JP2001026712A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition comprising polyphenylene ether (and/or polypropylene) and polyamides which is improved in salt damage resistance without seriously impairing the physical balance among excellent impact strength, rigidity, heat resistance, fluidity and the like. SOLUTION: This thermoplastic resin composition comprises the following ingredients A to D and is prepared by being compatibilized with the ingredient D: (A) 3-75 wt.% of at least one of thermoplastic resins selected from the group consisting of a polyphenylene ether and a polypropylene having a crystallinity of >=35%; (B) 10-95 wt.% of at least one of polyamides selected from the group consisting of polyamide 6, polyamide 6/6, polyamide 4/6 and polyamide 6-6/6; (C) 1-50 wt.% of at least one of polyamides selected from the group consisting of a copolyamide of polyamide 6-constituting units with >=8C aliphatic polyamide-constituting units and an aromatic polyamide where nuclei are hydrogenated; and (D) a compatibilizer.

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 polyphenylene ether-polyamide resin having improved impact resistance, salt damage resistance without impairing excellent rigidity and fluidity of polyphenylene ether-polyamide resin composition and polypropylene-polyamide resin composition. The present invention relates to a composition and a polypropylene-polyamide resin composition.

[0002]

2. Description of the Related Art Resin compositions containing polyphenylene ether or polypropylene and polyamide have been used in the fields of automobiles, electric and electronic fields mainly by injection molding, taking advantage of their excellent mechanical properties. However, the polyphenylene ether-polyamide resin composition and the polypropylene-polyamide resin composition usually cause cracks in stressed portions due to the action (salt damage) of an aqueous solution of calcium chloride, which is usually used as a snow melting agent on roads and the like. Can lead to destruction. In order to improve this drawback, attempts have been made to use polyamide having a large molecular weight, to add a large amount of rubber component, or to add an inorganic filler, but this is still insufficient.

[0003]

Under these circumstances, the problem to be solved by the present invention is to provide the polyphenylene ether-polyamide resin composition and the polypropylene-polyamide resin composition with excellent impact strength, moisture stiffness and fluidity. -Polyphenylene ether-polyamide resin composition and polypropylene with improved salt damage resistance without impairing
It is in providing a polyamide resin composition.

[0004]

That is, the present invention comprises the following components (A) to (D), wherein the content of (A) is 3
-75 wt%, the content of (B) is 10-95 wt%, the content of (C) is 1-50 wt%,
The content of (D) is a thermoplastic resin composition that is a sufficient amount to make (A) and (B) compatible with each other. It is obtained by adding (B) and (C) to the mixture and compatibilizing by a melt kneading process, or (A) to (C) are compatibilized by (D) in a melt kneading process. The present invention relates to the obtained thermoplastic resin composition. (A): at least one thermoplastic resin selected from the group of thermoplastic resins consisting of polyphenylene ether and polypropylene having a degree of crystallinity of 35% or more (B): polyamide 6, polyamide 66, polyamide 4
And at least one polyamide selected from polyamide 6 and polyamide 6-66 (C): a unit constituting polyamide 6 and carbon atoms of 8
At least one polyamide selected from the polyamide group consisting of a polyamide which is a copolymer of the above-mentioned aliphatic polyamide and a unit comprising a hydrogenated aromatic polyamide (D): a compatibilizer

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION (A) of the present invention is at least one thermoplastic resin selected from the group consisting of polyphenylene ether and polypropylene having a crystallinity of 35% or more.

The polyphenylene ether is preferably a polymer obtained by oxidatively polymerizing one or more of the phenol compounds represented by the following formulas with oxygen or an oxygen-containing gas using an oxidative coupling catalyst. (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 is
o-propyl, pri-, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl, allyl And so on.

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 polyphenylene ether, phenol compounds other than the above-mentioned formulas, for example, bisphenol-A, tetrabromobisphenol-A, resorcinol,
A copolymer of a polyvalent hydroxy aromatic compound such as hydroquinone or a novolak resin and a compound represented by the above formula may be used.

Preferred examples of the polyphenylene ether include a homopolymer of 2,6-dimethylphenol, a homopolymer of 2,6-diphenylphenol, a large amount of 2,6-xylenol and a small amount of 3-methyl-6. −
Copolymers of t-butylphenol and copolymers of a large amount of 2,6-xylenol and a small amount of 2,3,6-trimethylphenol are exemplified.

The polypropylene having a crystallinity of 35% or more is
It is crystalline and has a crystallinity of 35 as measured by X-ray diffraction.
% Or more, preferably 40% or more, more preferably 45%
Above, particularly preferably 50% or more. As this crystalline polypropylene, a homopolymer of propylene can be used, or a copolymer of propylene and another α-olefin can be used. Examples of other α-olefins used herein include α-olefins having 2 to 20 carbon atoms excluding propylene. Specifically, ethylene, butene-1, pentene-1,
Hexene-1, 4-methylpentene-1, octene-1, decene
-1 and mixtures thereof. The polypropylene used in the present invention contains a repeating unit derived from an α-olefin as described above in an amount of usually at most 50 mol%, preferably at most 40 mol%, most preferably at most 30 mol%. ing. The polypropylene therefore contains propylene-derived repeating units in an amount of usually at least 50 mol%, preferably at least 40 mol%, most preferably at least 70 mol%. The repeating unit derived from propylene and the repeating unit derived from α-olefin may be randomly bonded, or a unit in which a plurality of repeating units derived from propylene are bonded, and from the α-olefin. A unit in which a plurality of derived repeating units are bonded may be bonded. Further, for example, a multi-stage polymerization method (for example, a two-stage polymerization method) using a Ziegler-Natta-based catalyst containing a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components and an organic metal catalyst is used. Utilizing propylene chains and other α-olefins produced by using propylene and other α-olefins as monomers.
It may be a highly homogeneous composition in which olefin chains are uniformly mixed with a molecular level, or a block copolymer in which a bond is formed between both (in the present invention, both are collectively referred to as “block”). Copolymer ").

As the polypropylene having a high crystallinity as described above, a polypropylene having high isotacticity is used. In order to obtain isotactic polypropylene in a high yield, it is preferable to use a Ziegler-type catalyst containing a trichloride of Ti, V, Cr or Zr and an alkylaluminium. Further, a method of removing the non-isotactic polymer in the polypropylene by using a method such as extraction may be used.

In particular, in the present invention, the intrinsic viscosity of polypropylene as measured in decalin at 135 ° C. is usually in the range of 1 to 10 dl / g, preferably 1 to 5 dl / g, and is measured by ASTM-D1238. A crystalline polypropylene having a melt flow rate in the range of usually 0.01 to 500 g / 10 min, preferably 0.05 to 100 g / 10 min is used.

(B) of the present invention is at least one polyamide selected from polyamide 6, polyamide 66, polyamide 46 and polyamide 6-66. That is,
(B) is polyhexamethylene adipamide (polyamide 6
6), polytetramethylene adipamide (polyamide 4
6) or polyamides formed by ring opening of lactams; polycaprolactam (polyamide 6) and polyamide 66, which is a copolymer of polyamide 66 and polyamide 6,
At least one polyamide selected from the copolymer No. 6.

The polyamide 6 used in the present invention is usually called nylon 6, and is obtained by polymerization of ε-caprolactam or the like. Polyamide 66, polyamide 46 and polyamide 6-66 are equimolar amounts of saturated aliphatic dicarboxylic acids containing 4 or 6 carbon atoms and 6 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. in addition,
These polyamides are units of units of lactams of 6 carbon atoms or ω-amino acids of 6 carbon atoms, or equimolar amounts of compounds derived from aliphatic dicarboxylic acids of 6 carbon atoms and aliphatic diamines of 6 carbon atoms. It can be produced by self-condensation of a salt or the like.

Preferred as (B) is polyamide 6
6 or polyamide 6 or a mixture of nylon 6 and nylon 66 in any ratio. 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.

Further, an aromatic polyamide can be added. The aromatic polyamide is, for example, a copolyamide containing an aromatic component such as polyhexamethylene isophthalamide (nylon 6I). The aromatic polyamide is a polyamide containing an aromatic amino acid and / or an aromatic dicarboxylic acid as an aromatic component. Examples of the aromatic dicarboxylic acid include paraaminomethylbenzoic acid, paraaminoethylbenzoic acid, terephthalic acid, and isophthalic acid.

The copolymerization components used as required are not particularly limited, and may be lactams or units of 4 to 12 ω-amino acids of carbon source, or aliphatic dicarboxylic acids of 4 to 12 carbon atoms, and 2 to 2 carbon atoms. Compounds derived from 12 aliphatic diamines, such as 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), containing hexamethylenediamine / isophthalate or hexamethylenediamine / terephthalate as a main component,
Polyamide (nylon 6I, 6I / 6T, 6I / 1) containing adipate, bis (para-aminocyclohexyl) methane adipate, bis (3-methyl, 4-aminocyclohexyl) methane adipate or the like as a copolymer component
2, 6T / 66, 6I / PACM 6, 6I / DMPA
CM 6), bis (para-aminocyclohexyl) methane / isophthalate or bis (3-methyl, 4-aminocyclohexyl) methane / isophthalate as a main component, and hexamethylenediamine / dodecane diacid salt as a copolymer component. Polyamide (Nylon PACM I / 61
2,).

(C) The present invention relates to a polyamide group comprising a polyamide which is a copolymer of a unit constituting polyamide 6 and a unit constituting an aliphatic polyamide having 8 or more carbon atoms, and a nucleated hydrogenated aromatic polyamide. At least one polyamide selected from the group consisting of: As a specific example of the polyamide which is a copolymer of the unit constituting the polyamide 6 and the unit constituting the aliphatic polyamide having 8 or more carbon atoms, the unit constituting the polyamide 6 is ε-caprolactam. The units constituting the aliphatic polyamide having 8 or more carbon atoms include ω-laurolactam, lactams such as 11-aminoundecanoic acid and 12-aminododecanoic acid, or amino acids, and aliphatic dicarboxylic acids having 8 or more carbon atoms. Equimolar salts of hexamethylenediamine or aliphatic diamines having 8 or more carbon atoms with adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and the like.

In the component (C) of the polyamide constituting a copolymer which is a copolymer of the unit constituting the polyamide 6 and the unit constituting the aliphatic polyamide having 8 or more carbon atoms, the aliphatic polyamide having 8 or more carbon atoms is used. Components are (C) in weight ratio
It is preferably 15% or more of the whole, more preferably 30% or more. Preferably, it is a copolymer of ε-caprolactam and ω-laurolactam.

The hydrogenated aromatic polyamide is composed of a unit of an alicyclic dian inducer and a unit of an aliphatic dicarboxylic acid inducer, ε-caprolactam, ω-laurolactam, 11-aminoundecanoic acid, 12- At least one polyamide comprising a unit of a lactam such as aminododecanoic acid and an alicyclic diamine inducer, an aliphatic dicarboxylic acid inducer and, in some cases, an aromatic dicarboxylic inducer unit. Specific examples of alicyclic diamines include bis (p-aminocyclohexyl) methane, bis (p-aminocyclohexyl) propane, bis (3-methyl, 4-aminocyclohexyl) methane, and 1,3-bis (aminomethyl) cyclohexane , 1,4-bis (aminomethyl) cyclohexane. The aliphatic dicarboxylic acid is an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, and particularly preferably has 12 carbon atoms. Examples of the aromatic dicarboxylic acid include paraaminomethylbenzoic acid, paraaminoethylbenzoic acid, terephthalic acid, and isophthalic acid. Particularly, isophthalic acid is preferred.

Preferred examples of the hydrogenated aromatic polyamide include bis (3-methyl, 4-aminocyclohexyl)
Copolymer polyamide of methane and dodecanedicarboxylic acid, ω
-Copolyamide of laurolactam, bis (3-methyl, 4-aminocyclohexyl) methane and terephthalic acid.

(D) of the present invention is a compatibilizer, and specific examples thereof include the following (D1) to (D3). (D1): Compound having both (i) at least one unsaturated group, ie, a carbon-carbon double bond or a carbon-carbon triple bond, and (ii) at least one polar group in the same molecule. (D2): In a molecular structure (I) having both a carbon atom via an oxygen bridge, and (ii) at least a functional group selected from an ethylenic carbon-carbon double bond or a carbon-carbon triple bond and / or an amino group and a mercapto group. ,
A silane compound in which the functional group is not directly bonded to a silicon atom (D3): (i) (OR) (where R is hydrogen or an alkyl, aryl, acyl or carbonyldioxy group) in the same molecule; and (Ii) Compounds having at least two identical or different functional groups selected from carboxylic acids, acid halides, acid anhydrides, acid halide anhydrides, acid esters, acid amides, imides, imides, aminos and salts thereof.

(D) is that the polyphenylene ether or polypropylene (A) and the polyamide (B) have inherently low affinity, so they are simultaneously melt-kneaded so that the particles of the polyphenylene ether or polypropylene have a particle size of about 10 μm or more. In order to remedy the drawback of dispersing only in the particle size and not exhibiting sufficient mechanical properties, it is blended or preliminarily graft-polymerized.

The compatibilizing agent of the group (D1) includes an unsaturated group, that is, a carbon-carbon double bond or a carbon-carbon triple bond, a polar group, that is, an amide bond contained in a polyamide resin, and a compound present at a chain terminal. A compound having a functional group exhibiting an affinity for a carboxyl group or an amino group or a chemical reactivity 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, an acid azide, an acid halide, Or oxazoline, a functional group such as nitrile, an epoxy group, an amino group, a 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, Unsaturated epoxy compounds, 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, the formula (Where R represents an aliphatic or aromatic group), methylnadic anhydride, dichloromaleic anhydride, maleic amide, itaconic acid, itaconic anhydride, soybean oil, tung oil, Castor oil, linseed oil, hemp seed oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, natural oils such as 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,
Mycolipenic acid, 2,4-hexadienoic acid, diallylacetic acid, geranic acid, 2,4-decadienoic acid, 2,4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9.1
2-octadecadienoic acid, hexadecatrienoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, eicosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, Unsaturated carboxylic acids such as docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid, octacosenoic acid, and traacontenic acid, or esters, acid amides, anhydrides, or allyl alcohols of these unsaturated carboxylic acids 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-hexadien-3-ol, 3,5-hexadien-2-ol, 2,4-hexadien-1-ol, general formula C _n H _2n-5 OH, C _n H
_{2n-7 OH, C n 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-diol,
Unsaturated alcohols such as 1,5-hexadiene-3,4-diol and 2,6-octadiene-4,5-diol, or OH groups of such unsaturated alcohols are
Examples include unsaturated amines substituted with —NH ₂ groups, glycidyl (meth) acrylate, allyl glycidyl ether, and the like. Further, low polymerization of butadiene, isoprene or the like (for example, when the average molecular weight is 500 to 1000)
0) or a high molecular weight substance (for example, having an average molecular weight of 10,000 or more) to which maleic anhydride or phenols are added, or an amino group, a carboxylic acid group, a hydroxyl group, an epoxy group, etc. Allyl acid 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 more preferably maleic anhydride and fumaric acid are used.

The compatibilizers of group (D2) include, in the molecular structure, a) at least one silicon atom bonded to a carbon atom via an oxygen bridge, and b) at least an ethylenic carbon-carbon double A silane compound having both a 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, and gamma-aminopropitriethoxysilane , 2- (3-cyclohexyl) ethyltrimethoxysilane and the like can be used.

The compatibilizing agent of the group (D3) is an aliatic polycarboxylic acid, acid ester or acid amide, and has the general formula (R ₁ O) mR (COOR ₂ ) n (CONR
₃ R ₄ ) l (where R is a linear or branched saturated aliphatic hydrocarbon, 2 to 20, preferably 2 to 2)
R ₁ is hydrogen, an alkyl group, an aryl group, an acyl group, or a carbonyldioxy group, particularly preferably hydrogen, and R ₂ is a hydrogen, an alkyl group, or an aryl group. R ₃ and R ₄ are hydrogen, an alkyl group, or an aryl group having 1 to 10 carbon atoms, preferably 1 to 6, more preferably 1 to 4, m = 1, n + 1 is an integer of 2 or more, preferably 2 or 3, n is an integer of 0 or more, l is an integer of 0 or more, and (R ₁ O) is an α-position of a carbonyl group. Or 2 to 6 carbons between at least two carbonyl groups at the β-position. 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 acids include citric acid, malic acid, and agaric acid. The details of these compounds are described in Published Patent Publication No. 61-5021.
No. 95 discloses this. )

However, the compatibility improver in the present invention is:
It is not limited to the compounds exemplified herein, and may be any compound used for the purpose of improving the compatibility of polyphenylene ether or polypropylene and polyamide, even if a single or a plurality of compatibilizers are used simultaneously. Good. In addition,
(D) From the viewpoint of reactivity with polyphenylene ether or polypropylene and economic efficiency, at least one selected from the group consisting of maleic anhydride, maleic acid, fumaric acid, itaconic acid, citric acid, and malic acid is preferable. .
In addition, a radical initiator may be used in combination with a polyphenylene ether when a compatibilizing agent is blended. When used for polypropylene, it is preferable to use a radical initiator in combination. In particular, when performing a graft reaction on polypropylene, the graft efficiency can be improved by using a radical initiator. Known radical initiators such as organic peroxides, organic peresters, and azo compounds can be used as the radical initiator used here. When using a radical initiator,
This amount is usually 0.01 to 20 parts by weight based on 100 parts by weight of unmodified polypropylene.

As an example of the method of (A) for graft-polymerizing such a compatibilizer to polyphenylene ether or crystalline polypropylene, polyphenylene ether or crystalline polypropylene is suspended or dissolved in a solvent, and the suspension is dissolved. A method of adding a graft modifier to a liquid or a solution to cause a graft reaction (solution method), and a method of performing a graft reaction while melting a mixture of crystalline polypropylene and the graft modifier (melting method) can be exemplified. . Alternatively, these graft polymerizations may be performed in advance, and the remaining components (B) and (C) may be mixed in a melt-kneading process. When the graft polymerization is carried out by a melt kneading method, a method of mixing the remaining components (B) and (C) in a continuous step using one kneader is economically advantageous.

The resin composition of the present invention comprises the above (A) to
(D), the content of (A) is 3 to 75% by weight, the content of (B) is 10 to 95% by weight, and (C)
Is 1 to 50% by weight, and the content of (D) is an amount sufficient to make (A) and (B) compatible. Preferably, the content of (A) is 5 to 70% by weight,
The content of (B) is 15 to 91% by weight, the content of (C) is 3 to 40% by weight, more preferably the content of (A) is 10 to 50% by weight, ) Is 2
0 to 86% by weight, and the content of (C) is 3 to 30% by weight. If (A) is too small, the water absorption rigidity will be low,
On the other hand, when (A) is excessive, the fluidity is deteriorated. If (B) is too small, the fluidity will be poor, while if (B) is too large, the water absorption rigidity will be low. If the content of (C) is too small, the effect of improving the salt damage resistance is poor, while if the content of (C) is too large, the heat resistance is significantly reduced. The content of (D) is an amount sufficient to make (A) and (B) compatible, but 0.01
-10% by weight, more preferably 0.05-5%
% By weight. When the content of (D) exceeds 10% by weight, the heat stability may be reduced, or the strength may be significantly reduced due to decomposition or the like.

In the present invention, natural and synthetic polymer materials (rubber-like substances) which are elastic at room temperature can be used in order to improve the impact resistance of the resin composition. 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 the like, or a mixture thereof is used. Further, a modified rubber modified with a functional monomer containing another acid or epoxy may be used. The amount of the rubber-like substance is 10 parts by weight based on 100 parts by weight of the polyphenylene ether resin or the total of polypropylene and polyamide resin.
0 parts by weight or less. 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.

In the present invention, an alkenyl aromatic resin may be added in order to improve the fluidity of the resin. Examples of the alkenyl aromatic resin include a homopolymer of an alkenyl aromatic compound produced by ordinary radical polymerization or the like or a resin containing a monomer copolymerizable with the alkenyl aromatic compound. Examples of the alkenyl aromatic compound include styrene, α-methylstyrene, α-ethylstyrene, α-methylstyrene-p-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene. Substituted styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, dichlorostyrene, dibromostyrene, trichlorostyrene, trichlorostyrene, etc. And styrene and α-methylstyrene are preferred. Examples of monomers copolymerizable with the vinyl aromatic compound include, for example, acrylonitrile, methacrylonitrile, fumaronitrile, vinyl cyanide such as maleonitrile, and methyl methacrylate, methyl acrylate,
Examples thereof include methacrylic acid, acrylic acid, and maleic anhydride, and among them, acrylonitrile is preferable.

As long as the object of the present invention is not impaired, it does not prevent inclusion of various additives.
Lubricants, release agents, plasticizers, flame retardants, light stabilizers, heat stabilizers, and antioxidants can be mentioned. For example, as a lubricant, calcium stearate, aluminum stearate, ethylene bisstearylamide, as a release agent, sodium montanate, calcium montanate, as a plasticizer, polyethylene glycol, polypropylene glycol, a light stabilizer, and a heat stabilizer Manganese compounds and copper compounds are used as stabilizers, and hindered phenol compounds and hindered amine compounds are used as antioxidants.

The resin composition of the present invention is a polyphenylene ether or polypropylene-polyamide resin composition in which (A) to (C) have been made compatible by (D) in a melt-kneading process. That is, the method for producing the resin composition of the present invention is a method in which (A) to (C) are mixed in a molten state using an apparatus capable of batch or continuous melting and mixing. Specifically, a continuous kneading extruder such as a batch kneader such as a Banbury mixer or a twin screw kneader is used. Economically, a twin-screw kneader is preferred. In some cases, after the components (A), (B) and (D) are melt-mixed in advance to obtain a polyphenylene ether or a polypropylene / polyamide resin composition, the component (C) is molded during a melting process such as injection molding. May be added. In a particularly preferred method, the components (A) and (D) are melt-kneaded in a first stage using a twin-screw kneader, followed by (B) in a second stage.
And (C) or only (B) in the second step, and (C) in the subsequent third step.

The composition of the present invention can be formed into various parts by injection molding, extrusion molding, blow molding or the like. Its applications include automotive exterior parts, interior parts, and engine compartment parts. It can also be used for electrical, electronic and mechanical parts.

[0038]

The present invention will be described in detail with reference to the following examples. The scope of the present invention is not limited at all by the examples. The following methods were used for evaluation in Examples and Comparative Examples. (1) Melt Index (MI) Pellets of each resin composition were vacuum-dried at 140 ° C. for 4 hours, and the melt index at 280 ° C. under a load of 2.16 kg was determined. (2) Tensile elongation A tensile test was performed in a 23 ° C. atmosphere in accordance with ASTM D638 to measure elongation. (3) Flexural modulus According to ASTM D790, a flexural modulus at 23 ° C. was measured using a test piece having a thickness of ８ inch. (4) Izod Impact Strength A 1/8 inch notched Izod impact strength was measured at 23 ° C. according to ASTM D256. (5) Heat Deformation Temperature (HDT) (Heat Resistance) The heat distortion temperature under a load of 18.6 kg was measured using a test piece having a thickness of 1/4 inch in accordance with ASTM D648. (6) Evaluation of salt damage resistance Using the ASTM No. 1 tensile test piece, the following salt damage resistance was evaluated. Humidity control 80 ° C hot water 14hr Humidity control 23 ° C 50% Rh 6hr leave Jig installation R98 jig Water absorption 80 ° C 95% Rh 1hr Salt-calcium saturated sodium chloride aqueous solution 1hr
(Center part: about 20 mm, immersed in liquid using upper and lower gauze) Drying 100 ° C. Oven for 30 minutes Washing with running water Observation of the state was repeated 5 times, and then the occurrence of cracks was visually observed. The results were represented by （(no cracks generated) and X (cracked).

The following raw materials were used in Examples and Comparative Examples. Component (A) PPE: polyphenylene ether (poly (2,6-polydimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.46 dl / g measured at 30 ° C. in a chloroform solvent) PP: polypropylene KD650 (Sumitomo Chemical Component (B) PA6: A1030BRL (Nylon 6 manufactured by Unitika) Component (C) PA6 / 12: CF6S (PA6 and PA1 manufactured by EMS )
PA-HAMP: TR70 (nuclear hydrogenated aromatic polyamide manufactured by Ems Co.) component (D) MAH: maleic anhydride and other components SBS: styrene-butadiene-styrene copolymer of St / Bd = 52/48 Polymer Znst: zinc stearate ADD-1: GSYP101 (manufactured by Yoshitomi Chemical Co.) PO: Peroxide 1,3-bis (t-butylperoxy-isopropyl) -benzene diluted to 8 wt% with polypropylene PA-AMP: G21 (aromatic polyamide manufactured by EMS Co., Ltd.) The samples of the examples and comparative examples were prepared using a twin-screw kneader (TEM-50) manufactured by Toshiba Machine Co., Ltd.

Example 1 and Comparative Example 1 The above-mentioned mixed components were prepared for the compositions shown in Table 1, and
The fluidity impact resistance, flexural modulus, heat resistance, and salt damage resistance were evaluated (Table 1).

[0041]

[Table 1]

[0042]

As described above, according to the present invention, the polyphenylene ether or polypropylene-polyamide resin composition is improved in salt damage resistance without significantly impairing the balance of physical properties such as excellent impact strength, rigidity, heat resistance and fluidity. Polyphenylene ether or polypropylene
A polyamide resin composition could be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/544 C08L 71/12 C08L 23/10 C08K 5/54 L 71/12 FF term (Reference) 4J002 AE054 BB12W BB14W BL014 BL024 CD164 CH07W CL01X CL01Y CL03X CL03Y CL05X CL06X CL09Y EC036 EF046 EF066 EF076 EH076 EH096 EK007 EL036 EL136 EL146 EN026 EN096 EP026 EQ017 EQ026 ET006 EU026 FD06000 FD FD FD

Claims (7)

[Claims] 1. It contains the following components (A) to (D),
The content of (A) is 3 to 75% by weight, the content of (B) is 10 to 95% by weight, and the content of (C) is 1 to 5% by weight.
0% by weight, and the content of (D) is a thermoplastic resin composition which is a sufficient amount to make (A) and (B) compatible with each other. After grafting, (B) and (C) are added to the grafted material and the mixture is made compatible by a melt-kneading process, or (A)
-A thermoplastic resin composition obtained by compatibilizing (C) with (D) in a melt-kneading process. (A): at least one thermoplastic resin selected from the group of thermoplastic resins consisting of polyphenylene ether and polypropylene having a degree of crystallinity of 35% or more (B): polyamide 6, polyamide 66, polyamide 4
And at least one polyamide selected from polyamide 6 and polyamide 6-66 (C): a unit constituting polyamide 6 and carbon atoms of 8
At least one polyamide selected from the polyamide group consisting of a polyamide which is a copolymer of the above-mentioned aliphatic polyamide and a unit comprising a hydrogenated aromatic polyamide (D): a compatibilizer 2. The thermoplastic resin composition according to claim 1, wherein (D) is at least one selected from the following (D1) to (D3). (D1): Compound having both (i) at least one unsaturated group, ie, a carbon-carbon double bond or a carbon-carbon triple bond, and (ii) at least one polar group in the same molecule. (D2): In a molecular structure (I) having both a carbon atom via an oxygen bridge, and (ii) at least a functional group selected from an ethylenic carbon-carbon double bond or a carbon-carbon triple bond and / or an amino group and a mercapto group. ,
A silane compound in which the functional group is not directly bonded to a silicon atom (D3): (i) (OR) (where R is hydrogen or an alkyl, aryl, acyl or carbonyldioxy group) in the same molecule; and (Ii) Compounds having at least two identical or different functional groups selected from carboxylic acids, acid halides, acid anhydrides, acid halide anhydrides, acid esters, acid amides, imides, imides, aminos and salts thereof. 3. The thermoplastic resin composition according to claim 1, wherein (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. Polyamide 6 and polyamide 12 (C)
The thermoplastic resin composition according to claim 1, which is a copolymer of the following. 5. The thermoplastic resin composition according to claim 1, wherein in the component constituting (C), the aliphatic component having 8 or more carbon atoms accounts for 30% or more of the total weight of (C). 6. The thermoplastic resin composition according to claim 1, wherein (A) is a polyphenylene ether. 7. The thermoplastic resin composition according to claim 1, wherein (A) is a polypropylene having a crystallinity of 35% or more.