polyamide resin. It is not preferable because such problems occur. A preferred blending amount is 0.05 to 25 parts by weight. Further, when the compatibility improver is blended, a radical initiator may be used together.

The component (D) is preferably at least one selected from the group consisting of maleic anhydride, maleic acid, fumaric acid, itaconic acid, citric acid and malic acid. The content of the component (D) in the thermoplastic resin of the present invention is an amount sufficient to compatibilize the component (A) and the component (B), and the total amount of the component (A) and the component (B) is 100. The amount is usually 30 to 30 parts by weight, preferably 0.05 to 25 parts by weight, based on parts by weight. If the content is too large, the heat stability is lowered and the strength is remarkably lowered due to decomposition. In addition,
When compounding the compatibilizer, a radical initiator may be used together.

In the present invention, an alkenyl aromatic resin may be used in addition to the components (A) to (D). The resin has an elastic modulus of 10,000 kg / cm at room temperature.
^It is preferably ² or more, for example, styrene, α-
Examples thereof include polymers or copolymers such as methylstyrene and p-methylstyrene, and specifically, polystyrene, rubber-reinforced polystyrene, poly-α-methylylstyrene, poly-
Examples thereof include p-methylstyrene and styrene-acrylonitrile copolymers, and also include those obtained by grafting a styrene polymer onto polyphenylene ether.

The content of the alkenyl aromatic resin in the thermoplastic resin of the present invention is 60% by weight or less, preferably 1%.
~ 30% by weight. If the content is too large, impact resistance and heat stability of the thermoplastic resin may decrease.

In the present invention, a filler may be used for the purpose of improving rigidity and hardness. Suitable fillers include, for example, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, titanium oxide, magnesium oxide, aluminum silicate, magnesium silicate, calcium silicate, silicic acid,
Hydrous calcium silicate, hydrous aluminum silicate, mica, mineral fiber, xonotlite, potassium titanate / whisker, magnesium oxysulfate, glass balun, glass fiber, glass beads, carbon fiber, inorganic fiber such as stainless fiber, aramid fiber, carbon black And so on. You may use these in combination of 2 or more types.

To obtain the thermoplastic resin composition of the present invention,
The components (A) to (D), and if necessary, the alkenyl aromatic resin, the filler and the like may be blended by a known method and melt kneaded, and the blending and kneading order at that time is arbitrary, and each component After kneading each combination separately, each combination may be mixed and kneaded, or one extruder may be provided with a plurality of feed ports to sequentially feed one or more components along a cylinder. .

The thermoplastic resin composition of the present invention may further contain conventional additives such as flame retardants, plasticizers, antioxidants,
A weathering agent or the like may be added. In particular, additives of polyphenylene ether or nylon are most suitable.

The thermoplastic resin composition of the present invention maintains a good balance in impact resistance, coating film adhesion performance and heat resistance stability and is excellent in processability. Taking advantage of its excellent characteristics, For example, it can be optimally used for automobile outer panel materials, building materials, and the like.

[0046]

The present invention will be described in detail below with reference to examples, but this is merely an example and the present invention is not limited thereto. Formulation (A) shown in Tables 1 and 2,
(C) and (D) were charged into the first feed port of a TEM50 twin-screw kneader manufactured by Toshiba Machine Co., Ltd., and melt-kneaded at a cylinder temperature of 260 ° C. Further, using the second feed port provided between the first feed port and the die, the remaining blending components shown in Tables 1 and 2 were added and melt-kneaded again. Furthermore,
The molten resin extruded from the die was cooled in a water tank and then pelletized by a strand cutter. The pellets thus obtained were vacuum dried at 130 ° C. for 4 hours, and then a cylinder temperature of 270 was obtained by an injection molding machine IS220EN manufactured by Toshiba Machine.
Each test piece was molded under the conditions of ℃, injection pressure of 1200 kg / cm ² , and mold temperature of 80 ℃. The test piece thus molded was tested by the following method to obtain each data.

(1) Melt Index (MI) Pellets of each resin composition were vacuum dried at 140 ° C. for 4 hours, and then the melt index at 280 ° C. under a load of 2.16 kg was determined. (2) Impact resistance (Izod impact test) After molding a 3.2 mmt test piece for Izod test with an injection molding machine, a notch was inserted in accordance with ASTM D256 and an impact test was performed in an atmosphere of 23 ° C. . (3) Flexural Modulus After molding a 3.2 mmt test piece for bending test with an injection molding machine, the test piece was at 23 ° C. according to ASTM D790.
A bending test was performed in an atmosphere.

(4) Heat resistance stability (impact test after thermal aging) After molding a 3.2 mmt test piece for Izod test with an injection molding machine, 10 pieces were placed in a constant temperature bath at 140 ° C.
After leaving it for 0 hour and giving it a heat history, ASTM D256
According to the above, a notch was placed and an impact test was performed in an atmosphere of 23 ° C. (5) Heat Resistance (Heat Deformation Test: HDT) After molding a test piece for heat deformation test of 6.4 mmt with an injection molding machine, a heat deformation test was carried out in accordance with ASTM D648.

(6) Coating adhesion The evaluation was performed using a 150 × 150 × 3 mm plate obtained by injection molding. As the coating material, Recolac 440H (manufactured by Fujikura Kasei Co., Ltd.) was used, and was coated with a coating gun to a thickness of about 25 to 30 μm under normal conditions, and dried in an oven at 80 ° C. for 30 minutes. After drying, 1 hr, 2 hr, 5 hr, 12 hr,
After a lapse of 24 hours, a cellophane tape peeling test (100 cross-cuts having a width of about 2 mm are cross-cut with a knife, and then cellophane tape is applied to peel them off to measure the residual rate of the coating film.).
Was performed to determine the adhesion. The results show the following. All the examples satisfying the conditions of the present invention show satisfactory results in all evaluation items. on the other hand,
The comparative example which does not contain the component (C) which is an essential component of the present invention is inferior in impact resistance and heating stability (comparative examples 1 and 3) or coating film stability (comparative example 2).

[0050]

[Table 1] ----------------------- Example 1 2 3 4 5 Formulation * 1 (A) type PPE PPE PPE PPE PPE amount 48 48 40 40 40 (B) type PA-A PA-A PA-A PA-A PA-B amount 42 42 42 42 45 (C) type 1910P 1320P 1910P 1320P 1320P amount 10 10 20 20 15 (D) Type MAH MAH CA CA CA Amount 0.3 0.3 0.4 0.4 0.4 Other type-----Amount 0 0 0 0 0 Znst 0 0 0.2 0 0.2 −−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−

[0051]

[Table 2]

[0052]

[Table 3] ------------------ Example 1 2 3 4 5 Evaluation MI 24 21 27 25 53 Impact resistance 33 50 58 63 53 Flexural modulus 21600 21100 17900 17300 19800 Heat resistance HDT 188 186 158 161 177 Heat stability Stability Impact resistance after heat aging 21 29 40 43 37 Coating adhesion 1hr after 98 96 99 95 99 2hr after 99 98 100 98 100 5hr after 100 100 100 99 100 12hr after 100 100 100 100 100 24hr after 100 100 100 100 100 −−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−

[0053]

[Table 4]

* 1 Blending values are parts by weight blended. The meanings of the symbols are as follows. (A) PPE: A chloroform solution obtained by homopolymerizing 2,6-dimethylphenol (concentration:
Polyphenylene ether (B) PA-A: number average molecular weight 17500, nylon 6 PA-B: number average molecular weight 12,000, nylon 6 (C) 1910P: Nippon Synthetic Rubber Co., Ltd. hydrogenated styrene-butadiene copolymer, trade name DYNARON (registered trademark), bound styrene amount 30 wt%, hydrogenation rate% 1320P: Japan Synthetic Rubber Co., Ltd. hydrogenated styrene-butadiene copolymer, trade name DYNARON ( (Registered trademark), bound styrene content 10 wt%, hydrogenation rate%

(D) MAH: maleic anhydride CA: citric acid and others (components other than (A) to (D)) SBR: solution polymerization styrene-butadiene copolymer, styrene content 29 wt% SBS: Nippon Synthetic Rubber Co., Ltd. Styrene-butadiene-styrene block copolymer (alkenyl aromatic block copolymer), trade name TR2787, styrene / butadiene weight ratio = 30/70 SEBS: Shell Chemical Co. hydrogenated styrene-butadiene-styrene block copolymer (hydrogen Added alkenyl aromatic block copolymer), trade name Kraton G1
657 Znst: Zinc stearate

[0056]

As described above, according to the present invention, a thermoplastic resin composition containing polyphenylene ether and polyamide as a main component, which has a good balance of impact resistance, coating adhesion and heat stability. It was possible to provide a thermoplastic resin composition which was maintained and was excellent in processability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C08L 25/10 LEE 77/00 LQS LQV

Claims (8)

[Claims] 1. A composition comprising the following components (A) to (D):
The content of the component (A) is 1 to 60% by weight, the content of the component (B) is 40 to 99% by weight, and the content of the component (C) is that of the components (A) and (B). The thermoplastic resin composition is 1 to 50 parts by weight per 100 parts by weight in total, and the content of the component (D) is sufficient to compatibilize the components (A) and (B). (A): Polyphenylene ether (B): Polyamide (C): Hydrogenated conjugated diene-alkenyl aromatic random copolymer having an elastic modulus at room temperature of 10,000 kg / cm ² or less (D): Compatibilizer 2. The component (D) is the following (D1) to (D9).
The thermoplastic resin composition according to claim 1, which is at least one selected from the group consisting of: (D1): Epoxy compound having no ethylenic or acetylenic unsaturated bond (D2): (i) At least one unsaturated group, that is, carbon-carbon double bond or carbon-carbon triple bond and (ii) in the same molecule. ) Compound having at least one polar group (D3): Oxidized polyolefin wax (D4): In the molecular structure, (i) a carbon atom through an oxygen bridge, and (ii) at least an ethylenic carbon-carbon double bond Alternatively, a silane compound (D5) having both a carbon-carbon 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 (D5): (i) ) (OR) (wherein R is hydrogen or an alkyl, aryl, acyl or carbonyldioxy group) and (ii) a carboxylic acid, an acid halide, Compound having at least two identical or different functional groups selected from acid anhydride, acid halide anhydride, acid ester, acid amide, imide, imide, amino and salts thereof (D6): (i) in the same molecule ) Acid halide group and (ii)
Compound having at least one carboxylic acid, carboxylic acid anhydride, acid ester or acid amide group (D7): having a unit of vinyl aromatic compound and a unit of α, β-unsaturated dicarboxylic acid or dicarboxylic acid anhydride A unit of copolymer or vinyl aromatic compound and α,
Copolymer having unit of β-unsaturated dicarboxylic acid imide compound (D8): at least selected from the group consisting of (D1), (D2), (D4), (D5) and (D6) Polyphenylene ether functionalized with one compatibilizer (D9): Polyphenylene ether functionalized with at least one compatibilizer selected from the group consisting of (D1) to (D7) and a small amount thereof Composition obtained by melt-kneading the above polyamide 3. The thermoplastic resin composition according to claim 1, wherein the component (D) is at least one selected from the group consisting of maleic anhydride, maleic acid, fumaric acid, itaconic acid, citric acid and malic acid. 4. The thermoplastic resin composition according to claim 1, wherein the component (C) is a hydrogenated styrene-butadiene random copolymer. 5. The thermoplastic resin composition according to claim 4, wherein the amount of styrene in the component (C) is 5 to 65% by weight. 6. The amount of styrene in the component (C) is 10 to 40.
The thermoplastic resin composition according to claim 4, wherein the thermoplastic resin composition has a weight percentage. 7. The content of component (A) is 5 to 60% by weight, the content of component (B) is 40 to 85% by weight,
The thermoplastic resin composition according to claim 1, wherein the component (C) is a hydrogenated styrene-butadiene random copolymer, and the content of the component (C) is 5 to 30% by weight. 8. The component (A) to (D) according to claim 1 and an alkenyl aromatic resin, wherein the content of the component (A) is 1 to 60% by weight and the content of the component (B) is 40-9
9% by weight, the content of the component (C) is the component (A),
The total amount of the components (B) and (C) is 1 to 50 parts by weight per 100 parts by weight, and the content of the component (D) is sufficient to make the components (A) and (B) compatible with each other. And the content of the alkenyl aromatic resin is 60% by weight or less.