JPH0726072A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin compsn. improved in impact, strength and appearance of a molded product thereof without delamination by using a polyolefin resin, a PS resin, and a specific copolymer (salt). CONSTITUTION:100 pts.wt. in total of 5-95 pts.wt. polyolefin resin having functional groups reactive with an amino group, or compsn. comprising the above polyolefin resin and another polyolefin resin having no functional groups, and 95-5 pts.wt. compsn. comprising a PS resin having functional groups reactive with an amino group and/or a PS resin having no functional groups are blended with 0.05-20 pts.wt. copolymer (salt) having in the molecule thereof repeating formamide units of the formula (wherein R<1> and R<2> are each H, 1-6C alkyl, 6-8C aryl, 7-8C arylalkyl; R<3> is 1-18C alkylene, 5-17C cycloalkylene, 6-12C arylene, 7-17 arylalkylene; and R<5> is H or 1-6C alkyl).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition prepared by blending a polyolefin resin and a polystyrene resin.

[0002]

2. Description of the Related Art Polyolefin-based resins and polystyrene-based resins have good molding processability and are inexpensive, so resin molded products, home appliances, packaging containers, packaging materials, miscellaneous goods in the form of molded products, sheets, films, etc. Widely used for such purposes. However, polyolefin-based resins and polystyrene-based resins have respective advantages and disadvantages, and it is difficult for a single resin to satisfy all the required physical properties. For example, polyolefin-based resins have good chemical resistance, but poor printability / paintability, while polystyrene-based resins have good printability / paintability, but poor chemical resistance.

Therefore, attempts have been actively made to obtain a resin composition having two or more kinds of resins having different characteristics and blending or alloying them to complement the drawbacks of the both and to have new functional characteristics.

However, simply blending the polyolefin-based resin and the polystyrene-based resin does not mix well with each other, and the resulting resin composition has a reduced impact resistance. Further, when it is used as a molded product, the appearance itself is poor and there is a problem that delamination occurs.

It is known that the impact resistance can be improved to some extent by adding an elastomer component to such a resin composition, but on the contrary, there is a problem that the rigidity of the resin is lowered. It was Further, it does not essentially solve the problems such as delamination and poor appearance when the resin is used as a molded product.

[0006] In order to solve such problems, attempts have conventionally been made to improve the miscibility of resins to be blended with a compatibilizer.

As the compatibilizer used for such purpose, maleic anhydride-modified polypropylene, maleic anhydride-modified SEBS (hydrogenated styrene-butadiene-styrene block copolymer), maleic anhydride-modified EP
R, ethylene-ethyl acrylate-maleic anhydride copolymer, styrene-maleic anhydride copolymer, etc., a graft polymer or copolymer having a succinic anhydride group as a reactive group, or a low molecule thereof. Modified product of diol or low molecular weight diamine, ethylene-glycidyl methacrylate copolymer, ethylene-ethyl acrylate-
Glycidyl methacrylate copolymer, ethylene-vinyl acetate-copolymer having an epoxy group as a reactive group such as glycidyl methacrylate copolymer, styrene-vinyloxazoline copolymer, styrene-acrylonitrile-vinyloxazoline copolymer Thus, it is known to use a copolymer having an oxazoline group as a reactive group.

[0008] More specifically, for example, J. Appl. P
olym. Sci. Vol. 39, P.I. 655-678
In (1990), it is proposed to improve the compatibility between polystyrene and polyethylene by using, as a compatibilizing agent, a product obtained by reacting polystyrene having an oxazoline group and polyethylene modified with a carboxylic acid in a melt blend. .

Japanese Unexamined Patent Publication No. 4-285648 discloses that an epoxy group-containing olefin elastomer is used as a compatibilizing agent when blending carboxylic acid-modified polypropylene and polystyrene. In the publication, it is proposed to use a carboxylic acid-modified olefin elastomer as a compatibilizing agent when blending epoxy-modified polypropylene and polystyrene.

Further, Japanese Patent Laid-Open No. 4-53853 discloses that
There has been devised a method of increasing the compatibility between polyolefin and polystyrene by forming a composition of a mixture of polyolefin with epoxy-modified polyolefin and a mixture of polystyrene with carboxylic acid-modified polystyrene.

All of these utilize the reactivity between the epoxy group and the carboxyl group.

As a method using the same compatibilization principle, Japanese Patent Laid-Open No. 3-33151 discloses that when a polyphenylene ether resin and a polyolefin resin are blended, a carboxyl group that can react with an amino group as the polyphenylene ether resin is used. A modified polyolefin obtained by grafting a carbamic acid ester of a tertiary alcohol such as t-butylallyl carbamate (t-butyl ester of allylcarbamic acid) onto a polyolefin is used as the polyolefin-based resin by using a functionalized polyphenylene ether having an epoxy group or an epoxy group. Is proposed.

As the mechanism of action, the grafted t-butylallyl carbamate is decarboxylated at a temperature of 225 ° C. or higher and converted into an amino group, and the produced amino group is a carboxyl group or epoxy group of the functionalized polyphenylene ether. A mechanism for reacting with is proposed.

However, the miscibility of the resins with each other has not been sufficiently solved even by using or forming the above-mentioned conventionally known compatibilizer, and therefore the impact strength of the obtained resin composition is insufficient. Is. Further, when the resin composition is formed into a molded article, there are problems such as poor appearance and delamination.

Further, depending on the type of compatibilizer used,
For example, as in the case of using a compatibilizing agent modified with an allylcarbamic acid ester of a tertiary alcohol, a new problem may occur that the resin composition itself is colored due to the high temperature during molding.

Therefore, the present invention has been invented in view of the above-mentioned problems of the prior art, and an object thereof is to have an excellent impact strength, a good appearance at the time of molding and a delamination does not occur. A thermoplastic resin composition comprising a polyolefin resin and a polystyrene resin is provided.

[0017]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in view of the above-mentioned problems of the prior art, and as a result, as a compatibilizing agent when melting and kneading a polyolefin resin and a polystyrene resin. By using a copolymer or a graft copolymer having a specific functional group (formamide group, amino group, acylamino group or carbamate group), it has excellent impact resistance, good appearance even after molding and delamination occurs. It was found that such a thermoplastic resin composition can be obtained.

That is, the thermoplastic resin composition according to the present invention is a thermoplastic resin composition containing the following three components A, B and C.

(A) A polyolefin resin (A-1) having a functional group capable of reacting with an amino group, a polyolefin resin (A-2) having substantially no functional group, or the above-mentioned polyolefin resin (A- 1 to 5 to 95 parts by weight of a composition comprising the polyolefin resin (A-2),
(B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group, a polystyrene resin (B-2) having substantially no functional group, or the polystyrene resin (B-1) 95 to 5 parts by weight of the composition comprising the polystyrene resin (B-2) (provided that the component A-2 and B
-2 component), and (C) a copolymer having a repeating unit (a) or a repeating unit (b) represented by the general formula 9 in the molecule or a salt thereof in an amount of 0.05 to 20% by weight. Department.

[0020]

[Chemical 9]

Here, in the chemical formula 9, R ¹ and R ² are
Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms or an arylalkyl group having 7 or 8 carbon atoms, and R ³ represents an alkylene group having 1 to 18 carbon atoms or a carbon atom. A cycloalkylene group having 5 to 17 carbon atoms, an arylene group having 6 to 12 carbon atoms or an arylalkylene group having 7 to 17 carbon atoms, R ⁴ represents a hydrogen atom, a formyl group,
An acyl group or an alkoxycarbonyl group, and R ⁵ is
A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹ to
R ⁵ may be the same or different in each repeating unit.

The copolymer in the component C is
Ordinary copolymer obtained by polymerization of a monomer mixture,
It is a concept that includes a graft copolymer and a block copolymer.

In the thermoplastic resin composition according to the present invention, the functional groups capable of reacting with the amino groups in the components A and B have succinic anhydride groups, carboxyl groups, epoxy groups, ester groups, amide groups. , A cyclic iminoether group, a cyclic iminoamino group, a halogen, an isocyanate group, and an imide group, which is one or more functional groups selected from the group consisting of functional groups.

Component A-1 and A which can be used in the present invention
-2 and the combination of B-component B-1 and B-2 of Table B is shown in Table 1.
Shown in. As shown in Table 1, in the present invention, the components A-2 and B having no functional group capable of reacting with the amino group are present.
-No possible combination with the -2 component.

[0025]

[Table 1]

Hereinafter, each component in the thermoplastic resin composition of the present invention will be described in more detail.

[1] About Component A (i) Component A-1 Component A-1 in the present invention is a polyolefin resin having a functional group capable of reacting with an amino group at its side chain or molecular end. Examples of such functional groups include succinic anhydride group, carboxyl group, epoxy group, ester group, amide group, cyclic imino ether group, cyclic iminoamino group,
Examples include halogens, isocyanate groups and imide groups. Of these, the important and preferred functional groups are succinic anhydride groups, carboxyl groups and epoxy groups.

The polymer having a succinic anhydride group in the side chain is
Obtained by copolymerizing maleic anhydride or itaconic anhydride with an ethylenically unsaturated monomer, or by graft-polymerizing maleic anhydride or itaconic anhydride to a polymer such as polyolefin in the presence of a radical initiator. To be

Specific examples include ethylene-maleic anhydride copolymers and maleic anhydride grafted products of polymers such as polyethylene, polypropylene, ethylene-propylene rubber, ethylene-propylene-diene copolymer (EPDM). It can be illustrated.

The polymer having a carboxy group in the side chain is a copolymer of a carboxylic acid containing an ethylenically unsaturated bond such as acrylic acid or methacrylic acid and an ethylenically unsaturated monomer,
Obtained by graft-polymerizing a carboxylic acid containing an ethylenically unsaturated bond to a polymer such as polyolefin, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-maleic anhydride-acrylic acid copolymer Examples thereof include (meth) acrylic acid grafted products of polymers such as polyethylene, polypropylene, and ethylene propylene rubber.

Examples of the polymer having an epoxy group in the side chain include glycidyl acrylate, or a copolymer of glycidyl methacrylate and an ethylenically unsaturated monomer, such as ethylene-glycidyl methacrylate copolymer and propylene-glycidyl. A typical example is a methacrylate copolymer.

Examples of the polymer having an ester group as a side chain include ester group-containing ethylenically unsaturated monomers such as alkyl acrylate, alkyl methacrylate, and alkyl vinyl ester, and other ethylenically unsaturated monomers. A copolymer with a polymer can be used, and examples thereof include an ethylene-acrylic acid ester copolymer, an ethylene-methacrylic acid ester copolymer, and an ethylene-vinyl acetate copolymer.

As the polymer having an amide group in the side chain,
Examples thereof include copolymers of acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide and N, N-dimethylacrylamide with other ethylenically unsaturated monomers.

Examples of the polymer having a cyclic iminoether group in its side chain include 2-vinyloxazoline, a copolymer of 2-vinyloxazine and another ethylenically unsaturated monomer, and the like.

As a polymer having a cyclic iminoamino group in its side chain, there is a copolymer of 2-vinylimidazoline and another ethylenically unsaturated monomer.

Examples of the polymer having a halogen in the side chain include polyvinyl chloride, chlorinated polyolefin, chloroethyl vinyl ether copolymer, chloromethylated polystyrene and the like.

Examples of the polymer having an imide group in the side chain include a copolymer of N-phenylmaleimide, N-alkylmaleimide and another ethylenically unsaturated monomer.

As an example of the polymer having a carboxyl group at the terminal of the molecule, a radical initiator having a carboxyl group is used, and a chain transfer agent having a carboxyl group is optionally used to obtain a carboxyl group at one end obtained by radical polymerization. Examples of the contained polymer include a terminal carboxypolyisoprene and a terminal carboxy-polymethacrylic acid ester.

Among the A-1 components, the preferred A-1 component is a polyolefin or a polyolefin elastomer modified with succinic anhydride group, carboxyl group, epoxy group, ester group, halogen.

(Ii) Component A-2 The component A-2 in the present invention is selected from polyolefin resins having substantially no functional group, and will be described in more detail. -Based elastomers, polyolefin-based thermoplastic elastomers, ethylene-vinyl ester copolymers,
It is an ethylene-acrylic ester copolymer and the like, and also includes blends of these various polyolefins and copolymers.

Specific examples of the component A-2 include polyethylene [linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ultra low density polyethylene (V
LDPE), medium density polyethylene, high density polyethylene (HDPE), etc.], homopolymers of polypropylene, polybutene, polyisobutene, etc., ethylene-propylene copolymers, low crystalline ethylene-propylene copolymers, ethylene-propylene copolymers. Ethylene-α-olefin copolymers such as rubber (EPR), ethylene-butene copolymer (EBM), ethylene-propylene-diene copolymer (EPDM), ethylene-propylene-butene copolymer, ethylene-butylene copolymer Polymers, copolymers of propylene and other α-olefins such as propylene-butene copolymers,
Furthermore, various ethylene-based copolymers [ethylene-vinyl alcohol copolymer (EVOH), etc.], poly (4-methyl-1-pentene), butyl rubber, butadiene rubber, and blends of polypropylene and ethylene-propylene rubber are mainly used. And the like, and mixtures thereof. The term "copolymer" as used herein includes random copolymers, block copolymers, random block copolymers, and further graft copolymers.

[2] About Component B (i) Component B-1 Component B-1 in the present invention is a polystyrene polymer containing a functional group capable of reacting with an amino group at its side chain or molecular end. is there. Examples of such functional groups include succinic anhydride group, carboxyl group, epoxy group, ester group, amide group, cyclic imino ether group, cyclic iminoamino group,
Examples include halogens, isocyanate groups and imide groups. Among these, important and preferable functional groups are a succinic anhydride group, a carboxyl group, and a cyclic iminoether group.

Examples of the styrene-based polymer having a succinic anhydride group on its side chain include a styrene-maleic anhydride copolymer, a styrene-itaconic acid copolymer, and a maleic anhydride grafted product of the styrene-based polymer. Can be mentioned. Examples of such graft products include styrene-butadiene-
Examples thereof include hydrogenated products of styrene block copolymers (SEBS) and hydrogenated products of block copolymers of styrene-isoprene-styrene (SEPS), which are grafted with maleic anhydride.

Examples of the styrene-based polymer having a carboxyl group in the side chain include a copolymer of styrene and (meth) acrylic acid, and a grafted product of (meth) acrylic acid of SEBS or SEPS.

Examples of the styrene-based polymer having an epoxy group in its side chain include a styrene-glycidyl (meth) acrylate copolymer.

Examples of the styrene-based polymer having an ester group in the side chain include a styrene- (meth) acrylic acid ester copolymer.

Examples of the styrene-based polymer having an amide group in its side chain include a styrene- (meth) acrylamide copolymer.

A styrene-2-vinyloxazoline copolymer is an example of the styrene-based polymer having a cyclic imino ether in the side chain.

Examples of the styrene-based polymer having a cyclic iminoamino group in its side chain include a styrene-2-vinylimidazoline copolymer.

Examples of the styrene-based polymer having a halogen side chain include chloromethylated polystyrene.

Examples of the styrene polymer having an imide group in the side chain include a styrene-N-phenylmaleimide copolymer, a styrene-N-alkylmaleimide copolymer and the like.

As an example of the styrene-based polymer having a carboxyl group at the molecular end, a radical initiator having a carboxyl group is used, and if necessary, a chain transfer agent having a carboxyl group is used to obtain one end obtained by radical polymerization. Examples thereof include carboxyl group-containing polymers such as terminal carboxypolystyrene.

Of these B-1 components, preferred B-
One component is polystyrene modified with a succinic anhydride group, a carboxyl group, an amide group, or an oxazoline group or an elastomer thereof.

(Ii) Component B-2 Component B-2 in the present invention is selected from polystyrene-based resins having substantially no functional group, specifically, styrene, α-methylstyrene and p-. Examples thereof include homopolymers and copolymers of methylstyrene, and examples thereof include general-purpose polystyrene (GPPS) and high-impact polystyrene (HIP).
S), and further examples include SEBS resin, SEPS resin, SEP resin, etc., which are styrene-based thermoplastic elastomers.

Among such polystyrene resins, general-purpose polystyrene (GPPS) and high impact polystyrene (H
IPS) is preferable, and its average molecular weight is 20,
000 to 300,000, preferably 30,000 to 2
Those of 0,000 are preferred.

Further, as the polystyrene resin of the component B-2, a resin containing a so-called ABS resin can be mentioned, and the kind thereof is not particularly limited, and a resin by a graft method or a polymer blend method can be used. Further, AS resin (acrylonitrile-styrene resin), AES resin (acrylonitrile-EPDM-styrene resin) and the like can be used, but ABS resin is preferable.

[3] Component C As described above, the component C (compatibilizer) in the thermoplastic resin composition of the present invention is a repeating unit (a) represented by the general formula 10 in the molecule or A copolymer having the repeating unit (b) or a salt thereof is used.

[0058]

[Chemical 10]

In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon atom having 6 to 8 carbon atoms.
Or an arylalkyl group having 7 or 8 carbon atoms, R ³ is an alkylene group having 1 to 18 carbon atoms,
Cycloalkylene group having 5 to 17 carbon atoms, 6 to 12 carbon atoms
Represents an arylene group or an arylalkylene group having 7 to 17 carbon atoms, R ⁴ represents a hydrogen atom, a formyl group, an acyl group or an alkoxycarbonyl group, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. And R ^{1 to} R ⁵ are
They may be the same or different for each repeating unit.

The above repeating unit (a) and repeating unit
(b) may be present in the main chain of the copolymer or may be present in the side chain of the copolymer. Further, the term "copolymer" as used herein is a general concept including a general copolymer, a graft copolymer and a block copolymer obtained by polymerizing a monomer mixture.

Repeating unit (a) represented by the above general formula 10
Include the formamide repeat unit (Ia), the amino repeat unit (II
a), an acylamino repeating unit (IIIa) and a carbamate repeating unit (IVa), and the repeating unit (b) represented by the general formula 10 above includes a formamide repeating unit (Ib), an amino repeating unit (IIb), There are acylamino repeat units (IIIb) and carbamate repeat units (IVb).

That is, the formamide repeating unit (Ia), amino repeating unit (IIa), acylamino repeating unit (IIIa) and carbamate repeating unit (IVa) are each represented by the general formula 1
It is represented by Formula 1, Formula 12, Formula 13, and Formula 14.

[0063]

[Chemical 11]

[0064]

[Chemical 12]

[0065]

[Chemical 13]

[0066]

[Chemical 14]

In the formulas 11 to 14, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or 7 carbon atoms or 8 represents an arylalkyl group, wherein R ³ has 1 to 1 carbon atoms
An alkylene group having 8 carbon atoms, a cycloalkylene group having 5 to 17 carbon atoms, an arylene group having 6 to 12 carbon atoms or 7 to 17 carbon atoms
Shows the arylalkylene group, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁶ is 1 to carbon atoms
8 represents an alkyl group, a phenyl group or a benzyl group, and R
⁷ represents a primary or secondary alkyl group having 1 to 8 carbon atoms, and R ^{1 to} R ³ and R ^{5 to} R ⁷ may be the same or different for each repeating unit.

On the other hand, the formamide repeating unit (Ib), amino repeating unit (IIb), acylamino repeating unit (IIIb) and carbamate repeating unit (IVb) are represented by general formulas 15, 15, 16 and 18, respectively. Is a repeating unit.

[0069]

[Chemical 15]

[0070]

[Chemical 16]

[0071]

[Chemical 17]

[0072]

[Chemical 18]

Here, in Chemical formulas 15 to 18, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or 7 carbon atoms or 8 represents an arylalkyl group, wherein R ³ has 1 to 1 carbon atoms
An alkylene group having 8 carbon atoms, a cycloalkylene group having 5 to 17 carbon atoms, an arylene group having 6 to 12 carbon atoms or 7 to 17 carbon atoms
Represents an arylalkylene group of R ⁶ and R ⁶ has 1 to 8 carbon atoms.
An alkyl group, a phenyl group or a benzyl group of R ⁷
Represents a primary or secondary alkyl group having 1 to 8 carbon atoms, and R ^{1 to} R ³ and R ^{6 to} R ⁷ may be the same or different for each repeating unit.

These repeating units (Ia), (IIa), (IIIa), (IVa),
A copolymer having two or more repeating units of (Ib), (IIb), (IIIb) and (IVb) in the molecule or a salt thereof is used as the C component in the thermoplastic resin composition of the present invention. You may use.

The C component having the above-mentioned constitution can be easily produced by polymerizing a copolymer having a succinic anhydride group in its main chain or side chain as a raw material.

Specific examples of the copolymer having a succinic anhydride group in the main chain used as a raw material include styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer. Coalesced, ethylene
Propylene-maleic anhydride copolymer, isobutylene-
Maleic anhydride copolymer, methyl vinyl ether-maleic anhydride copolymer, styrene-isoprene-maleic anhydride copolymer, ethylene-maleic anhydride-ethyl acrylate copolymer, ethylene-maleic anhydride-methyl acrylate Examples thereof include copolymers, ethylene-vinyl acetate-maleic anhydride copolymers and styrene-butadiene-maleic anhydride copolymers.

Specific examples of the copolymer having a succinic anhydride group in the side chain used as a raw material include α-olefin polymers such as polyethylene and polypropylene, ethylene-propylene copolymer rubber (EPR) and styrene. -Butadiene-styrene block copolymer hydrogenated product (S
EBS), a hydrogenated product of a styrene-isoprene-styrene block copolymer (SEPS), or the like is added to a thermoplastic (co) polymer using a known peroxide or an initiator, and maleic anhydride or methylmaleic anhydride is used. Examples thereof include a graft copolymer obtained by graft-reacting an unsaturated dicarboxylic acid anhydride such as acid, 1,2-dimethylmaleic acid, ethylmaleic anhydride, phenylmaleic anhydride, and itaconic anhydride.

Of these, the preferred graft copolymer is a copolymer obtained by graft reaction of maleic anhydride with SEBS or SEPS. Commercially available polymers (maleic acid-modified EPR, maleic acid-modified SEBS) graft-reacted with the above-mentioned unsaturated dicarboxylic acid anhydride are used.
Etc.) can be used as a raw material copolymer.

Various methods can be adopted for converting the raw material copolymer having a succinic anhydride group into the component C used in the resin composition of the present invention, and the method is not particularly limited. The method described in JP-A-43972 is adopted.

That is, a diamine (V) represented by the general formula 19 or a diamine (VI) represented by the general formula 20 is reacted with a formyl group-containing compound such as formamide, formic acid ester and formic acid. By reacting the product obtained, with the succinic anhydride group-containing raw material copolymer described above,
Formamide repeating unit represented by the general formula 11
(Ia) or the formamide repeating unit represented by the general formula 15
A copolymer (C component) having (Ib) in the molecule is obtained.

[0081]

[Chemical 19]

[0082]

[Chemical 20]

(However, in Chemical formula 19 and Chemical formula 20, R ³
Represents an alkylene group having 1 to 18 carbon atoms, a cycloalkylene group having ⁵ to 17 carbon atoms, an arylene group having 6 to 12 carbon atoms or an arylalkylene group having 7 to 17 carbon atoms, and R ⁵
Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )
By hydrolyzing the thus obtained copolymer having the formamide repeating unit (Ia) or (Ib) in the molecule, by using a mineral acid such as hydrochloric acid or sulfuric acid or an organic acid such as p-toluenesulfonic acid as a catalyst. A copolymer (component C) having the amino repeating unit (IIa) represented by the general formula 12 or the amino repeating unit (IIb) represented by the general formula 16 in the molecule can be obtained. In this case, the formamide repeating unit (Ia)
Alternatively, it is not always necessary to hydrolyze all the formyl groups of (Ib), and it is also possible to partially hydrolyze some of the formyl groups to leave a part of the formyl groups.

Further, the amino repeating unit (IIa) or (I
The copolymer having Ib) in the molecule includes an acyl halide having 1 to 8 carbon atoms, a carboxylic acid anhydride, a benzoyl halide,
By reacting phenylacetyl chloride and an alkyl halocarbonate having a primary or secondary alkyl group having 1 to 8 carbon atoms (eg, ethyl chlorocarbonate), the acylamino repeating unit (IIIa) represented by the above general formula 13 Having an acylamino repeating unit (IIIb) represented by general formula 17, a carbamate repeating unit (IVa) represented by general formula 14 or a carbamate repeating unit (IVb) represented by general formula 18 in the molecule. A copolymer is easily obtained.

Diamine (V) represented by the above general formula 19
There are two types of non-substituted diamines and N-substituted diamines.

Specific examples of the diamine (V) which is an unsubstituted diamine include ethylenediamine; 1,3-diaminopropane; 1,4-diaminobutane; 1,5-diaminopentane; hexamethylenediamine; 7-diaminoheptane; 1,8-diaminooctane; 1,9-
Diaminononane; 1,10-diaminodecane; 2,2
5-trimethylhexanediamine; linear or branched aliphatic alkylenediamines such as 2,2,4-trimethylhexanediamine, isophoronediamine; 1,3-bis (aminomethyl) cyclohexane; bis (4-aminocyclohexyl) Methane; bisaminomethylhexahydro-4,7-methaneindane; 1,4-cyclohexanediamine; 1,3-cyclohexanediamine; 2-methylcyclohexanediamine; 4-methylcyclohexanediamine; bis (4-amino-3,5 Alicyclic diamines such as -dimethylcyclohexyl) methane; m-xylylenediamine; arylalkyldiamines such as p-xylylenediamine; p-phenylenediamine; aryldiamines such as 4,4'-diaminodiphenylether. .

Among the specific examples of diamine (V), N-substituted diamines include N-methylmethylenediamine; N-ethylmethylenediamine; N-propylmethylenediamine; N-butylmethylenediamine; N-methyl. Ethylenediamine; N-ethylethylenediamine; N
-Propylethylenediamine; N-butylethylenediamine; N-methyl-1,3-propanediamine; N-ethyl-1,3-propanediamine; N-propyl-1,
3-propanediamine; N-butyl-1,3-propanediamine; N-methyl-1,4-butanediamine; N-
Ethyl-1,4-butanediamine; N-propyl-1,
4-butanediamine; N-butyl-1,4-butanediamine; N-methyl-1,6-hexanediamine; N-ethyl-1,6-hexanediamine; N-propyl-1,
6-hexanediamine; N-butyl-1,6-hexanediamine; N-methyl-1,8-octanediamine; N
-Ethyl-1,8-octanediamine; N-methyl-
1,12-dodecanediamine; N-ethyl-1,12-
Dodecanediamine; N-propyl-1,12-dodecanediamine; N-butyl-1,12-dodecanediamine;
N-methyl-1,18-octadecanediamine; N-ethyl-1,18-octadecanediamine; N-propyl-1,18-octadecanediamine; N-butyl-1,
N-lower alkyl-substituted linear aliphatic diamine such as 18-octadecanediamine, N-methyl-2,2,5-trimethyl-1,6-hexanediamine; N-ethyl-2,
2,5-Trimethyl-1,6-hexanediamine; N-
Propyl-2,2,5-trimethyl-1,6-hexanediamine; N-butyl-2,2,5-trimethyl-1,
N-lower alkyl-substituted branched aliphatic diamine such as 6-hexanediamine, N-methyl-isophoronediamine; N
-Ethyl-isophoronediamine; N-propyl-isophoronediamine; N-butyl-isophoronediamine; 1-
N-methylaminomethyl-3-aminomethyl-cyclohexane; N-lower alkyl-substituted alicyclic diamine such as 1-N-ethylaminomethyl-3-aminomethyl-cyclohexane, N-methyl-m-xylylenediamine; N -Ethyl-p-xylylenediamine; N-methyl-p-xylylenediamine; N-lower alkyl-substituted arylalkyldiamines such as N-ethyl-p-xylylenediamine,
N-methyl-p-phenylenediamine; N-ethyl-p
-Phenylenediamine; N-Methyl-m-phenylenediamine; N-, such as N-ethyl-p-phenylenediamine
Lower alkyl-substituted aryldiamine and the like can be mentioned.

Of these, ethylenediamine, 1,3
-Diaminopropane, 1,4-diaminobutane, hexamethylenediamine, N-methylethylenediamine; N-
Ethyl ethylenediamine; N-methyl-1,3-propanediamine; N-ethyl-1,3-propanediamine;
N-methyl-1,4-butanediamine; N-ethyl-
Aliphatic and alicyclic diamines such as 1,4-butanediamine; N-methyl-1,6-hexanediamine; N-ethyl-1,6-hexanediamine are preferred.

On the other hand, specific examples of the diamine (VI) represented by the general formula 20 include N-aminomethylpiperazine; N-aminoethylpiperazine; N-aminopropylpiperazine; N-aminobutylpiperazine; N- Aminohexylpiperazine; N-aminooctylpiperazine;
Examples thereof include N- (4-amino-2,2-dimethylbutyl) piperazine. Of these, N-aminoethylpiperazine; N-aminopropylpiperazine; N-aminobutylpiperazine; N-aminohexylpiperazine are preferred.

As described above, C in the resin composition of the present invention is
The component is a copolymer having the repeating unit (a) or the repeating unit (b) represented by the general formula 10 in the molecule or a salt thereof, and the C component of the repeating unit (a) or (b) The content in the resin composition varies depending on the physical properties and appearance of the desired thermoplastic resin composition and cannot be determined unconditionally, but is usually 0.05 to 30.
%, Preferably 1.0 to 20% by weight.

If the content is less than 0.05% by weight, the miscibility of the resins in the finally obtained resin composition will be poor, and if it exceeds 30% by weight, the thermoplastic resin composition will Not only is it uneconomical to produce the resin, but it may deteriorate the physical properties of the resin composition obtained on the contrary.

Regarding the content of the repeating units (a) and (b) in the C component, when the repeating units are amino repeating units (IIa) and (IIb), the content can be determined by potentiometric titration. . In addition, the repeating unit is the formamide repeating unit (Ia), (I
In the case of b), 1650-
Observing the absorption intensity peculiar to the formyl group at 1700 cm ^-1 ,
When the repeating unit is an acylamino repeating unit (IIIa) or (IIIb), the infrared absorption spectrum shows 1650 to 1700c.
observing acylamino group specific absorption intensity m ^-1, the repeating units carbamate repeating units (IVa), a carbamate-specific absorption intensity 1720～1730Cm ^-1 by infrared absorption spectrum in a (IVb) Observed, 720 cm ^-1 based on these absorption intensity and the main chain of C component copolymer
Alternatively, the content of each repeating unit can be determined by comparing the absorption intensity at 1460 cm ^-1 .

[4] About composition ratio of thermoplastic resin composition: The thermoplastic resin composition of the present invention comprises the above [1] to
The component A, the component B, and the component C described in [3] are essential constituent components, but if necessary, other additives (reinforcing material such as glass fiber and carbon fiber, inorganic filler, Heat stabilizer, antistatic agent, antioxidant, light stabilizer, flame retardant, weathering agent, etc.) may be added.

The blending ratios of the components A, B and C in the thermoplastic resin composition of the present invention are as follows.
The component A is mixed in an amount of 5 to 95 parts by weight, preferably 20 to 95 parts by weight, and the component B is 9
The amount is 5 to 5 parts by weight, preferably 80 to 5 parts by weight. A
When the mixing ratio of the component and the component B is out of the above range, there arises a problem that mechanical strength such as rigidity is lowered and molding processability is deteriorated in the obtained resin composition.

The mixing ratio of the component C is 0.05 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the components A and B. If the blending ratio of the component C is less than 0.05 parts by weight, the mixing of the resins of the component A and the component B will be insufficient, and various physical properties such as impact strength of the resulting resin composition will not be sufficiently improved. Further, even if the blending ratio of the C component exceeds 20 parts by weight, the effect of improving various physical properties corresponding to the blending amount of the C component is not recognized, and rather the impact strength of the resin composition tends to decrease. Moreover, it is economically disadvantageous in producing the resin composition.

[5] Regarding Method for Producing Thermoplastic Resin Composition: In order to produce the thermoplastic resin composition of the present invention, the order of addition of the components A, B and C, the timing of addition, and the addition method are not particularly limited. There is no.

As the simplest example, the components A, B and C may be heated and melted at the same time, or a mixture of the components B and C previously melted and kneaded may be added to the component A and melted and kneaded. Of course, various combinations of addition order, timing and method can be adopted.

In the method for producing the thermoplastic resin composition of the present invention, specifically, a kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneading roll, or a mixer such as a Henschel mixer is used. Then, the above components may be kneaded in a heat-melted state. The kneading temperature varies depending on the types of constituent components used, the amount of the components used, the physical properties of the resin composition to be produced, and the like, and cannot be unambiguously determined, but it is usually selected in the range of 180 to 340 ° C.

It should be noted that chemical formula 11, chemical formula 12, chemical formula 13, and chemical formula 14
Repeating units (Ia), (IIa), (IIIa) and (IV
When a thermoplastic resin composition is produced by using the C component having a), those having R ⁵ of hydrogen tend to be slightly colored, whereas those having an alkyl group do not show coloring, and From the viewpoint, it is preferable to use one in which R ⁵ is an alkyl group.

[0100]

In the thermoplastic resin composition of the present invention, the component C has the function of increasing the miscibility of the thermoplastic resin of the component A with the thermoplastic resin of the component B or its composition. Is estimated as follows in consideration of the polymer structure of the C component.

That is, first, when an amino group is present in the C component, this essentially reacts with the B component. Also,
When the C component has a formamide group, an acylamide group or a carbamic acid ester group, these are decomposed by the action of heat during kneading and converted into an amino group. Then, this amino group is subjected to an amidation reaction, an esterification reaction, a transesterification reaction, a transamidation reaction, etc. with a functional group capable of reacting with the amino group contained in the A-1 component or the B-1 component, and the C component. And A-1 component or B-1 component are combined. As a result, the compound of the C component and the A-1 component or the B-1 component exhibits a compatibilizing action, and the miscibility of the resins of the A component and the B component is enhanced, and as a result, impact resistance, peeling property, etc. It is considered that various physical properties of are improved.

[0102]

According to the present invention, by using a compatibilizing agent (component C) having an amino group, a formamide group, an acylamino group and a carbamic acid ester group, a polyolefin resin of component A and polystyrene of component B are used. The miscibility with the system resin is enhanced, whereby a thermoplastic resin composition having excellent impact resistance can be obtained, and a thermoplastic resin composition that has a good appearance even when molded and does not cause delamination can be obtained. Further, it is possible to achieve a remarkable effect that a thermoplastic resin composition which is not colored even when molded at a high temperature and has a good hue of a molded product is obtained.

[0103]

EXAMPLES Examples of the present invention will be described below.
The invention is not limited to these examples.

(1) Synthesis Examples 1 to 1 of Compatibilizer (Component C)
3 The compatibilizer (component C) shown in Table 2 below was synthesized.

[0105]

[Table 2]

Synthesis Examples 1 to 13 will be described below.

<Synthesis Example 1> 80 ml of DMF and neutralization equivalent of 8.54 meq / g of N-methyl were added to a flask having an internal capacity of 1 liter equipped with a thermometer, a stirrer, a dropping funnel, and a Dean-Stark water separator. 1,3-Propanediamine and 5.6 g of a reaction product of DMF were charged, heated and melted at 80 ° C.

Next, a styrene-maleic anhydride (molar ratio 95/5) copolymer (Mw = 52,000) was added to the flask.
A solution of 71 g of (0, Mn = 25,000) dissolved in 350 ml of xylene was gradually added dropwise with a dropping funnel.

After completion of the dropwise addition, a part of the reaction mixture was sampled and the infrared absorption spectrum was measured. As a result, the absorption based on the ring of the acid anhydride at 1780 cm ^-1 was completely disappeared.

Thereafter, heating and heating were continued, and since water azeotroped with the reflux of xylene from around 140 ° C., this was separated by a Dean-Stark water separator.

The reaction was continued at 140 ° C. for 9 hours, the reaction was terminated when the generation of new water was not observed, the reaction mixture was poured into 5 liters of methanol, and the product was recovered as a precipitate. After thoroughly washing this precipitate with methanol,
Dried. The yield of the obtained copolymer was 73.8 g.

Further, when a toluene cast film was prepared and the infrared absorption spectrum was measured, it was 1775 cm.
^-1 , 1695 cm ^-1 in addition to absorption based on the imide ring 16
There was absorption of formamide group at 65 cm ^-1 (shoulder). However, no absorption based on the amino group was observed.

On the other hand, in the nuclear magnetic resonance ( ¹³ C-NMR) spectrum by isotope carbon measured in CDCI ₃ , it is 1
A peak of the carbonyl carbon of the imide ring appeared at 76 to 180 ppm, and a peak showing the presence of the carbonyl carbon of the formamide group appeared at 162 ppm.

<Synthesis Example 2> The compound obtained in Synthesis Example 1 was hydrolyzed in hydrochloric acid / methanol to obtain a compatibilizer of Synthesis Example 2.

<Synthesis Example 3> The compound of Synthesis Example 2 was acetylated with acetic anhydride to obtain the compatibilizer of Synthesis Example 3.

<Synthesis Example 4> The compatibilizer of Synthesis Example 2 was carbamate with isopropyl chlorocarbonate to obtain the compatibilizer of Synthesis Example 4.

<Synthesis Example 5> SEBS as a raw material copolymer
(Maleic acid graft product of hydrogenated product of styrene-butadiene-styrene block copolymer; styrene / butadiene = 3/7, Mw = 85,000, Mn = 48.0
No. 00, grafted amount of maleic anhydride = 1.6% by weight), and using N-aminoethylpiperazine as the diamine, a compatibilizer of Synthesis Example 5 was obtained in the same manner as in Synthesis Example 1.

<Synthesis Example 6> The compatibilizer of Synthesis Example 5 was hydrolyzed with hydrochloric acid methanol and then acylated with butyric anhydride to obtain a compatibilizer of Synthesis Example 6.

<Synthesis Example 7> The compatibilizing agent of Synthesis Example 5 was hydrochloric acid /
After hydrolyzing with methanol, it was carbamate with ethyl chlorocarbonate to obtain a compatibilizer of Synthesis Example 7.

<Synthesis Example 8> As a raw material copolymer, ethylene propylene rubber (maleic anhydride grafted product of ethylene / propylene = 65/35 (Mw = 38,000, M
n = 18,000, maleic anhydride graft amount = 0.8
(% By weight) and hexamethylenediamine was used as the diamine to carry out the same reaction as in Synthesis Example 1 to obtain a compatibilizer of Synthesis Example 8.

<Synthesis Example 9> The same procedure as in Synthesis Example 9 was repeated except that N-ethyl-1,12-dodecanediamine was used in place of N-aminoethylpiperazine in Synthesis Example 5. A compatibilizer was obtained.

<Synthesis Example 10> The same procedure as in Synthesis Example 5 was repeated except that N-methyl-isophoronediamine was used instead of N-aminoethylpiperazine in Synthesis Example 5, and the compatibilizer of Synthesis Example 10 was used. Obtained.

<Synthesis Example 11> The compatibilizing agent of Synthesis Example 5 was hydrolyzed with methanol and then acylated with phenylacetyl chloride to obtain the compatibilizing agent of Synthesis Example 11.

<Synthesis Example 12> The compatibilizer of Synthesis Example 5 was hydrolyzed with methanolic hydrochloric acid and then acylated with benzoyl chloride to obtain a compatibilizer of Synthesis Example 12.

<Synthesis Example 13> A maleic anhydride grafted product of polypropylene (Mw = 60, as a raw material copolymer)
000, Mn = 28,000, maleic anhydride graft amount = 2.0% by weight), and N-aminoethylpiperazine was used as the diamine to react in the same manner as in Synthesis Example 1 and the compatibilizer of Synthesis Example 13 was used. Got

(2) Examples 1 to 15 Specific examples of the thermoplastic resin composition according to the present invention will be described. When obtaining the thermoplastic resin composition, A-
The one shown in Table 3 is used as the one-component resin, the one shown in Table 7 is used as the A-2 component resin, and the one shown in Table 5 is used as the B-1 component resin. The resin shown in Table 6 was used as the resin.

[0127]

[Table 3]

[0128]

[Table 4]

[0129]

[Table 5]

[0130]

[Table 6]

These A, B and C components were used in the proportions shown in Table 7 to obtain the thermoplastic resin compositions of Examples 1 to 15 according to the present invention. That is, the components A, B and C were dry blended at a predetermined ratio and dried, and then melt-kneaded using a biaxial extractor (KRC kneader, manufactured by Kurimoto Tekkosho) and taken out, and then pelletized.

The pelletized resin composition was processed by using an injection molding machine (Hipershot 3000, manufactured by Niigata Iron Works) to obtain a molded product. The Izod impact strength of this molded product, the presence or absence of delamination and the appearance were examined and evaluated. The results are also shown in Table 7.

[0133]

[Table 7]

(3) Evaluation Method The evaluation method of the above molded article will be described. For Izod impact strength, Izod impact value is JIS K71
The measurement temperature is 23 ° C. and −30.
℃ was made.

Further, the presence or absence of delamination of the molded product was inspected by a base stitch test. That is, a 1 mm × 1 mm rectangle 100 is formed by making a notch on the surface of a test piece with a knife.
The individual pieces are formed into a matrix. Then, the cellophane tape is pressure-bonded and then peeled off with a strong force, and the number of the short shapes which are not attached to the cellophane tape and are not peeled off from the test piece is counted. The larger the number is, the more difficult the layered peeling is.

Further, regarding the appearance and hue of the molded product,
The generation of flow marks, fluffiness, silver, and the degree of coloring were visually determined. In Table 7, those having a good appearance are indicated by ◯, those having a somewhat poor appearance are indicated by Δ, and those having a poor appearance are indicated by x.

<Comparative Examples 1 to 11> In each of Examples 1 to 11, examples in which the component C (compatibilizer) was not blended are shown in Table 7 as Comparative Examples 1 to 11. In addition, as Comparative Example 9, the case where the following compatibilizing agent was used is also shown in Table 7.

<Comparative Example 12> Polypropylene (Mw = 6)
4,000, Mn = 30,000).
According to the method of No. 51, 5.1 wt% of allylcarbamic acid-t-butyl ester was graft-reacted (comparative synthesis example).

With reference to Table 7, Examples 1 to 15 in which the resin composition of the present invention was molded and processed, and Comparative Examples 1 to 11 in which the component C (compatibilizer) was not blended in Examples 1 to 11 In comparison with Comparative Example 12 containing the compatibilizing agent of Comparative Synthesis Example, the impact strengths of the molded articles of Examples 1 to 15 correspond to both measurement temperatures of 23 ° C and -30 ° C. It is superior to the impact strength of the molded products of Comparative Examples 1-12. In addition, regarding the presence or absence of delamination of the molded product by the base stitch test, the molded products of Examples 1 to 15 were 100/100.
100, which did not cause delamination at all,
In most of the molded articles of Comparative Examples 1 to 12, layered peeling property was generated.

Further, the appearances of the molded articles of Examples 1 to 15 were all good, whereas the appearances of the molded articles of Comparative Examples 1 to 12 were poor in almost all cases. Further, comparing Example 8 and Comparative Example 12, allylcarbamic acid-t-
In the case of Comparative Example 12 in which the butyl ester was graft-reacted, a certain degree of compatibilizing effect was recognized in terms of impact strength and peelability. However, the molded product obtained in Comparative Example 12 was markedly colored, which was a problem for practical use.

Claims (17)

[Claims] 1. A thermoplastic resin composition comprising the following three components A, B and C. (A) A polyolefin resin (A-1) having a functional group capable of reacting with an amino group, or a polyolefin resin (A-2) having substantially no functional group together with the polyolefin resin (A-1). 5 to 95 parts by weight of the composition containing (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group (B-1) and a polystyrene resin (B-2) having substantially no functional group. ), Or 95 to 5 parts by weight of a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2), a total of 100 parts by weight, and (C) a general formula in the molecule. A copolymer having a formamide repeating unit (Ia) represented by the formula
5 to 20 parts by weight. [Chemical 1] (In Chemical Formula 1, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or an arylalkyl group having 7 or 8 carbon atoms, R ³ is an alkylene group having 1 to 18 carbon atoms, 5 carbon atoms
To 17 cycloalkylene group, an arylene group having 6 to 12 carbon atoms or an arylalkylene group having 7 to 17 carbon atoms, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹ ~ R ³ and R ⁵ may be the same or different for each repeating unit. ) 2. A thermoplastic resin composition comprising the following three components A, B and C. (A) 5 to 95 parts by weight of a polyolefin resin (A-2) having substantially no functional group, and (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group,
Alternatively, a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2) having substantially no functional group is 95 to 5 parts by weight in total of 100 parts by weight, and (C). A copolymer having a formamide repeating unit (Ia) represented by the general formula 1 or a salt thereof is added in an amount of 0.05 to 20.
Parts by weight. 3. A thermoplastic resin composition comprising the following three components A, B and C. (A) A polyolefin resin (A-1) having a functional group capable of reacting with an amino group, or a polyolefin resin (A-2) having substantially no functional group together with the polyolefin resin (A-1). 5 to 95 parts by weight of the composition containing (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group (B-1) and a polystyrene resin (B-2) having substantially no functional group. ), Or 95 to 5 parts by weight of a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2), a total of 100 parts by weight, and (C) a general formula in the molecule. The copolymer having the formamide repeating unit (Ib) represented by the formula
5 to 20 parts by weight. [Chemical 2] (In Chemical Formula 2, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or an arylalkyl group having 7 or 8 carbon atoms, R ³ is an alkylene group having 1 to 18 carbon atoms, 5 carbon atoms
To 17 cycloalkylene group, and an aryl alkylene group an arylene group or a C 7-17 having 6 to 12 carbon atoms, R ¹ to R ³ may be the same or different for each repeating unit . ) 4. A thermoplastic resin composition comprising the following three components A, B and C. (A) 5 to 95 parts by weight of a polyolefin resin (A-2) having substantially no functional group, and (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group,
Alternatively, a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2) having substantially no functional group is 95 to 5 parts by weight in total of 100 parts by weight, and (C). A copolymer having a formamide repeating unit (Ib) represented by the general formula 2 or a salt thereof is added in an amount of 0.05 to 20.
Parts by weight. 5. A thermoplastic resin composition comprising the following three components A, B and C. (A) A polyolefin resin (A-1) having a functional group capable of reacting with an amino group, or a polyolefin resin (A-2) having substantially no functional group together with the polyolefin resin (A-1). 5 to 95 parts by weight of the composition containing (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group (B-1) and a polystyrene resin (B-2) having substantially no functional group. ), Or 95 to 5 parts by weight of a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2), a total of 100 parts by weight, and (C) a general formula in the molecule. The copolymer having an amino repeating unit (IIa) represented by Chemical formula 3 or a salt thereof is added in an amount of 0.05 to
20 parts by weight. [Chemical 3] (In Chemical Formula 3, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or an arylalkyl group having 7 or 8 carbon atoms, R ³ is an alkylene group having 1 to 18 carbon atoms, 5 carbon atoms
To 17 cycloalkylene group, an arylene group having 6 to 12 carbon atoms or an arylalkylene group having 7 to 17 carbon atoms, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹ ~ R ³ and R ⁵ may be the same or different for each repeating unit. ) 6. A thermoplastic resin composition comprising the following three components A, B and C. (A) 5 to 95 parts by weight of a polyolefin resin (A-2) having substantially no functional group, and (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group,
Alternatively, a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2) having substantially no functional group is 95 to 5 parts by weight in total of 100 parts by weight, and (C). Amino repeating unit (I
0.05 to 20 parts by weight of the copolymer having Ia) or a salt thereof. 7. A thermoplastic resin composition comprising the following three components A, B and C. (A) A polyolefin resin (A-1) having a functional group capable of reacting with an amino group, or a polyolefin resin (A-2) having substantially no functional group together with the polyolefin resin (A-1). 5 to 95 parts by weight of the composition containing (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group (B-1) and a polystyrene resin (B-2) having substantially no functional group. ), Or 95 to 5 parts by weight of a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2), a total of 100 parts by weight, and (C) a general formula in the molecule. The copolymer having an amino repeating unit (IIb) represented by Chemical formula 4 or a salt thereof is added in an amount of 0.05 to
20 parts by weight. [Chemical 4] (In the formula 4, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or an arylalkyl group having 7 or 8 carbon atoms, R ³ is an alkylene group having 1 to 18 carbon atoms, 5 carbon atoms
To 17 cycloalkylene group, and an aryl alkylene group an arylene group or a C 7-17 having 6 to 12 carbon atoms, R ¹ to R ³ may be the same or different for each repeating unit . ) 8. A thermoplastic resin composition comprising the following three components A, B and C. (A) 5 to 95 parts by weight of a polyolefin resin (A-2) having substantially no functional group, and (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group,
Alternatively, a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2) having substantially no functional group is 95 to 5 parts by weight in total of 100 parts by weight, and (C). Amino repeating unit (I
0.05 to 20 parts by weight of the copolymer having Ib) or a salt thereof. 9. A thermoplastic resin composition comprising the following three components A, B and C. (A) A polyolefin resin (A-1) having a functional group capable of reacting with an amino group, or a polyolefin resin (A-2) having substantially no functional group together with the polyolefin resin (A-1). 5 to 95 parts by weight of the composition containing (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group (B-1) and a polystyrene resin (B-2) having substantially no functional group. ), Or 95 to 5 parts by weight of a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2), a total of 100 parts by weight, and (C) a general formula in the molecule. The copolymer having an acylamino repeating unit (IIIa) represented by Chemical formula 5 or a salt thereof is
05-20 parts by weight. [Chemical 5] (In the formula 5, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or an arylalkyl group having 7 or 8 carbon atoms, R ³ is an alkylene group having 1 to 18 carbon atoms, 5 carbon atoms
To 17 cycloalkylene group, an arylene group having 6 to 12 carbon atoms or an arylalkylene group having 7 to 17 carbon atoms, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁶ represents It represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group, and R ^{1 to} R ³ , R ⁵ and R
⁶ may be the same or different in each repeating unit. ) 10. A thermoplastic resin composition comprising the following three components A, B and C. (A) 5 to 95 parts by weight of a polyolefin resin (A-2) having substantially no functional group, and (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group,
Alternatively, a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2) having substantially no functional group is 95 to 5 parts by weight in total of 100 parts by weight, and (C). A copolymer having an acylamino repeating unit (IIIa) represented by the general formula 5 or a salt thereof is added in an amount of 0.05 to 2
0 parts by weight. 11. A thermoplastic resin composition comprising the following three components A, B and C. (A) A polyolefin resin (A-1) having a functional group capable of reacting with an amino group, or a polyolefin resin (A-2) having substantially no functional group together with the polyolefin resin (A-1). 5 to 95 parts by weight of the composition containing (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group (B-1) and a polystyrene resin (B-2) having substantially no functional group. ), Or 95 to 5 parts by weight of a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2), a total of 100 parts by weight, and (C) a general formula in the molecule. The copolymer having an acylamino repeating unit (IIIb) represented by Chemical formula 6 or a salt thereof is
05-20 parts by weight. [Chemical 6] (In Chemical Formula 6, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or an arylalkyl group having 7 or 8 carbon atoms, R ³ is an alkylene group having 1 to 18 carbon atoms, 5 carbon atoms
To 17 cycloalkylene group, an arylene group having 6 to 12 carbon atoms or an arylalkylene group having 7 to 17 carbon atoms, and R ⁶ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group. , R ^{1 to} R ³ and R ⁶ may be the same or different for each repeating unit. ) 12. A thermoplastic resin composition comprising the following three components A, B and C. (A) 5 to 95 parts by weight of a polyolefin resin (A-2) having substantially no functional group, and (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group,
Alternatively, a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2) having substantially no functional group is 95 to 5 parts by weight in total of 100 parts by weight, and (C). A copolymer having an acylamino repeating unit (IIIb) represented by the general formula 6 or a salt thereof is added in an amount of 0.05 to 2
0 parts by weight. 13. A thermoplastic resin composition comprising the following three components A, B and C. (A) A polyolefin resin (A-1) having a functional group capable of reacting with an amino group, or a polyolefin resin (A-2) having substantially no functional group together with the polyolefin resin (A-1). 5 to 95 parts by weight of the composition containing (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group (B-1) and a polystyrene resin (B-2) having substantially no functional group. ), Or 95 to 5 parts by weight of a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2), a total of 100 parts by weight, and (C) a general formula in the molecule. The copolymer having a carbamate repeating unit (IVa) represented by Chemical formula 7 or a salt thereof is
05-20 parts by weight. [Chemical 7] (In Chemical Formula 7, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or an arylalkyl group having 7 or 8 carbon atoms, R ³ is an alkylene group having 1 to 18 carbon atoms, 5 carbon atoms
To 17 cycloalkylene group, an arylene group having 6 to 12 carbon atoms or an arylalkylene group having 7 to 17 carbon atoms, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁷ represents It represents a primary or secondary alkyl group having 1 to 8 carbon atoms, and R ^{1 to} R ³ , R ⁵ and R ⁷ may be the same or different for each repeating unit. ) 14. A thermoplastic resin composition comprising the following three components A, B and C. (A) 5 to 95 parts by weight of a polyolefin resin (A-2) having substantially no functional group, and (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group,
Alternatively, a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2) having substantially no functional group is 95 to 5 parts by weight in total of 100 parts by weight, and (C). A copolymer having a carbamate repeating unit (IVa) represented by the general formula 7 or a salt thereof is added in an amount of 0.05 to 2
0 parts by weight. 15. A thermoplastic resin composition comprising the following three components A, B and C. (A) A polyolefin resin (A-1) having a functional group capable of reacting with an amino group, or a polyolefin resin (A-2) having substantially no functional group together with the polyolefin resin (A-1). 5 to 95 parts by weight of the composition containing (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group (B-1) and a polystyrene resin (B-2) having substantially no functional group. ), Or 95 to 5 parts by weight of a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2), a total of 100 parts by weight, and (C) a general formula in the molecule. The copolymer having a carbamate repeating unit (IVb) represented by Chemical formula 8 or a salt thereof is
05-20 parts by weight. [Chemical 8] (In the chemical formula 8, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or an arylalkyl group having 7 or 8 carbon atoms, R ³ is an alkylene group having 1 to 18 carbon atoms, 5 carbon atoms
To 17 cycloalkylene group, an arylalkylene group arylene group or a C 7-17 having 6 to 12 carbon atoms, R ⁷ indicates a primary or secondary alkyl group having 1 to 8 carbon atoms, R ^{1 to} R ³ and R ⁷ may be the same or different for each repeating unit. ) 16. A thermoplastic resin composition comprising the following three components A, B and C. (A) 5 to 95 parts by weight of a polyolefin resin (A-2) having substantially no functional group, and (B) a polystyrene resin (B-1) having a functional group capable of reacting with an amino group,
Alternatively, a composition containing the polystyrene-based resin (B-1) and the polystyrene-based resin (B-2) having substantially no functional group is 95 to 5 parts by weight in total of 100 parts by weight, and (C). A copolymer having a carbamate repeating unit (IVb) represented by the general formula 8 or a salt thereof is added in an amount of 0.05 to 2
0 parts by weight. 17. The functional group capable of reacting with an amino group in the component A and the component B is a succinic anhydride group, a carboxyl group, an epoxy group, an ester group, an amide group, a cyclic iminoether group, or a cyclic iminoamino group. 17. The thermoplastic resin composition according to claim 1, which is one or more functional groups selected from the group consisting of and halogen.