JP3358496B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a polymer alloy containing polyphenylene ether and polyamide having excellent fluidity, which can be molded by injection molding.

[0002]

2. Description of the Related Art Polyamide resin is a thermoplastic resin excellent in mechanical properties, solvent resistance, workability, etc., but is poor in impact resistance, heat stability, etc., and has a large water absorption. The dimensional stability is remarkably poor, and the mechanical properties are significantly reduced due to water absorption. On the other hand, 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 remarkably poor impact resistance and solvent resistance, and also has poor workability due to its high melt viscosity.
In order to make up for the drawbacks of these resins, it has been proposed to use both resins by blending them. However, simply blending loses the good mechanical properties of both resins. Therefore, various blending agents are added at the time of blending a polyphenylene ether resin and a polyamide resin to improve dispersibility and improve mechanical properties (for example, Japanese Patent Publication No. 60-11966, See JP-B-61-10494, JP-A-59-66452, and JP-A-56-49753.) The polyphenylene ether / polyamide resin composition thus obtained is applied to electric / electronic and automotive fields as a material having excellent mechanical properties, heat resistance, solvent resistance, processability, dimensional stability, and moisture absorption. Is being done. Furthermore, in order to improve the fluidity of these resin compositions, it has been proposed to use a low molecular weight polyphenylene ether or polyamide, or to use a fluidity improver for an ester compound or an amide compound. It is still inadequate due to remarkable deterioration, instability of molding processability, and mold contamination.

[0003]

In view of the above situation, an object of the present invention is to provide a thermoplastic resin composition containing a polyamide and a polyphenylene ether as main components, and having excellent fluidity (molding and processing). Gender),
An object of the present invention is to provide a thermoplastic resin composition having an excellent balance between mechanical strength, impact resistance and heat stability.

[0004]

That is, the present invention comprises the following components (A) to (D), the content of the component (A) is 1 to 80% by weight, and the content of the component (B) is Is 20-9
9% by weight, and the content of the component (C) is an amount sufficient to make the components (A) and (B) compatible with each other;
The content of the component is 10 in total of the components (A) and (B).
0.01 to 1 part by weight per 0 parts by weight of component (A)
And the component (B) are compatibilized by the component (C) in the melt-kneading process, and then the fluidity is improved by the component (D). (A): polyphenylene ether (B): polyamide (C): compatibilizer (D): at least one selected from the group consisting of carboxylic acids having two or more carboxyl groups in the molecule or amines containing a nitrogen atom Compound of

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the present invention is a polyphenylene ether, and one or more phenolic compounds represented by the following formula are oxidized with oxygen or an oxygen-containing gas using an oxidative coupling catalyst. Polymers obtained by polymerization are preferred.

[0006]

(Wherein R _{1 to} R ₅ are each independently _one selected from hydrogen, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, at least one of which 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,
Ethylphenyl, allyl and the like can be mentioned.

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
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 formula, for example, a polyvalent hydroxy aromatic compound such as bisphenol-A, tetrabromobisphenol-A, resorcin, hydroquinone, and novolak resin, is represented by the above formula. May be used.

The preferred components (A) include:
2,6-dimethylphenol homopolymer, 2,6-diphenylphenol homopolymer, copolymer of a large amount of 2,6-xylenol and small amount of 3-methyl-6-t-butylphenol, large amount And a small amount of 2,3,6-trimethylphenol.

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

The crystalline aliphatic polyamide used in the present invention includes, for example, those shown below.

These compounds have an equimolar amount of 4-1 carbon atoms.
Saturated aliphatic dicarboxylic acids containing two and 2 to 12 carbon atoms
In this case, a diamine or the like can be used, if necessary, so as to provide an excess of amine terminal groups over carboxyl terminal groups in the polyamide, if desired. Conversely, dibasic acids can be used to provide excess acid groups. Similarly, these polyamides can be successfully prepared from the acid- and amine-forming derivatives of the acids and amines, such as esters, acid chlorides, amine salts, and the like. Representative aliphatic dicarboxylic acids used to make this polyamide include adipic acid, pimelic acid, azelaic acid, suberic acid, sebacic acid, and dodecandionic acid, while typical aliphatic diamines include hexamethylene Diamines and octamethylenediamine are included. In addition, these polyamides are derived from lactams or units of ω-amino acids having 4 to 12 carbon atoms, or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, and aliphatic diamines having 2 to 12 carbon atoms. Compounds, for example, lactams such as ε-caprolactam, ω-laurolactam, 11-aminoundecanoic acid, 12-aminododecanoic acid, or amino acids, and equimolar salts of the above-mentioned various diamines with adipic acid, azelaic acid, sebacic acid, etc. Can be produced by self-condensation or the like.

Examples of polyamides include polyhexamethylene adipamide (nylon 66), polyhexamethylene azeramid (nylon 69), polyhexamethylene sebasamide (nylon 610), and polyhexamethylene dodecanoamide (nylon 612), poly-bis- (p-aminocyclohexyl) methandodecanamide, polytetramethylene adipamide (nylon 46) or polyamides resulting from ring opening of lactams; ie, polycaprolactam (nylon 6), and polylauryl lactam. included. Further, polyamides produced by polymerizing at least two kinds of amines or acids used in producing the above-mentioned polymer, for example, polymers produced from adipic acid, sebacic acid, and hexamethylenediamine can be used. . Further, copolymers such as nylon 66/6, which is a copolymer of nylon 66 and nylon 6, and nylon 6/12 are included.

Among these crystalline polyamides, nylon 46, nylon 6, nylon 66, nylon 11, nylon 12, and the like are preferably used. More preferably, nylon 6, nylon 66 or a mixture of nylon 6 and nylon 66 in any ratio is used. As the terminal functional groups of these polyamides, those having many amine terminals, those having many carboxy terminals, those having a balance between them, and mixtures having any ratio thereof are suitably used.

The aromatic polyamide used in the present invention is a copolyamide containing an aromatic component such as polyhexamethylene isophthalamide (nylon 6I). The thermoplastic copolyamide containing such an aromatic component can be melt-polymerized with aromatic amino acids and / or aromatic dicarboxylic acids such as paraaminomethylbenzoic acid, paraaminoethylbenzoic acid, terephthalic acid, and isophthalic acid as main components. Mean polyamide.

Diamines as 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 and the like can be used. Isocyanates can be used instead of diamines. For example, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate and the like.

The copolymerization component used if necessary is not particularly limited, and may be lactam or ω-C 4 -C 12.
Compounds derived from units of amino acids, or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, and aliphatic diamines having 2 to 12 carbon atoms, for example, ε-caprolactam;
ω-laurolactam, 11-aminoundecanoic acid, 12
-Lactams such as aminododecanoic acid or amino acids, and equimolar salts of the above-mentioned various diamines with adipic acid, azelaic acid and sebacic acid can be used.

Representative examples of thermoplastic aromatic copolyamides comprising these components include copolymerized polyamides of paraaminomethylbenzoic acid and ε-caprolactam (nylon AMBA / 6), 2,2,4- / 2,4 Polyamide (Nylon TMDT, TMDT / 6) containing 4,4-trimethylhexamethylenediamine terephthalate as a main component
I), hexamethylenediamine, isophthalate and / or
Or hexamethylenediamine / terephthalate as a main component, and bis (paraaminocyclohexyl) methane / isophthalate and / or terephthalate or bis (3
-Methyl, 4-aminocyclohexyl) methane isophthalate and / or terephthalate or bis (paraaminocyclohexyl) propaneisophthalate and / or
Or a polyamide (nylon 6I) containing bis (paraaminocyclohexyl) propane terephthalate as a copolymerization component
/ PACM I, nylon 6I / DMPACMI, nylon 6I / PACP I, nylon 6I / 6T / PAC
MI / PACM T, nylon 6I / 6T / DMPA
CM I / DMPACM T, nylon 6I / 6T / P
ACP I / PACP T), which contains hexamethylenediamine / isophthalate or hexamethylenediamine / terephthalate as a main component, ε-caprolactam, 12
Polyamide (nylon) containing aminododecanoic acid, hexamethylenediamine adipate, bis (paraaminocyclohexyl) methane adipate, bis (3-methyl, 4-aminocyclohexyl) methane adipate as a copolymer component 6I, 6I / 6T, 6I / 12, 6
T / 6, 6T / 66, 6I / PACM 6, 6I / DM
PACM 6), bis (para-aminocyclohexyl) methane / isophthalate or bis (3-methyl, 4-aminocyclohexyl) methane, isophthalate as a main component, hexamethylenediamine / dodecane diacid, 12-aminododecanoic acid, etc. (Nylon PACM I / 612, Nylon DMPACM)
I / 12).

Among these aromatic polyamides, amorphous aromatic polyamides are preferably used.

Among the constituent components of the resin used in the present invention,
(A) / (B) content weight ratio of 1/99 to 80/20,
Preferably it is 3/97 to 70/30. More preferably, it is 5/95 to 50/50. When the amount of the component (A) is too small (the amount of the component (B) is too large), the high-temperature stiffness is reduced. On the other hand, when the amount of the component (A) is too large (the component (B) is too small), the impact resistance and the fluidity are reduced. It is not possible to obtain a preferable molded article having a remarkable decrease in the properties.

In the present invention, the component (C) is a compatibilizer, and specific examples thereof include the following (C1) to (C8)
Can be given. (C1): an epoxy compound having no ethylenic or acetylenic unsaturated bond. (C2): (ii) at least one unsaturated group, ie, a carbon-carbon double bond or a carbon-carbon triple bond, in the same molecule; ) Compound having at least one polar group (C3): oxidized polyolefin wax (C4): (i) a carbon atom via a cross-linking of oxygen in the molecular structure, and (ii) at least an ethylenic carbon-carbon double bond Or a silane compound 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 (C5): ) (OR) wherein R is hydrogen or an alkyl, aryl, acyl or carbonyldioxy group; and (ii) a carboxylic acid, acid halide, Compounds having at least two identical or different functional groups selected from acid anhydrides, acid halide anhydrides, acid esters, acid amides, imides, imides, aminos and salts thereof (C6): (i) in the same molecule ) Acid halide groups and (ii)
Compound having at least one carboxylic acid, carboxylic anhydride, acid ester, or acid amide group (C7): having a unit of a vinyl aromatic compound and a unit of an α, β-unsaturated dicarboxylic acid or a dicarboxylic anhydride. Copolymer, or units of vinyl aromatic compound and α,
Copolymer having units of imide compound of β-unsaturated dicarboxylic acid (C8): (C1), (C2), (C4),
Polyphenylene ether functionalized with at least one compatibilizer selected from the group consisting of (C5) and (C6)

The component (C) used in the present invention comprises (A)
Since the polyphenylene ether as the component and the polyamide as the component (B) originally have poor affinity, they are melt-kneaded at the same time, and the polyphenylene ether particles are dispersed only with a particle diameter of about 10 μm or more. It is blended in order to improve the disadvantage of not showing.

The compatibilizer of the (C1) group used in the present invention includes (1) a condensate of polyhydric phenol (for example, bisphenol A, tetrabromobisphenol A, resorcin, etc.) and epichlorohydrin, and coal, propylene glycol, Polyethylene glycol, etc.) and epicudolhydrin.

The compatibilizer of the group (C2) used in the present invention comprises an unsaturated group, that is, a carbon-carbon double bond or a carbon-carbon triple bond, and a polar group, that is, an amide bond contained in a polyamide resin. It is a compound having a functional group exhibiting affinity or chemical reactivity with a carboxyl group or an amino group existing at the chain end in the same molecule. Examples of such a functional group include a carboxylic acid group, a group derived from a carboxylic acid, that is, various salts and esters substituted with a hydrogen atom or a hydroxyl group of a carboxyl group, an acid amide, an acid anhydride, an imide,
Acid azide, acid halide, or oxazoline, functional group such as nitrile, epoxy group, amino group, hydroxyl group,
Or, an isocyanate group and the like, and 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 and unsaturated isocyanates are used.

Specifically, maleic acid, maleic anhydride, fumaric acid, maleimide, maleic hydrazide,
A reaction product of maleic anhydride and a diamine, for example,

[0027]

(Where R represents an aliphatic or aromatic group)
Those having a structure represented by, for example, methylnadic anhydride, dichloromaleic anhydride, maleic 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, 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-dodesenic acid, 5-dodesenic acid, 4-tetradecenoic acid, 9-tetradecenoic acid,
9-hexadecenoic acid, 2-octadecenoic acid, 9-octadecenoic acid, eicosenoic acid, docosenoic acid, erucic acid, tetracosenoic acid, mycolipene acid, 2,4-hexadienoic acid,
Diallylacetic acid, geranic 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, eleostearin acid,
Oleic acid, eicosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid,
Unsaturated carboxylic acids such as docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid, octacosenic acid, and traaconic 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-undecene-1-ol, propargyl alcohol, 1,4
-Pentadien-3-ol, 1,4-hexadiene-
3-ol, 3,5-hexadien-2-ol, 2,
4-hexadien-1-ol, general formula Cn H _2n-5 O
_{H, Cn H 2n-7 OH} , Cn H 2n-9 OH ( where, n is a positive integer) the alcohol represented by the 3-butene-1,2
Diol, 2,5-dimethyl-3-hexene-2,5-
Diols, 1,5-hexadiene-3,4-diol,
Unsaturated alcohols such as 2,6-octadiene-4,5-diol, or O
Examples thereof include an unsaturated amine in which the H group is replaced by a —NH ₂ group, glycidyl (meth) acrylate, and allyl glycidyl ether.

In addition, low polymerization (for example, those having an average molecular weight of about 500 to 10,000) or high molecular weight substances (for example, having an average molecular weight of 1 to 4), such as butadiene and isoprene.
0000 or more) to which maleic anhydride and phenols are added, or those into which an amino group, a carboxylic acid group, a hydroxyl group, an epoxy group, etc. are introduced, and allyl isocyanate.

In the present invention, the definition of a compound having both an unsaturated group and a polar group in the same molecule includes a compound containing two or more unsaturated groups and two or more (same or different) polar groups. 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 more preferably maleic anhydride and fumaric acid are used.

The compatibilizer of the group (C3) used in the present invention is usually adjusted by oxidizing a polyolefin wax in the air or in a suspension, and a polyethylene wax or the like is preferable.

The compatibilizers of the group (C4) used in the present invention include, in the molecular structure, a) at least one silicon atom bonded to a carbon atom via an oxygen bridge;
A silane compound having at least both an ethylenic carbon-carbon double bond or 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 bonded to a silicon atom; Yes, gamma aminopropitriethoxysilane, 2- (3-cyclohexyl) ethyltrimethoxysilane, and the like can be used.

The compatibilizing agent of the (C5) group used in the present invention is an aliphatic polycarboxylic acid, acid ester or acid amide and has the general formula (R ₁ O) m R (COOR)
₂ ) n (CONR ₃ R ₄ ) l (where R is a linear or branched saturated aliphatic hydrocarbon, from 2 to 20)
, Preferably 2 to 10 carbon atoms, and R ₁ is hydrogen, an alkyl group, an aryl group, an acyl group,
Or carbonyldioxy group, particularly preferably hydrogen, R ₂ is hydrogen, an alkyl group, or an aryl group having 1 to 20, preferably 1 to 10 carbon atoms, and R ₃ and R ₄ are hydrogen, an alkyl group, Or an aryl group having 1 to 10 carbon atoms,
Preferably 1-6, more preferably 1-4, m =
And n + 1 is an integer of 2 or more, preferably 2 or 3.
Wherein n is an integer of 0 or more; l is an integer of 0 or more; (R ₁ O) is located at the α-position or β-position of the carbonyl group; There are ~ 6 carbons. A) a saturated aliphatic polycarboxylic acid and a derivative compound thereof. (Specifically, examples thereof include ester compounds, amide compounds, anhydrides, hydrates, and salts of saturated aliphatic polycarboxylic acids.
Examples of the saturated aliphatic polycarboxylic acid include citric acid, malic acid, agaric acid and the like. Details of these compounds are disclosed in Published Patent Publication No. 61-502195. )

The compatibilizing agent of the group (C6) used in the present invention has the general formula ((I) -Z- (II)) wherein
(I) is at least a compound of the formula: (X—CO) — (where 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 ester group, an amino group or a hydroxyl group, and the groups (I) and (II) are divalent hydrocarbon bonds. It is covalently bonded through Z. ). (Specific examples include chloroformyl succinic anhydride, chloroethanoyl succinic anhydride, trimellitic anhydride 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:
It is not limited to the compounds exemplified herein, and any compound used for the purpose of improving the compatibility between polyphenylene ether and polyamide may be used, and a single or a plurality of compatibilizers may be used simultaneously. The compatibility improver (C) is added in an amount of 0.01 to 30 parts by weight, based on 100 parts by weight of the polyphenylene ether-based resin (A) and the polyamide resin (B) in total. Exceeding this is not preferred because a drop in heat stability and a significant drop in strength due to decomposition and the like occur. The preferred amount is 0.05
It is from 25 parts by weight to 25 parts by weight.

The component (C) is preferably at least one selected from the group consisting of maleic anhydride, maleic acid, fumaric acid, itaconic acid, citric acid and malic acid.
When compounding the compatibilizer, a radical initiator may be used in combination.

The component (D) used in the present invention is at least one compound selected from the group consisting of carboxylic acids having two or more carboxyl groups in the molecule, acid anhydrides, and amines containing two or more nitrogen atoms. is there. Specific compounds of carboxylic acids having two or more carboxyl groups in the molecule include succinic acid, glutaric acid, adipic acid, pimelic acid,
Suberic acid, sebacic acid, azelaic acid, nonamethyldicarboxylic acid, undecamethylenedicarboxylic acid, methylsuccinic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, tetramethylsuccinic acid, pinaconic acid, d-camphoric acid, acetyl anhydride Malic acid, isovaleric anhydride, isobutyric anhydride, succinic anhydride, heptanoic anhydride, methylsuccinic anhydride, d-tartaric acid, 1-tartaric acid, 1-malic acid,
Dioxytartaric acid, dl-bromosuccinic acid, dl-dibromosuccinic acid, 1,4-pyrone-2,6-dicarboxylic acid,
dl-aspartic acid, dl-isocamphoric acid, 1-
1 cyclopropanedicarboxylic acid, dl-citramalic acid,
Maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, aconitic acid, citric acid, malic acid, agaric acid, and the like. Specific compounds of amines containing two or more nitrogen atoms include hexamethylenediamine, hexamethylenetetramine, octamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2 , 4,4-trimethylhexamethylenediamine, meta-xylylenediamine,
Para-xylylenediamine, bis (p-aminocyclohexyl) methane, bis (p-aminocyclohexyl) propane, bis (3-methyl, 4-aminocyclohexyl)
Examples thereof include methane, 1,3-bis (aminomethyl) cyclohexane, and 1,4-bis (aminomethyl) cyclohexane. Among them, saturated aliphatic dicarboxylic acids and their anhydrides are particularly preferred. Most preferred are succinic acid, methyl succinic acid, succinic anhydride, methyl succinic anhydride, adipic acid, sebacic acid. The method of adding the compound of the component (D) is as follows. The component (A) and the component (B) are added after being compatibilized by the component (C) in the melt-kneading process. An improvement in performance is achieved. When compatibilizing the component (A) and the component (B) with the component (C) in the melt-kneading process, if the component (D) of the fluidity improver is present, the compatibilizing action of the compatibilizing agent (C) is reduced. Undesirably inhibits. The component (B) to be compatibilized in the melt-kneading process by the component (A) and the component (C) is preferably at least 30% or more of the component (B) finally contained in the composition. If it is less than 30%, a decrease in mechanical strength is extremely undesirable. At this time, the remaining component (B) is preferably added together with the component (D).

In order to improve the impact resistance of the resin used in the present invention, natural and synthetic polymer materials (rubber-like substances) which are elastic at room temperature can be used. Particularly preferred rubbers include ethylene propylene rubber, ethylene-propylene-non-conjugated diene rubber, ethylene-butene-1 rubber, ethylene-butene-1-non-conjugated diene rubber, polybutadiene, styrene-butadiene block copolymer rubber,
Styrene-butadiene-styrene block copolymer rubber,
Styrene-butadiene copolymer rubber, partially hydrogenated styrene
Butadiene-styrene block copolymer rubber, styrene-
Isoprene block copolymer rubber, partially hydrogenated styrene-isoprene block copolymer rubber, polyurethane rubber, styrene graft-ethylene-propylene-non-conjugated diene rubber, styrene-graft-ethylene-propylene rubber,
Styrene / acrylonitrile-graft-ethylene-propylene-non-conjugated diene rubber, styrene / acrylonitrile-graft-ethylene-propylene rubber, or a mixture thereof is used. Further, a modified rubber modified with a functional monomer including another acid or epoxy may be used. The compounding amount of the rubber-like substance is 100 total of polyphenylene ether resin and polyamide resin.
0 to 100 parts by weight based on parts by weight. If the amount of the rubber-like substance is more than 100 parts by weight, the rigidity of the resin composition is not significantly reduced.

An alkenyl aromatic resin may be used as the resin used in the present invention. The resin preferably has an elastic modulus at room temperature of 10,000 kg / cm ² or more. For example, styrene, α-methylstyrene, p-
Polymers or copolymers such as methyl styrene,
Specifically, polystyrene, rubber-reinforced polystyrene, poly-α-methylelstyrene, poly-p-methylstyrene,
Styrene-acrylonitrile copolymer and the like,
Further, those obtained by grafting a styrene-based polymer to polyphenylene ether are also included.

The content of the alkenyl aromatic resin is 60% by weight or less, preferably 1 to 30% by weight. If the content is excessive, the impact resistance and heat resistance of the thermoplastic resin are undesirably reduced.

In the resin used in the present invention, various fillers may be used in addition to mica in order to increase mechanical strength. 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, talc, kaolin, mica And inorganic fibers such as mineral fibers, zonotolite, potassium titanate whisker, magnesium oxysulfate, glass balun, glass fibers, glass beads, carbon fibers and stainless steel fibers, aramid fibers, and carbon black. These may be used in combination of two or more.

The thermoplastic resin composition of the present invention may further contain conventional additives such as a flame retardant, a plasticizer, an antioxidant,
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 has heat resistance,
It has good impact resistance and heat stability, and is particularly excellent in workability, and is used for thin molded products and large molded products by utilizing its excellent features. It can also be used as a material for automobile outer panels and building materials.

[0045]

The present invention will be described in detail with reference to the following examples.
However, this is merely an example, and the present invention is not limited to this.
It is not something to be done. The resin compositions of Examples and Comparative Examples are shown in Tables.
Biaxial kneading of TEM50 made by Toshiba Machine with the composition shown in 1 and 2.
From the upstream side of the feed port using a
The raw materials are charged and melted at a cylinder temperature of 260 ° C.
Melt and knead, cool the molten resin extruded from the die in a water bath
After rejection, it was obtained by pelletizing with a strand cutter. Next
The pellets were vacuum dried at 110-130 ° C for 4 hours.
After that, the injection molding machine IS220EN manufactured by Toshiba Machine Co., Ltd.
Temperature 290 ° C, injection pressure 1200kg / cm ^Two,
A tape for measuring mechanical strength at a mold temperature of 80 ° C
A piece was molded.

(1) Melt Index (MI) The pellets of each resin composition were vacuum-dried at 140 ° C. for 5 hours, and the melt index was determined at 280 ° C. under a load of 2.16 kg. (2) Impact resistance (Izod impact test) After a 3.2 mmt Izod test test piece was molded by an injection molding machine, a notch was inserted according to ASTM D256, and an impact test was performed in a 23 ° C atmosphere. . (3) Tensile elongation After molding a 3.2 mmt tensile test test piece with an injection molding machine, the test piece was cooled to 23 ° C. in accordance with ASTM D638.
A tensile test was performed in an atmosphere.

From the above results, it can be understood that the examples of the present invention have remarkably improved fluidity, and that when the fluidity is improved, the decrease in mechanical strength such as tensile elongation and impact strength is usually small.

[0048]

Table 1----------------------------------------Example 1 Example 2 Example 3 Comparison Example 1 Comparative Example 2 Formulation * 1 Feed position (A) Type 1 PPE PPE PPE PPE PPE amount 40 40 40 40 40 (E) Type 1 EPSA EPSA EPSA EPSA EPSA EPSA amount 12 12 12 12 12 (C) Type 1 MAH MAH MAH MAH MAH amount 0.4 0.4 0.4 0.4 0.4 (B) Type 2 PA6-A PA6-A PA6-A PA6-A PA6-A amount 38 38 38 48 38 (B) Type 3 PA6-A PA6-A PA6-A PA6- A amount 10 10 10 10 (D) Type 3 DADD MAH SAH STA amount 0.2 0.2 0.1 0.5 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−− MI (dg / min) 6.0 9.5 16 5 7.4 Mechanical strength Impact resistance (kg ・ cm / cm) 18 18 19 47 14 Tensile elongation (%) 55 50 61 68 42 −−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

[0049]

Table 2 Table 3 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Formulation * 1------------------------------------------------------------------------------ Feed position (A) Type 1 PPE PPE PPE PPE amount 40 40 40 40 (E) Type 1 EPSA EPSA EPSA EPSA amount 12 12 12 12 (C) Type 1 MAH MAH MAH MAH MAH amount 0.4 0.4 0.4 0.4 (B) Type 2 PA6 -B PA6-A PA6-A PA6-A amount 48 48 48 38 (B) Type 3 PA6-A amount 10 (D) Type 1 SAH amount 0.1 (D) Type 2 SAH amount 0.1 −−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−− MI (dg / min) 16 18 17 4 Mechanical strength Impact resistance (kg ・ cm / cm) 4 9 12 50 Tensile elongation (%) 10 20 24 65 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

[0050]

Table 3--------------------------------------------------------------------------------------------------------- Example 7 Example 6 Formulation * 1 Feed position (A) Type 1 PPE PPE PPE PPE PPE amount 34 34 34 34 34 (E) Type 1 EPSA EPSA EPSA EPSA EPSA EPSA amount 8 8 8 8 8 (C) Type 1 MAH MAH MAH MAH MAH amount 0.8 0.8 0.8 0.8 0.8 (B) type 2 PA12-A PA12-A PA12-A PA12-A PA12-A amount 28 28 38 38 28 (B) type 2 PA12-B PA12-B PA12-B PA12- B PA12-B amount 20 20 20 20 20 (B) type 3 PA12-A PA12-A PA12-A amount 10 10 10 (D) type 3 SAH SAH SEA amount 0.1 0.2 0.2 (D) type 1 amount (D) type 2 SAH amount 0.1 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− MI (dg / min) 21 61 30 9 25 Mechanical strength Impact resistance (kg ・ cm / cm) 40 18 11 51 31 Tensile elongation (%) 66 48 40 60 56 −−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−

* 1 Formulation Numerical values are parts by weight blended. The meanings of the symbols are as follows. (A) PPE: chloroform solution obtained by homopolymerizing 2,6-dimethylphenol (concentration: 0.5 g)
/ Dl), polyphenylene ether having a logarithmic viscosity at 30 ° C. of 0.40 (B) PA6-A: nylon 6 having a number average molecular weight of 12,000 PA6-B: nylon 6 PA12-A having a number average molecular weight of 10,000: relative viscosity of 1.6 Nylon 12 PA12-B: Nylon 12 with relative viscosity of 1.8 (C) Compatibilizer MAH: Maleic anhydride (D) Flow improver DADD: Diaminododecane STA: Stearylamine MAH: Maleic anhydride SAH: Succinic anhydride Acid SEA: Sebacic acid (E) Impact modifier EPSA: Styrene-acrylonitrile-graft-E
PDM

[0052]

As described above, the thermoplastic resin composition according to the present invention has excellent fluidity (moldability).
A thermoplastic resin composition having a good balance of mechanical strength, impact resistance and heat stability was provided.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 71/12 C08L 91:06 // (C08L 77/00 C08K 5/15 71:12 5/54 91:06) (56) References Japanese Unexamined Patent Publication No. 9-217001 (JP, A) Japanese Unexamined Patent Publication No. 1-129059 (JP, A) Japanese Unexamined Patent Publication No. Hei 7-157651 (JP, A) Japanese Unexamined Patent Publication No. 2-284595 (JP, A) (58) Int.Cl. ⁷ , DB name) C08L 71/10-71/12 C08L 77/00-77/12 C08K 5/00-5/59

Claims (6)

(57) [Claims] 1. It comprises the following components (A) to (D):
The content of the component (A) is 1 to 80% by weight, the content of the component (B) is 20 to 99% by weight, and the content of the component (C) is a combination of the components (A) and (B). The amount of the component (D) is 0.01 to 1 part by weight per 100 parts by weight of the total amount of the components (A) and (B). And a component (B), which is compatibilized by the component (C) in the melt-kneading process, and then has a fluidity improved by the component (D). (A): polyphenylene ether (B): polyamide (C): compatibilizer (D): selected from the group consisting of carboxylic acids having two or more carboxyl groups in the molecule or amines having two or more nitrogen atoms At least one compound 2. The component (C) comprises the following components (C1) to (C8)
The thermoplastic resin composition according to claim 1, which is at least one selected from the group consisting of: (C1): an epoxy compound having no ethylenic or acetylenic unsaturated bond. (C2): (ii) at least one unsaturated group, ie, a carbon-carbon double bond or a carbon-carbon triple bond, in the same molecule; ) Compound having at least one polar group (C3): oxidized polyolefin wax (C4): (i) a carbon atom via a cross-linking of oxygen in the molecular structure, and (ii) at least an ethylenic carbon-carbon double bond Or a silane compound 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 (C5): ) (OR) wherein R is hydrogen or an alkyl, aryl, acyl or carbonyldioxy group; and (ii) a carboxylic acid, acid halide, Compounds having at least two identical or different functional groups selected from acid anhydrides, acid halide anhydrides, acid esters, acid amides, imides, imides, aminos and salts thereof (C6): (i) in the same molecule ) Acid halide groups and (ii)
Compound having at least one carboxylic acid, carboxylic anhydride, acid ester, or acid amide group (C7): having a unit of a vinyl aromatic compound and a unit of an α, β-unsaturated dicarboxylic acid or a dicarboxylic anhydride. Copolymer, or units of vinyl aromatic compound and α,
Copolymer having units of imide compound of β-unsaturated dicarboxylic acid (C8): at least selected from the group consisting of (C1), (C2), (C4), (C5) and (C6) Polyphenylene ethers functionalized with a kind of compatibilizer 3. The thermoplastic resin composition according to claim 1, wherein the component (C) 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 (D) is at least one selected from the group consisting of saturated aliphatic dicarboxylic acids and anhydrides thereof. 5. The method according to claim 1, wherein the component (D) is succinic acid, methylsuccinic acid, succinic anhydride, methylsuccinic anhydride, adipic acid,
The thermoplastic resin composition according to claim 1, which is at least one selected from the group consisting of sebacic acid. 6. The component (B) first compatibilized in the melt-kneading process by the component (A) and the component (C) is from 30% to 90% of the component (B) finally contained in the composition. The thermoplastic resin composition according to claim 1, which is obtained by adding the remaining component (B) together with the component (D) in a subsequent step and melt-kneading the mixture.