JPH0639549B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention has a balance of impact resistance represented by impact strength, rigidity represented by flexural modulus, heat resistance represented by heat distortion temperature, and weather resistance. And an excellent thermoplastic resin composition.

<Prior Art> As typical impact resistant resins, acrylonitrile-butadiene-styrene terpolymer resin (ABS resin) and methyl methacrylate-butadiene-styrene terpolymer resin (MBS resin) are widely used. Used in the field. As a resin having improved weather resistance of these resins, an acrylonitrile-styrene graft copolymer resin (A containing ethylene-propylene rubber or acrylic rubber as a pace rubber) is used.
ES resins and AAS resins) have also been used.

On the other hand, a resin composition in which a carboxylic acid-containing olefin polymer is blended with polyamide has also been proposed for the purpose of increasing the impact of polyamide. (Japanese Patent Publication No. 42-12546, Japanese Patent Publication No. 55-4
4108 publication etc. ) Further, in order to improve the hygroscopicity of polyamide, α, β-
A new copolymer in which a styrene copolymer containing an unsaturated carboxylic acid imidized compound as a copolymerization component and a polyamide are chemically bonded has also been proposed (JP-A-57-57719).

<Problems to be Solved by the Invention> However, since impact-resistant resins represented by ABS resins have poor weather resistance, the flexural modulus decreases when an attempt is made to increase impact strength. Moreover, it is not possible to obtain a highly rigid resin. Although AES resin and AAS resin have improved weather resistance, they cannot have high impact resistance and high rigidity like ABS resin.

A resin composition comprising a polyamide and a carboxylic acid-containing olefin polymer can obtain high impact strength, but cannot obtain a sufficient flexural modulus. In addition, the resin composition has a defect that the flexural modulus is further significantly reduced by moisture absorption.

Further, a sufficiently high impact strength cannot be obtained with a polyamide and a styrene copolymer containing an α, β-unsaturated carboxylic acid imide.

That is, a resin having high impact resistance, high rigidity, high heat resistance, and excellent weather resistance has not yet been obtained, and under the present circumstances, the development of a resin having these properties is desired.

The present inventors have conducted intensive studies for the purpose of developing a resin having a high impact strength and a high flexural modulus, and having excellent heat resistance and weather resistance. As a result, a specific vinyl copolymer, a polyamide and a specific modified resin have been obtained. The present invention has been accomplished by finding that the above object can be achieved by blending a polyolefin in a specific ratio.

<Means for Solving Problems> That is, the present invention provides at least one selected from the group consisting of (A) (a) aromatic vinyl-based monomers and (meth) acrylate-based monomers.
5 to 95% by weight of vinyl monomers (b) Maleimide monomers 5 to 9 represented by the following formula (I)
5% by weight (In the formula, R ₁ , R ₂ and R ₃ each represent hydrogen, halogen, a substituted or unsubstituted hydrocarbon having 1 to 20 carbon atoms) and (c) with (a) and / or (b) Vinyl-based polymer obtained by polymerizing 0 to 50% by weight of another polymerizable vinyl-based monomer. (B) Polyamide and (C) selected from the group consisting of carboxylic acid group, metal carboxylate group and acid anhydride group. The modified polyolefin having at least one functional group is (A) 5 to 90% by weight, (B) 3 to 90% by weight, and
The present invention provides a thermoplastic resin composition obtained by mixing (C) in a proportion of 5 to 60% by weight.

Vinyl-based copolymer used in the present invention (A), polyamide (B),
The modified polyolefin (C) will be described below.

In the vinyl copolymer (A) used in the present invention, the vinyl monomer (a) means styrene, α-methylstyrene, P-
Aromatic vinyl monomers such as methylstyrene, Pt-butylstyrene, vinyltoluene and P-chlorostyrene, and methyl methacrylate and ethyl methacrylate.
At least one vinyl selected from the group consisting of (meth) acrylic acid ester-based monomers such as -t-butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, methyl acrylate, ethyl acrylate, and propyl acrylate. It is a system monomer.

Among the above vinyl-based monomers (a), styrene, α-methylstyrene, P-methylstyrene and methyl methacrylate are particularly preferable, and these can be used alone or in combination of two or more.

The maleimide-based monomer (b) is not particularly limited as long as it satisfies the formula (I), but specific examples include maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N. -T-butylmaleimide, N-phenylmaleimide, Nm-methylphenylmaleimide, N-o-methylphenylmaleimide,
Np-methylphenylmaleimide, N-cyclohexylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-
Hydroxyphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, N-o-chlorophenylmaleimide, Nm-chlorophenylmaleimide, Np-chlorophenylmaleimide, N -O-
Examples thereof include carboxyphenylmaleimide, Np-carboxyphenylmaleimide, Nm-carboxyphenylmaleimide, dichloromaleimide and N-naphthylmaleimide.

Among these, N-phenylmaleimide, N-cyclohexylmaleimide, Nt-butylmaleimide, N
-Isopropylmaleimide and Nm-methylphenylmaleimide are preferred.

These can be used alone or in combination of two or more.

Other vinyl monomers (c) include (a) and / or (b)
There is no particular limitation as long as it is a vinyl-based monomer other than (a) and / or (b) that is copolymerizable with (a) and / or (b). Methacrylic acid, maleic anhydride, etc. can be mentioned. Of these, acrylonitrile is particularly preferable.

In the polymerization of the vinyl-based copolymer (A), the proportion of the monomers (a), (b) and (c) is such that (a) is 5 to 95% by weight, preferably 15
To 90% by weight, particularly preferably 25 to 85% by weight, (b)
Is 5 to 95% by weight, preferably 10 to 85% by weight, particularly preferably 15 to 75% by weight and (c) is 0 to 50% by weight, preferably 0 to 40% by weight, particularly preferably 0 to 3% by weight.
It is 5% by weight.

Vinyl copolymer if (a) is less than 5% by weight or more than 95% by weight, (b) is less than 5% by weight or more than 95% by weight, or (c) is more than 50% by weight. The mechanical properties, thermal stability, and melt flowability of (A) are inferior, and a resin composition having desired performance cannot be obtained, which is not preferable. (A) exceeds 95% by weight, or
When (b) is less than 5% by weight, the thermal denaturation temperature of the vinyl-based copolymer (A) is low, and the vinyl-based copolymer (A) and polyamide
The miscibility with (B) and / or the modified polyolefin (C) is poor, and the heat distortion temperature and mechanical properties of the obtained resin composition are poor, which is not preferable.

Further, in the polymerization of the vinyl copolymer (A), polybutadiene (PBD), acrylonitrile-butadiene copolymer rubber (NBR), styrene-butadiene copolymer rubber (SBR), polybutyl acrylate rubber, ethylene −
Polymerization of (a), (b) and (c) in a given ratio in the presence of various rubber-like polymers such as propylene copolymer rubber (EPR) and ethylene-propylene-non-conjugated diene copolymer rubber (EPDM). It is also possible to do so.

There is no particular limitation on the polymerization method of the vinyl-based copolymer (A), in the presence or absence of a radical-generating initiator, bulk polymerization, solution polymerization, bulk-suspension polymerization, suspension polymerization,
It is carried out using a generally known method such as emulsion polymerization. There are also no particular restrictions on the charging method of the vinyl-based monomers (a), (b) and (c), they may be charged all at once in the initial stage, or part or all of the charged monomers may be continuously charged or divided. Polymerization may be carried out while charging.

Further, an α, β-unsaturated dicarboxylic acid typified by maleic anhydride or a copolymer obtained by copolymerizing the anhydride thereof with ammonia or an amine such as methylamine, ethylamine, t-butylamine, cyclohexylamine or aniline is used. It is also possible to produce by reacting and imidizing.

α, β-unsaturated dicarboxylic acid or its anhydride and (a) aromatic vinyl-based monomer and / or (meth) acrylic acid ester-based monomer and, if necessary, (c) other vinyl-based monomer The copolymer obtained by imidizing a copolymer consisting of a polymer with ammonia or amines is substantially the same as the vinyl-based copolymer (A) obtained by copolymerizing each of the above monomers. If the final composition is the same, it is included in the vinyl copolymer (A) in the present invention.

The polyamide (B) used in the present invention is a polyamide obtained by ring-opening polymerization of lactams such as ε-caprolactam and ω-dodecalactam, 6-aminocaproic acid, 1
Polyamides derived from amino acids such as 1-aminoundecanoic acid and 12-aminododecanoic acid, ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4 -Aliphatic, alicyclic, aromatic such as trimethylhexamethylenediamine, 1,3- and 1,4-bis (aminomethyl) cyclohexane, bis (4,4'-aminocyclohexyl) methane, meta and paraxylylenediamine Group diamine and adipic acid,
Suberic acid, sebacic acid, dodecanedioic acid, 1,3 and 1,4-cyclohexanedicarboxylic acid, isophthalic acid,
Polyamides derived from aliphatic, alicyclic and aromatic dicarboxylic acids such as terephthalic acid and dimer acid, and copolyamides and mixed polyamides thereof. Of these, polycaproamide (nylon 6), polyundecane amide (nylon 11), polydodecane amide (nylon 12), polyhexamethylene adipamide (nylon 66) and copolyamides containing these as the main components are usually used. It is useful. As a method for polymerizing the polyamide, generally known melt polymerization, solid phase polymerization and a method combining these can be adopted. The polymerization degree of the polyamide is not particularly limited, and the relative viscosity (polymer 1 g is 98% concentrated sulfuric acid 100 m
A polyamide which is dissolved in the above and has a range of 2.0 to 5.0 when measured at 25 ° C. can be arbitrarily selected according to the purpose.

The modified polyolefin (C) used in the present invention is not particularly limited as long as it is a polyolefin having at least one functional group selected from the group consisting of a carboxylic acid group, a carboxylate metal base and an acid anhydride group. Typical examples are ethylene / alkyl acid copolymers, ethylene-methacrylic acid copolymers, ethylene / fumaric acid copolymers, ethylene / methacrylic acid / zinc methacrylate copolymers, ethylene / acrylic acid / sodium methacrylate copolymers. Polymer, ethylene / isobutyl acrylate / methacrylic acid / zinc methacrylate copolymer, ethylene / methyl methacrylate / methacrylic acid / magnesium methacrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / ethyl acrylate / Acrylic acid copolymer, ethylene / maleic anhydride copolymer, ethylene / propylene / maleic anhydride copolymer, ethylene-g-maleic anhydride copolymer (“g”)
Represents a graft. same as below. ), Ethylene / propylene-g-maleic anhydride copolymer, ethylene / propylene-g-acrylic acid copolymer, ethylene / 1-butene-g-fumaric acid copolymer, ethylene / 1-hexene-g
-Itaconic acid copolymer, ethylene / propylene-g-endobicyclo [2,2,1] -5-heptene-2,3-
Dicarboxylic anhydride copolymer, ethylene / propylene /
1,4-hexadiene-g-maleic anhydride copolymer,
Ethylene / propylene / dicyclopentadiene-g-fumaric acid copolymer, ethylene / propylene / dicyclopetanediene-g-maleic anhydride copolymer, ethylene / propylene / 5-ethylidene-2-norbornene-g-maleic anhydride Examples thereof include acid copolymers, ethylene / propylene / 5-ethylidene-2-norbornene-g-maleic acid copolymers and ethylene / vinyl acetate-g-acrylic acid copolymers, but are not limited thereto. is not. It is also possible to use two or more of these modified polyolefins in combination.

Modified polyolefin (C) is usually a known method, for example,
Japanese Patent Publication No. 39-6810, Japanese Patent Publication No. 52-43677, Japanese Patent Publication No. 5
3-5716 publication, JP-B-53-19037 publication, JP-B-53-41173
It can be produced by the method described in Japanese Patent Publication No. 56-29925, etc. Regarding ethylene-based ionomers, "Surlyn", "Himilan",
Various grades marketed under the trade name of "COPOLEN" can be used.

The vinyl-based copolymer in the thermoplastic resin composition of the present invention
The compounding ratio of (A), polyamide (B) and modified polyolefin (C) is 5 to 90% by weight of (A), preferably 15 to 80% by weight, particularly preferably 20 to 70% by weight, and 3 of (B). ~ 9
0% by weight, preferably 5-80% by weight, particularly preferably 10-70% by weight, and (C) 5-60% by weight, preferably 10-50% by weight, particularly preferably 15-40% by weight. It is a ratio. If the content of (A) is less than 5% by weight, the rigidity and heat distortion temperature will be poor, and if the content of (A) exceeds 90% by weight, the impact resistance will be poor, such being undesirable. If (B) is less than 3% by weight or (C) is less than 5% by weight, the impact resistance is poor, and if (B) is more than 90% by weight or (C) is more than 60% by weight, the rigidity is low. It is inferior and not preferable.

The method for producing the thermoplastic resin composition of the present invention is not particularly limited, and a generally known method can be adopted.
That is, vinyl copolymer (A), polyamide (B) and modified polyolefin (C) pellets, powder, in the state of small pieces, after uniformly mixing using a high-speed stirrer, etc., uniaxial or with sufficient kneading ability Various methods such as a method of melt-kneading with a multi-screw extruder and a method of melt-kneading with a Banbury mixer or a rubber roll machine can be adopted. Further, vinyl-based copolymer (A) and polyamide (B), polyamide (B) and modified polyolefin (C), vinyl-based copolymer
A method is also possible in which (A) and the modified polyolefin (C) and the like are pre-kneaded in advance, and the kneading is performed after adjusting the mixing ratio to a predetermined value.

The thermoplastic resin composition of the present invention is a vinyl-based copolymer (A),
In addition to the polyamide (B) and modified polyolefin (C), polystyrene (PS), styrene / acrylonitrile copolymer (SAN), polymethylmethacrylate (PMMA), styrene / methylmethacrylate / acrylonitrile copolymer, as required. Coalescence, α-methylstyrene / acrylonitrile machine copolymer, α-methylstyrene / styrene / acrylonitrile copolymer, α-methylstyrene / methyl methacrylate / acrylonitrile copolymer, p-methylstyrene / acrylonitrile copolymer, styrene / Vinyl-based polymers such as maleic anhydride copolymer, acrylonitrile-butadiene-styrene terpolymer (ABS)
Resin, methacrylic acid resin-butadiene-styrene terpolymer (MBS) resin, AES resin, AAS resin, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, or other thermoplastic resin is appropriately mixed, polyethylene, polypropylene, ethylene / propylene. Copolymer, ethylene / butene-1 copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / 1,4-hexadiene copolymer It is also possible to adjust to more desirable physical properties and characteristics by appropriately mixing polyolefin rubber such as ethylene / vinyl acetate copolymer and ethylene / butyl acrylate copolymer. Depending on the purpose, pigments and dyes, glass fibers, metal fibers, metal flakes,
Reinforcing materials and fillers such as carbon fibers, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, antistatic agents and flame retardants can be added.

<Example> Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Izod impact strength is ASTM D256
-56, Method A, flexural modulus is ASTM D790-
61, the heat distortion temperature was measured according to ASTM D648-56. The weather resistance was evaluated by irradiating a notched Izod impact test piece with a sunshine weatherometer for 400 hours and measuring the change in Izod impact strength. The Izod impact strength was measured in an absolutely dry state. The flexural modulus was measured in an absolutely dry state and in a state where the test piece was immersed in water at 23 ° C. for 48 hours to absorb water. Below,% is weight%,
The number of parts represents parts by weight.

Reference Example 1 (Production of Vinyl Copolymer (A)) Vinyl copolymers (A-1) to (A-6) having the compositions shown in Table 1 were produced by the following method.

A-1: 70 parts of styrene and 0.5 part of azoisobutyronitrile were charged into a polymerization tank, the temperature was adjusted to 80 ° C., and while stirring,
A solution consisting of 30 parts of N-phenylmaleimide and 80 parts of methyl ethyl ketone was charged at a constant rate over 8 hours. Then, the temperature was raised to 90 ° C. and kept for 2 hours. A transparent and viscous solution was obtained, and the solvent was removed to produce a vinyl-based copolymer (A-1).

A-2: 35 parts of styrene, 65 parts of N-cyurohexylmaleimide, 0.5 part of benzoyl peroxide and 100 parts of methyl ethyl ketone were charged in a polymerization tank, and the polymerization was carried out at 80 ° C. for 8 hours and then at 90 ° C. for 2 hours for polymerization. . A transparent and viscous solution was obtained, and the solvent was removed to produce a vinyl polymer (A-2).

A-3 to A-6: 200 parts of water and a saponification degree of 8 in the polymerization tank
Charge 0.3% of 0% polyvinyl alcohol (suspension stabilizer), then charge 100 parts of the monomer mixture having the composition shown in Table 1 and 0.5 part of azoisobutyronitrile, and stir at high speed to obtain a suspension state. did. While maintaining the suspension state, polymerization was carried out at 80 ° C. for 6 hours and further at 90 ° C. for 1 hour to produce granular vinyl copolymers (A-3) to (A-6).

Reference Example 2 (Production of Polyamide (B)) The following nylon 6, nylon 66, and nylon 12 were produced by the melt polymerization method.

Nylon 6: Relative viscosity of concentrated sulfuric acid from ε-caprolactam 2.
75 nylon 6 were polymerized.

Nylon 66: Nylon 66 having a relative viscosity of concentrated sulfuric acid of 2.60 was polymerized from a molar salt of hexamethylenediamine and adipic acid.

Nylon 12: Nylon 12 having a relative viscosity of 2.35 in concentrated sulfuric acid was polymerized from 12-aminododecanoic acid.

Reference Example 3 (Production of modified polyolefin (C)) C-1: 85% by weight of ethylene and 15% by weight of methacrylic acid
Is copolymerized in the presence of a peroxide according to the production conditions of high-pressure polyethylene, and to the obtained copolymer is added an amount of zinc acetate capable of neutralizing and ionizing 75% of the contained methacrylic acid,
Evenly knead at 180 ° C using a roll mill to obtain ethylene /
A methacrylic acid / zinc methacrylate copolymer (ionomer resin) C-1 was produced.

C-2: 79% by weight of ethylene, isobutyl acrylate 1
After copolymerizing 1% by weight and 10% by weight of methacrylic acid according to the production conditions of high-pressure polyethylene, after adding zinc acetate in an amount capable of neutralizing and ionizing 72% of methacrylic acid contained in the obtained copolymer. , C-1, and ethylene / isobutyl acrylate / zinc methacrylate copolymer (ionomer resin) C-2 was produced.

C-3: α, α′-bis-t dissolved in a small amount of acetone based on 100 parts by weight of an ethylene / propylene copolymer composed of 70 mol% of ethylene and 30 mol% of propylene.
-Butylperoxy-p-diisopropylbenzene 0.03
After adding 1 part by weight and 1.0 part by weight maleic anhydride,
An ethylene / propylene-g-maleic anhydride copolymer (“g” represents a graft) was obtained by kneading and pelletizing at 230 ° C. using an extruder having a diameter of 40 mm.
C-3 was produced.

C-4: 0.1 part by weight of di-t-butyl peroxide and 1.0 part by weight of acrylic acid dissolved in a small amount of acetone based on 100 parts by weight of an ethylene / propylene copolymer consisting of 80 mol% of ethylene and 20 mol% of propylene. After the addition, use an extruder with a diameter of 40 mm as in C-3 to
By kneading and pelletizing at 00 ℃ ethylene /
Propylene-g-acrylic acid copolymer C-4 was produced.

C-5: ethylene-propylene-5-ethylidene-2-norbornene (EPD) having Mooney viscosity of 60 and iodine value of 12
M) Terpolymer (ethylene / propylene = 68.5 / 31.5)
(Mole ratio)) To 100 parts by weight of di-t-butyl peroxide dissolved in a small amount of acetone 0.1 parts by weight and maleic anhydride 0.5 parts by weight were added, followed by extrusion with a 40 mmφ caliber as in C-3. EPDM-g-maleic acid anhydride C-5 was produced by kneading at 230 ° C. using a machine and pelletizing.

Example 1 Vinyl-based copolymer (A) and polyamide (B) produced in Reference Example
The modified polyolefin (C) and the modified polyolefin (C) were mixed at the compounding ratio shown in Table 2, melt-kneaded using an extruder having a diameter of 40 mm and pelletized. The extrusion temperature was 260 ° C. when nylon 6 and nylon 12 were used as the polyamide (B), and 290 ° C. when nylon 66 was used. Next, the pellets were vacuum dried, and then a test piece for measuring physical properties was molded by injection molding. During injection molding, the cylinder temperature is 260 ° C when nylon 6 and nylon 12 are used as polyamide (B), and 2 when nylon 66 is used.
It was set at 90 ° C. The mold temperature was set to 80 ° C.

The measurement results are shown in Table 2.

Comparative Example Vinyl-based copolymer (A) produced in Reference Example, polyamide
(B), the modified polyolefin (C), the following vinyl-based copolymer and the polyolefin were mixed at the compounding ratio shown in Table 2, and the physical properties were measured by the same methods as in Example 1. The measurement results are shown in Table 2.

Vinyl-based (co) polymer A-7: polystyrene A-8: 72% by weight of styrene and acrylonitrile 2
Copolymer consisting of 8% by weight Polyolefin C-6: Ethylene / propylene copolymer consisting of 70 mol% of ethylene and 30 mol% of propylene C-7: Ethylene-propylene-5-ethylidene having Mooney viscosity of 60 and iodine value of 12 2-norbornene (EPD
M) Terpolymer (ethylene / propylene = 68.5 / 31.5)
(Molar ratio) From the results of Example 1 and Comparative Example, the following is clear. All of the resin compositions (NO. 1 to 13) of the present invention have high Izod impact strength, heat deformation temperature and flexural modulus. The Izod impact strength does not decrease even after irradiation with a sunshine weatherometer for 400 hours, and the weather resistance is excellent. The flexural modulus remains relatively high even after water absorption treatment. That is, the resin composition of the present invention is a resin composition having high impact resistance, high rigidity, high heat resistance, and excellent weather resistance. On the other hand, the resin compositions (NO. 14 to 16) composed only of the vinyl-based copolymer (A) containing no polyamide and the modified polyolefin (C) have low impact strength. The resin composition (NO. 17 to 19) in which the polyamide (B) not containing the vinyl copolymer (A) and the modified polyolefin (C) alone has a low flexural modulus. The water absorption treatment further reduces the flexural modulus significantly. In addition, it has disadvantages such as a low heat deformation temperature under a high load (18.56 kg / cm ² ), which is not preferable.
Vinyl-based copolymer (A) containing no modified polyolefin (C)
And a resin composition consisting only of polyamide (B) (NO. 20, 2
1) has a low impact strength. Modified polyolefin (C) 60
The composition (NO.22) containing more than the above portion has a significantly low flexural modulus. If the vinyl-based copolymer (A) does not contain a maleimide-based monomer, a resin composition (NO.
3, 24) has a low impact strength. Modified polyolefin (C)
The resin composition (NO. 25, 26) containing no carboxylic acid group, metal carboxylate group or acid anhydride group therein has extremely low impact strength.

Example 2 Vinyl Copolymer (A) and Polyamide Produced in Reference Example
(B), the modified polyolefin (C), the vinyl-based (co) polymer shown in Comparative Example, and the polyolefin were mixed at the compounding ratio shown in Table 2, and the physical properties were measured by the same method as in Example 1.

The measurement results are shown in Table 2. In addition to vinyl-based copolymer (A), polyamide (B) and modified polyolefin (C), vinyl-based (co) polymers such as styrene / acrylonitrile copolymer and ethylene / propylene copolymer rubber (E
A desirable resin composition having excellent impact strength, flexural modulus, heat resistance and weather resistance can be obtained by mixing a polyolefin rubber such as PR).

<Effects of the Invention> As described above, the resin composition of the present invention has impact resistance represented by impact strength, rigidity represented by flexural modulus, heat resistance represented by heat distortion temperature and weather resistance. They are excellent in balance and are expected to be applied to various fields by taking advantage of these characteristics.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 51/06 LLE 7142-4J 77/00 LQS 9286-4J

Claims (1)

[Claims] 1. At least one vinyl-based monomer selected from the group consisting of (A) (a) aromatic vinyl-based monomers and (meth) acrylic acid ester-based monomers in an amount of 5 to 95% by weight. (B) Maleimide-based monomers 5 to 9 represented by the following formula (I)
5% by weight (In the formula, R ₁ , R ₂ and R ₃ each represent hydrogen, halogen, a substituted or unsubstituted hydrocarbon having 1 to 20 carbon atoms) and (c) with (a) and / or (b) Vinyl-based polymer obtained by polymerizing 0 to 50% by weight of another polymerizable vinyl-based monomer. (B) Polyamide and (C) selected from the group consisting of carboxylic acid group, metal carboxylate group and acid anhydride group. The modified polyolefin having at least one functional group is (A) 5 to 90% by weight, (B) 3 to 90% by weight, and
A thermoplastic resin composition obtained by mixing (C) in a proportion of 5 to 60% by weight.