JPH07126524A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. excellent in molded appearance and heat resistance by mixing nylon 46, a specific styrenic polymer obtd. by the polymn. in the presence of an ethylene-alpha-olefin rubber, and a specific copolymer in such a manner that disperse phase in the resulting mixture has a specified shape. CONSTITUTION:A resin compsn. is obtd. by mixing 40-87wt.% polytetramethyleneadipamide (nylon 46) or uts copolyamide, 10-57wt.% sryrenic polymer obtd. by polymerizing an arom. vinyl comd. or a vinyl cyanide compd. in the presence of an ehtylene-alpha-olefin rubber, and 3-40wt.% pref. 1-15wt.% copolymer obtd. by copolymerizing an arom. vinyl compd. or a vinyl cyanide compd. with an unsated. compd. having at least one such as a carboxyl, acid anhydride, or epoxy group in such a manner that the disperse phase formed by the styrenic polymer and the copolymer in the resulting mixture has a nearly circular section with a number-average diameter of 0.3-3mum.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition which is excellent in impact resistance, appearance of a molded product (especially weld appearance) and heat resistance (deflection temperature under load).

[0002]

2. Description of the Related Art Polytetramethylene adipamide (hereinafter referred to as
Nylon 4,6. ) Is a known polyamide, and is known to be a resin having excellent properties as an engineering plastic, particularly excellent heat resistance. Generally, polyamide resins have excellent mechanical properties such as strength, impact resistance, and abrasion resistance, and have high heat resistance and chemical resistance. It is used in various applications such as general machine parts. Among them, nylon 4 and 6 have excellent heat resistance as indicated by their high melting point, and have a short crystallization cycle due to their high crystallization rate, and also have good melt flowability due to their low melt viscosity. I have As described above, nylons 4 and 6 are excellent in chemical resistance of polyamide, and also excellent in heat resistance and moldability, and thus are expected to be applied as engineering plastics from various fields.

On the other hand, an AES resin obtained by polymerizing acrylonitrile and styrene in the presence of an ethylene-propylene rubbery polymer has excellent impact resistance and molding processability, so that it can be used in the fields of automobiles, weak electric fields, etc. Widely used in.

Excellent heat resistance and AE of polyamide resin
Several studies have already been conducted to obtain a resin material having both the excellent impact resistance of S resin and the appearance of a molded product. Generally, the polyamide resin and the AES resin have poor compatibility, and even if they are simply mixed, they become a very brittle resin material. However, they are obtained by copolymerizing a carboxylic acid or an acid anhydride during the polymerization of the AES resin. The composition of the modified AES resin and the polyamide resin has improved compatibility with each other and has excellent impact resistance (Japanese Patent Application Laid-Open No. HEI 2).
-86657, Japanese Patent Laid-Open No. 2-113062). However, the appearance of the molded product (weld appearance) was still insufficient.

In order to improve not only the impact resistance but also the appearance of the molded product, an example in which nylon 4,6 is used among polyamides has already been disclosed before the above-mentioned example, JP-A-63-16275.
Seen at 0. Generally, the appearance of the molded product is considered to depend on the dispersion state of the AES resin component in the polyamide resin,
The dispersion state is considered to be greatly influenced by the viscosity characteristics of both. Among polyamide resins, nylon 4,6
The advantage of using is that the viscosity of the AES resin at the processing temperature of nylon 4,6 is similar to that of nylon 4,6, so the dispersion state of the AES resin component in nylon 4,6 is finer. It will be something like that. for that reason,
In Japanese Patent Laid-Open No. 63-162750, a resin composition having excellent impact resistance and a molded product appearance (weld appearance) is obtained. However, if the dispersion state of the AES resin component in nylon 4,6 becomes too fine, impact resistance and the appearance of the molded product will not be impaired, but heat resistance, which is one of the important features of nylon 4,6, will decrease. There was a case to do.

[0006]

[Problems to be Solved by the Invention] Nylon 4, 6 and AE
The impact resistance and the appearance of the molded product of the resin composition containing the S resin component are not improved when the size of the dispersed phase formed by the AES resin component is not too large, and are improved as the size of the dispersed phase is smaller. Tends to. On the other hand, the heat resistance typified by the deflection temperature under load does not decrease when the size of the dispersed phase is large, but tends to significantly decrease when the size is too small. That is, it has been found that the size of the dispersed phase that improves the impact resistance and the appearance of the molded product and the size of the dispersed phase that maintains the heat resistance are in conflict with each other. Therefore, it is considered that there exists a desirable range of the dispersed phase size in order to improve the impact resistance and the appearance of the molded product while maintaining the heat resistance which is an advantage of nylons 4 and 6.
In view of such circumstances, an object of the present invention is to develop a thermoplastic resin composition having excellent impact resistance, appearance of a molded article, and heat resistance, focusing on the dispersion state of the AES resin component in nylon 4,6. To provide.

[0007]

The present invention provides an aromatic vinyl compound in the presence of (A) 40 to 87% by weight of polytetramethylene adipamide and (B) an ethylene-α-olefin rubbery polymer. An aromatic vinyl compound, a vinyl cyan compound and a carboxyl group in the presence of 10 to 57% by weight of a styrene polymer obtained by polymerizing a vinyl cyan compound, and (C) an ethylene-α-olefin rubber polymer. A composition comprising 3 to 40% by weight of a copolymer obtained by copolymerizing an unsaturated compound having at least one functional group selected from an acid anhydride group, an epoxy group, a hydroxyl group and an amino group, and A thermoplastic resin composition having a number average diameter of 0.3 to 3.0 microns when the cross-sectional shape of the dispersed phase formed by the components (B) and (C) in the composition is approximated to a circle is provided. To serve. The present invention will be described below.

(A) Nylon 4, 6 has the general formula:

[0009]

[Chemical 1]

A polyamide resin consisting essentially of the repeating structural unit represented by Nylon 4,6 is a conventionally used polyamide, that is, polycaproamide (nylon 6), polylauryl lactam, polyhexamethylene adipamide (nylon 6,6), polyhexamethylene azeramide (nylon 6,). 9), polyhexamethylene sebacamide (nylon 6,10), polyundecamethylene adipamide (nylon 6,11), polyhexamethylene dodecamide (nylon 6,12), polyundecane amide (nylon 11), It has a melting point higher than that of polyamides represented by polydodecamide (nylon 12) and their copolyamides and mixed polyamides. That is, the melting point of nylon 4,6 is about 295 ° C, which is higher than that of nylon 6,6 by about 30 ° C.

The nylons 4 and 6 used in the present invention include
It includes a polytetramethylene adipamide obtained from tetramethylene diamine and adipic acid and a copolyamide having a polytetramethylene adipamide unit as a main constituent. Further, other polyamide may be contained as a mixed component within a range not impairing the properties of nylons 4 and 6.
The copolymerization component is not particularly limited, and a known amide-forming component can be used.

Typical examples of the copolymerization component include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminoundecanoic acid and para-aminomethylbenzoic acid, lactams such as ε-caprolactam and ω-lauryllactam. , Hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-
/ 2,4,4-trimethylhexamethylenediamine, 5
-Methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl)
Cyclohexane, 1-amino-3-aminomethyl-3,
Diamines such as 5,5-trimethylcyclohexane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (aminoprosyl) piperazine and aminoethylpiperazine Adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalate Examples thereof include acids, dicarboxylic acids such as hexahydroisophthalic acid and diglycolic acid, and other polyamides used as a mixed component may include those composed of these components.

Nylon 4,6 used in the present invention
The manufacturing method of is arbitrary. For example, a method in which a prepolymer having a small number of cyclic end groups is produced under specific conditions and then solid-phase polymerized in a steam atmosphere to prepare high-viscosity nylons 4, 6, or 2-pyrrolidone or N-methylpyrrolidone There is a method of obtaining it by heating in a polar organic solvent such as. The degree of polymerization of nylon 4,6 is not particularly limited, but nylon 4, which has a relative viscosity in the range of 1.5 to 6.0 at 25 ° C. and 96% sulfuric acid at 1 g / dl.
6 is preferably used.

The proportion of nylon 4,6 in the thermoplastic resin composition of the present invention is 40 to 87% by weight, preferably 45 to 8%.
It is 0% by weight. 40% by weight of nylon 4,6 used
If it is less than 87%, the heat resistance is remarkably inferior, and if it exceeds 87% by weight, the impact resistance and the appearance of the molded product are not improved.

Ethylene-α- which is the component (B) of the present invention.
The olefin rubber polymer modified styrene polymer is obtained by polymerizing an aromatic vinyl compound and a vinyl cyan compound in the presence of an ethylene-α-olefin rubber polymer.

Ethylene-α-olefin Rubber Polymer The ethylene-α-olefin rubber polymer is a copolymer of ethylene and α-olefin, or a copolymer of ethylene, α-olefin and polyene. The α-olefin used here is an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, specifically, propylene, butene-1, pentene-1, hexene-1, heptene-1, 4, -Methylbutene-1, 4-methylpentene-
1 and the like. Particularly preferred are propylene and butene-1.

As the polyene compound, 1,4-pentadiene, 1,5-hexadiene, 2-methyl-1,
5-hexadiene, 3,3-dimethyl-1,5-hexadiene, 1,7-octadiene, 1,9-decadiene,
6-methyl-1,5-hexadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 9-methyl-1,9-undecane, 1,3-pentadiene, 1,
4,9-decatriene, 4-vinyl-1-cyclohexane, cyclopentadiene, 2-methyl-2,5-norbornadiene, 5-methyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2.
-Norbornene, 5-isopropenyl-2-norbornene, disixpentadiene, tricyclopentadiene and the like. When the polyene compound is used, the iodine value is preferably in the range of 2-40.

When propylene is used as the α-olefin, the weight ratio of ethylene to propylene is generally 95: 5.
˜5: 95, preferably 95: 5 to 20:80, and more preferably 92: 8 to 60:40. Furthermore, it is particularly preferably 70:30 to 5 from the viewpoint of low temperature impact.
It is within the range of 0:50. When butene-1 is used as the α-olefin, the weight ratio of ethylene and butene-1 is generally 95:40 to 5:60, preferably 95: 6.
0-5: 40, more preferably 95: 70-5: 30
Within the range of. Further, the ethylene-α-olefin rubbery polymer may be mixed with another rubbery polymer for use. Other rubbery polymers mixed and used here include:
Acrylic rubber, polychloroprene, polyisoprene, ethylene ionomer and the like can be mentioned.

The amount of the ethylene-α-olefin rubbery polymer in the component (B) is not particularly limited, but industrially 10
-60% by weight is advantageous. The amount of the resinous polymer grafted to the ethylene-α-olefin rubbery polymer is preferably in the range of 10 to 100% by weight based on 100% by weight of the rubbery polymer. In order to achieve the object of the present invention, the amount of the ethylene-α-olefin rubber polymer in the thermoplastic resin composition of the present invention is 3 to 30% by weight.
It is preferable to set it as the range.

Aromatic Vinyl Compound The aromatic vinyl compound used here is styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene. , P-tert-butyl styrene, ethyl styrene, vinyl naphthalene, etc., and preferably styrene and α-methyl styrene. These are 1 or 2
Used in seeds and above.

Vinyl Cyan Compound Examples of the vinyl cyan compound include acrylonitrile and methacrylonitrile. The ratio of the aromatic vinyl compound and the vinyl cyan compound used in the component (B) is generally aromatic vinyl compound / vinyl cyan compound = 95/5.
It is within the range of -60/40, preferably 90 / 10-65 / 35 (% by weight).

Other Vinyl Compounds Copolymerizable Further, other vinyl compounds copolymerizable therewith can be copolymerized within a range not impairing the object of the present invention. Other copolymerizable vinyl compounds include (meth)
There are alkyl acrylates, maleimide compounds and the like, and these are used alone or in combination of two or more.

Examples of the (meth) acrylic acid alkyl ester include methyl acrylate, ethyl acrylate,
Acrylic alkyl esters such as propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate and benzyl acrylate, and methyl methacrylate, ethyl methacrylate, butyl methacrylate. , Amylmethacrylate, hexylmethacrylate, octylmethacrylate, 2-ethylhexylmethacrylate, cyclohexylmethacrylate, dodecylmethacrylate, octadecylmethacrylate, phenylmethacrylate, benzylmethacrylate, and other methacrylic acid alkyl esters.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-ethylmaleimide,
N-butyl maleimide, N-lauryl maleimide, N-
Cyclohexylmaleimide, N-phenylmaleimide,
Examples thereof include hydroxyphenyl maleimide and N- (p-bromophenyl) maleimide.

The amount of the other copolymerizable vinyl compound used is generally 0 to 50% by weight, preferably 0 to 50% by weight in the component excluding the ethylene-α-olefin rubbery polymer as the component (B). It can be used within the range of 30% by weight. The proportion of the component (B) in the thermoplastic resin composition of the present invention is 10 to 57% by weight, preferably 16 to 50% by weight. When the proportion of the component (B) is less than 10% by weight, impact resistance is poor, and when it exceeds 57% by weight, heat resistance is poor.

The component (C) is an ethylene-α-olefin rubbery polymer-modified styrene polymer. In the component (C), a carboxyl group, an acid anhydride group, an epoxy group,
It is necessary to contain an unsaturated compound having at least one functional group selected from a hydroxyl group and an amino group as a copolymerization component. The ethylene-α-olefin rubbery polymer-modified styrene-based polymer is achieved by copolymerizing the unsaturated compound having the functional group with the styrene-based polymer.

The amount of the unsaturated compound having a specific functional group to be copolymerized is preferably 0.5 to 20 in the ethylene-α-olefin rubbery polymer-modified styrene polymer.
%, More preferably 0.5 to 15% by weight, particularly preferably 1 to 15% by weight. The proportion of the component (C) in the thermoplastic resin composition of the present invention is 3 to 40% by weight, preferably 4 to 25% by weight. If the amount used in the component (C) is less than 3% by weight, impact resistance and molding appearance are poor, and if it exceeds 40% by weight, heat resistance decreases.

Carboxyl Group-Containing Unsaturated Compound Examples of the carboxyl group-containing unsaturated compound used here include acrylic acid, methacrylic acid, crotonic acid,
There are cinnamic acid, itaconic acid, maleic acid and the like, and acrylic acid and methacrylic acid are preferable. These are used alone or in combination of two or more.

Acid Anhydride Group-Containing Unsaturated Compound Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride and the like. And a particularly preferred unsaturated acid anhydride is maleic anhydride. These are used alone or in combination of two or more.

Epoxy Group-Containing Unsaturated Compound The epoxy group-containing unsaturated compound is a compound having an unsaturated group capable of copolymerizing with an olefin and an ethylenically unsaturated compound, and an epoxy group in the molecule. For example, unsaturated glycidyl esters represented by the following general formulas (I), (II) and (III), unsaturated glycidyl ethers, epoxy alkenes, unsaturated epoxy compounds such as p-glycidyl styrenes. .

[0031]

[Chemical 2] (R is a C _2-18 hydrocarbon group having an ethylenically unsaturated bond.)

[0032]

[Chemical 3] (R is C _{2 ~ 18} hydrocarbon group having an ethylenically unsaturated bond .X is _{-CH 2 -O -, - C 6} H 6 -O- or -C ₆ H ₆ - and is.)

[0033]

[Chemical 4] (R is a C _2-18 hydrocarbon group having an ethylenically unsaturated bond. R'is hydrogen or a methyl group.)

Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butenecarboxylic acid esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxybutene. , 3,4-epoxy-3-methyl-1-butene, 3,
4-epoxy-1-pentene, 3,4-epoxy-3-
Methyl pentene, 5,6-epoxy-1-hexene, vinyl cyclohexene monoxide, p-glycidyl styrene and the like can be mentioned. These may be used alone or in combination of two or more.

Hydroxyl Group-Containing Unsaturated Compound The hydroxyl group-containing unsaturated compound is a compound having at least one unsaturated bond (double bond, triple bond) and containing a hydroxyl group. Typical examples thereof include an alcohol having a double bond, an alcohol having a triple bond, an ester of a monovalent or divalent unsaturated carboxylic acid and an unsubstituted dihydric alcohol, and an unsubstituted trivalent unsaturated carboxylic acid. Examples thereof include esters with polyhydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted pentavalent or higher alcohols.

Of the hydroxyl compounds used in the present invention, typical examples of suitable compounds include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene and trans-. 4-hydroxy-2-butene, 3-hydroxy-2-methyl-1
-Propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, cis-1,4
-Dihydroxy-2-butene, trans-1,4-dihydroxy-2-butene, 2-hydroxyethyl acrylate, 2-hydroxyl ethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl crotonate, 2,3,4,5,6-pentahydroxyhexyl acrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-tetrahydroxypentyl acrylate, 2,3,4,5 -Tetrahydroxypentyl methacrylate. These are used alone or in combination of two or more.

Amino Group-Containing Unsaturated Compound The amino group-containing unsaturated compound has the following general formula:

[0038]

[Chemical 5]

(In the formula, R ₁ is hydrogen, a methyl group,
Represents an ethyl group, R ₂ is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, and 6 to 6 carbon atoms.
A phenyl group having 12 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, or a derivative thereof is shown. ) Is a vinyl-based monomer having at least one of an amino group or a substituted amino group, and specific examples thereof include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, aminopropyl methacrylate. , Alkyl ester derivatives of acrylic acid or methacrylic acid such as phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine, methacrylamine and N- Allylamine derivatives such as methylallylamine and aminostyrenes such as p-aminostyrene are used. Among them, allylamine, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene and the like are particularly preferably used since they are economically available on an industrial scale. These amino group- or substituted amino group-containing unsaturated compounds may be one type or two types.
Used in seeds and above.

[0040] As a method for obtaining components of Polymerization present invention (B) and (C), the emulsion polymerization is a well-known polymerization method, solution polymerization, bulk polymerization, suspension polymerization, bulk - solution polymerization, bulk - suspension A turbid polymerization method or the like can be used, but among them, an emulsion polymerization method and a solution polymerization method are preferable. When the emulsion polymerization method is used, an emulsified ethylene-α-olefin rubber polymer is used.
The ethylene-α-olefin rubber polymer particles dispersed in the polymer have an average of 2,000 to 10,000 angstroms, preferably 2,000 to 5,000 angstroms, and particularly preferably 2,300 to 3,500. It is desirable that the particles have a diameter within the range of angstrom. When the solution polymerization method is used, the polymerization temperature is generally 60 to
At 150 ° C., the polymerization pressure is generally in the range of 0.1 to 4 kg / cm ² . The ethylene-α-olefin rubber polymer particles dispersed in the polymer have an average of 2,000 to 30,0.
00 Angstrom, preferably 2,000-20,
It is desirable that the particles have a diameter within the range of 000 angstroms.

The ethylene-α-olefin rubbery polymer modified styrene polymer modified with the unsaturated compound having a functional group obtained by the above-mentioned polymerization generally has an aromatic vinyl compound unit of 12 to 85% by weight, Preferably from 23 to 81% by weight, vinyl cyanide compound units generally being 1
To 36% by weight, preferably 3.5 to 31% by weight, generally 10 to 60 ethylene-α-olefin rubbery polymer.
%, Preferably 10 to 50% by weight, generally 0.5 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 15% by weight, of unsaturated compound units having functional groups.

The number average diameter when the cross-sectional shape of the dispersed phase formed by the components (B) and (C) in the composition comprising the components (A), (B) and (C) is approximated to a circle is 0. .3-3.
It is 0 micron, preferably 0.31 to 2.8 micron. If the diameter is less than 0.3 micron, heat resistance is poor, while if it exceeds 3.0 micron, weld appearance and impact resistance are poor.

Manufacture of Composition The thermoplastic resin composition of the present invention is prepared by using various extruders, Banbury mixers, kneaders, rolls, etc., for the respective constituents thereof, generally at 200 to 350 ° C., preferably 280 to 330 ° C.
It can be obtained by kneading in the temperature range of. As a preferable kneading method, a method using an extruder is used, and a particularly preferable method is a method of kneading using a twin-screw extruder at a maximum barrel setting temperature of 290 to 330 ° C.

Other compounding agents Although the thermoplastic resin composition of the present invention can be used as it is, the ethylene-α-olefin rubbery polymer-modified styrene copolymer in the composition is added to the thermoplastic resin composition. A graft blend type copolymer obtained by blending an aromatic vinyl-vinyl cyanide copolymer with a polymer, or a blend rubber-modified styrene copolymer obtained by blending a rubber-modified styrene graft copolymer having a different rubber-like polymer, or It is also possible to mix the blend rubber modified styrene graft copolymer and the aromatic vinyl-vinyl cyanide copolymer.

Further, in the thermoplastic resin composition of the present invention, other polymers may be added depending on the performance required from the application.
For example, polyptadiene (PB), polyethylene (PB)
E), ethylene-propylene copolymer (EP and EP
DM), butadiene-styrene copolymer, styrene-ethylene-butadiene-styrene copolymer (SEBS),
Arryl rubber (AR), fluororubber (FR), polystyrene (PS), polyethylene terephthalate (PE
T), polybutylene terephthalate (PBT), polyester mixture, polycarbonate (PC), polysulfone, polyether sulfone (PES), polyimide (P
I), PPS, polyether ether ketone (PEE)
K), vinylidene fluoride polymer (PVDF etc.), polyoxymethylene (POM), polytetrafluoroethylene (PTFE), polyphenylene ether (PPE),
Polyamides other than nylon 4,6, crosslinked particles and the like, and modified products thereof can be appropriately blended.

In addition, the thermoplastic resin composition of the present invention passes the V-0 or V-1 standard in a flammability test according to the UL-94 test method of Underwriters Laboratories, depending on the application. It may be required to do so. Therefore, in that case, it is naturally necessary to add and introduce a flame retardant represented by halogenated polystyrene or the like and a flame retardant auxiliary represented by a zinc compound, an antimony compound, an iron compound or the like. However, even in this case, since the resin composition for reflow of the present invention does not impair the performance which is the object of the present invention, there is no problem in adding a flame retardant or a flame retardant auxiliary agent represented by the above-mentioned compounds. .

The inorganic fillers that can be added to the thermoplastic resin composition of the present invention as required are various fillers having a fibrous, powdery, granular, plate-like, needle-like, cloth-like or mat-like shape. . As typical examples of such inorganic fillers, glass fiber, asbestos fiber, carbon fiber, graphite fiber, calcium carbonate, talc, catalbot, wollastonite, silica, alumina, silica-alumina, diatomaceous earth,
Clay, calcined clay, kaolin, mica (fine mica),
Granular glass, glass flakes, glass balloons (hollow glass), gypsum, red iron oxide, metal fibers, titanium dioxide, potassium titanate whiskers, magnesium oxide,
Examples thereof include calcium silicate, asbestos, sodium aluminate, calcium aluminate, aluminum, aluminum oxide, aluminum hydroxide, copper, stainless steel, zinc oxide, and metal whiskers. For the purpose of the present invention, glass fiber, carbon fiber, kaolin, mica,
Talc is especially preferred.

Surface treatment may be carried out as long as the moldability and physical properties of the present invention are not impaired. Among them, those subjected to surface treatment represented by aminosilane treatment, acrylsilane treatment, vinyl treatment and the like are preferable. preferable.

Of course, only one kind of the above-mentioned inorganic filler may be added to the thermoplastic resin composition of the present invention, but two or more kinds may be used in combination. These fillers are preferably 2 to 200% by weight, more preferably 5 to 150% by weight with respect to 100% by weight of the thermoplastic resin composition.
%, Particularly preferably 7 to 100% by weight.

The thermoplastic resin composition of the present invention contains other components, such as pigments, dyes, colorants, organic reinforcing materials, heat-resistant agents, copper compounds and hindered phenols, as long as the moldability and physical properties are not impaired. Stabilizers represented by compounds and the like, antioxidants, photoprotective agents, crosslinking agents represented by styrene maleic anhydride and epoxy compounds, weathering agents, light stabilizers, crystal nucleating agents, lubricants, release agents, A plasticizer, an antistatic agent, etc. can be added and introduced.

[0051] Applications The thermoplastic resin composition of the present invention, the molding method used for conventional thermoplastic resins such as injection molding, extrusion molding, blow molding, vacuum forming, molding or the like compression molding as various molded articles Can be used. Various molded products can be mainly used for exterior / interior members such as automobiles and motorcycles, and various electric / electronic-related parts and housings by utilizing their excellent properties.

Examples and Comparative Examples Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by weight and% by weight, respectively.

(1) Production of polytetramethylene adipamide resin Polytetramethylene adipamide resin was prepared from 1,4-diaminobutane and adipic acid according to the method of Example 1 of JP-A-56-149431. Was manufactured. The resulting resin had a relative viscosity η _rel (measured with a solution of 1 g of polymer in 100 ml of 96% sulfuric acid at 25 ° C.) of 3.5.

(2) Ethylene-α-olefin rubber polymer The following polymers were used. In addition, rubbery polymerization resistance No.
1 was, in an autoclave reactor of 200 liters, n-hexane supply amount (liter / hr) 80 gas phase ethylene / propylene (molar ratio) 1.0, gas phase hydrogen concentration (mol%) 12, and as a polymerization solvent , Ethylaluminum sesquichloride (mol / liter-hexane) 4.1 × 10 ⁻³ Vanadium oxytrichloride (mol / liter-hexane) 5.1 × 10 ⁻³ , and the polymerization temperature (° C.) 38 polymerization Continuous polymerization of ethylene, propylene and DCP was carried out under the polymerization conditions of pressure (kg / cm ² ) 6.5. A small amount of water as a reaction terminator was added to the polymerization liquid extracted from the reactor, the solvent was driven out of the system by steam distillation, and the rubber was dried in the finishing step.
The characteristics of the obtained rubbery polymer are shown in Table 1.

(3) Styrene-based polymer No. Production of rubber polymer No. 1 in a 10-liter stainless steel reaction vessel equipped with a paddle type stirring blade. 1 part 20 parts, acrylamide 10 parts, acrylonitrile 18 parts, styrene 52 parts,
Further, 100 parts of toluene was charged, and the mixture was stirred at 50 ° C. until the rubber was completely dissolved, 0.2 parts of ter-dodecyl mercaptan and ter-butyl peroxybenzoate of 0.1 part were added.
After adding 5 parts, a polymerization reaction was carried out at 100 ° C. for 10 hours. The solvent was removed by a conventional method, dried, pelletized using an extruder, and dried at 80 ° C. for 10 hours, and then the styrene polymer No. 1 shown in Table 2 was used. Got 1. No. In the same manner as No. 1 in Table 2, No. A few styrene-based polymers were obtained.

(4) Production of thermoplastic resin composition The polytetramethylene adipamide resin produced by the above method and the styrene polymer were mixed in the mixing ratio shown in Table 3. A co-rotating twin-screw extruder was used as the extruder, the temperature of the highest part of the barrel was set to 315 ° C., and kneading was performed at a screw rotation speed of 200 rpm. The pelletized thermoplastic resin composition thus obtained was sufficiently dried with a dehumidifying dryer, and then a test piece was prepared with an injection molding machine, and evaluated according to the following evaluation criteria.

Impact resistance : Measured in accordance with ASTM D256 at a thickness of 1/4 ", with a notch and at 23 ° C. Weld appearance Weld portions of weld strength evaluation test pieces were visually observed and evaluated according to the following evaluation criteria. ◯: Weld part is hardly noticeable Δ: Weld part is slightly noticeable ×: Weld part is noticeable Measured at a deflection temperature under load ASTM D648 and a load of 18.6 kg / cm ^2. Average diameter of dispersed phase A test piece injection-molded by liquid nitrogen was used. The cross-sectional shape of the dispersed phase obtained by observing the fractured surface in an electron microscope was input to an electronic calculator, and the number average diameter when the shape was approximated to a circle was calculated. .

Examples 1 to 15 The evaluation results are shown in Table 3 (1).

Comparative Examples 1 to 5 Compositions and proportions were changed to those shown in Table 3 (2). In addition, as nylon 6,6, Toray Industries, Inc.
Manufactured by Amiran CM3001N was used.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3 (1)]

[0063]

[Table 3 (2)]

[0064]

EFFECTS OF THE INVENTION The thermoplastic resin composition of the present invention has excellent impact resistance, appearance of molded articles and heat resistance. Due to its excellent performance, it is used as an engineering material such as a material for automobile parts, a material for electric / electronic parts and the like. , Is an industrially extremely useful material.

Claims (1)

[Claims] 1. (A) Polytetramethylene adipamide 4
Styrene polymer obtained by polymerizing an aromatic vinyl compound and a vinyl cyan compound in the presence of 0 to 87% by weight of (B) an ethylene-α-olefin rubber polymer.
In the presence of 57% by weight, and (C) an ethylene-α-olefin rubber polymer, from an aromatic vinyl compound, a vinyl cyan compound and a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, and an amino group. A composition comprising 3 to 40% by weight of a copolymer obtained by copolymerizing an unsaturated compound having at least one selected functional group, and the components (B) and (C) are formed in the composition. A thermoplastic resin composition having a number average diameter of 0.3 to 3.0 microns when the cross-sectional shape of the dispersed phase is approximate to a circle.