JPH03244647A - Resin composition - Google Patents

Abstract

PURPOSE:To prepare a resin compsn. having excellent heat resistance, impact strength, etc., and undergoing no degradation in physical properties due to absorption of water by compounding a specific styrenic multicomponent copolymer, an ethylene-propylene copolymer rubber, an ethylenic multicomponent copolymer, and a polyamide resin, each in a specified amt. CONSTITUTION:The title compsn. comprises, each in a specified amt., a styrenic multicomponent copolymer comprising at least 20 wt.% styrenic compd. (e.g. styrene), 5.0-60 wt.% alpha,beta-unsatd. dicarboxylic acid imide (e.g. N- phenylmaleimide), and 0.1-30 wt.% unsatd. carboxylic acid and/or unsatd. dicarboxylic anhydride (e.g. acrylic acid); a polyamide resin (e.g. nylon-66); an ethylene-propylene copolymer rubber modified with an alpha,beta-unsatd. carboxylic acid and/or unsatd. dicarboxylic anhydride (e.g. maleic anhydride); and an ethylenic multicomponent copolymer contg. 1-50 wt.% alpha,beta-ethylenically unsatd. carboxylic ester (e.g. methyl methacrylate) and 0.05-20 wt.% unsatd. dicarboxylic acid (deriv.)(e.g. maleic anhydride).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a resin composition having excellent chemical resistance, impact resistance and heat resistance. More specifically, it relates to resin compositions consisting of styrene-based multi-component copolymers, polyamide resins, modified ethylene-propylene" (polymerized rubber and engineered tyrene-based multi-component copolymers, and has chemical resistance, impact resistance and An object of the present invention is to provide a resin composition with excellent heat resistance.

[Conventional technology]

Due to its excellent physical and chemical properties, polyamide resin is widely used as an engineering plastic in automobile parts, electrical equipment parts, electronic equipment parts, mechanical parts, etc. However, polyamide resins have the drawback of not having sufficient impact resistance. To improve this point, α and β-
Compositions containing modified polyolefins obtained by grafting unsaturated carboxylic acids have been proposed (JP-A Nos. 50-9G442, 52-151348, 55-9681, 55-9962, Same 55-
1 [No. 15922, No. 57-11296, No. 57-2
No. 00.948, etc.), some of these compositions are in practical use.

[Problem to be solved by the invention]

However, although these compositions have improved impact resistance, they not only have poor heat resistance;
There is also a problem of decreased rigidity, and there is also a problem with water resistance.

In order to improve these points, the present inventors have proposed (^) at least a styrene compound, an imide compound of an α,β-unsaturated dicarboxylic acid, and an α,β-unsaturated carboxylic acid and/or an α,β-unsaturated dicarboxylic acid. - a styrenic multi-component copolymer consisting of an unsaturated dicarboxylic acid anhydride, (n) a polyamide resin and (C) modified with an α,β-unsaturated carboxylic acid and/or an α,β-unsaturated dicarboxylic acid anhydride; Tsutsumi has already proposed a resin composition consisting of ethylene-propylene copolymer rubber (Special Department Hr (63-20192)).
No. 5). However, the composition of the present invention cannot always be said to have a satisfactory balance between impact resistance and heat resistance depending on its use.

From the above, the composition of the present invention not only has excellent impact resistance, which is a characteristic of the composition of the present invention, but also has good heat resistance, has excellent rigidity, and has lower physical properties due to water absorption. The object of the present invention is to provide a resin composition that has a characteristic of having a small amount of heat resistance, and particularly has an improved balance between impact resistance and heat resistance.

[Means and effects for solving the problems] According to the present invention, these problems are solved by (A) at least a styrene compound, an imide compound of an α,β-unsaturated dicarboxylic acid, and an unsaturated carboxylic acid and/or (B) polyamide resin; (C) ethylene modified with α,β-unsaturated carboxylic acid and/or unsaturated dicarboxylic acid anhydride;
The copolymerization ratio of propylene copolymer rubber (hereinafter referred to as "modified ethylene-propylene rubber") and (D) α,β-type unsaturated carboxylic acid ester is 0.1 to 50% by weight, and A composition consisting of an ethylene-based multicomponent copolymer in which the copolymerization ratio of U-based unsaturated carboxylic acid or its derivative is 0.05 to 20% by weight, and the composition ratio of polyamide resin in the composition is 30% by weight. The composition ratio of the styrene multi-component copolymer in the total amount of the modified ethylene-propylene rubber, the ethylene multi-component copolymer and the styrene multi-component copolymer is 30 to 90% by weight, and the modified ethylene -The composition ratio of the ethylene-based multi-component copolymer in the total amount of propylene-based rubber and ethylene-based multi-component copolymer is 1
5 to 85% by weight, and the copolymerization ratio of unsaturated carboxylic acid and unsaturated dicarboxylic acid anhydride in the polymer is 0.1 to 30% by weight as their total amount.
and the copolymerization ratio of the imide compound is 5.0 to 6.
0% by weight, but the copolymerization proportion of the styrenic compound is at least 20% by weight. The present invention will be explained in detail below.

(A) Styrenic multi-component copolymer The styrene compound which is a copolymerization component of the styrenic multi-component copolymer used in the present invention is styrene or a derivative thereof. Examples of the derivative include α-methylstyrene, 0- Methylstyrene, m-methylstyrene, p-
Mention may be made of methylstyrene, chlorstyrene and bromstyrene.

Examples of imide compounds of α,β-unsaturated dicarboxylic acids include those whose numerical formula is represented by formula (1).

3 In formula (I), R, R and R3 are the same 2 - but 'l? , seeds, hydrogen atoms, hydrocarbons with at most 12 carbon atoms.

Representative examples of the imide compounds include maleimide, N-
Phenylmaleimide, N-methylphenylmaleimide,
Examples include N-ethylphenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-p-chlorophenylmaleimide, and the like.

Furthermore, the α,β-unsaturated carboxylic acids include α,β-unsaturated monocarboxylic acids having at most 30 carbon atoms (preferably 25 or less) and α,β-unsaturated monocarboxylic acids having at most 30 carbon atoms (preferably 25 or less carbon atoms). α, β-unsaturated dicarboxylic acids (less than or equal to 1). Representative examples of preferred α,β-unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid.

Preferred α,β-unsaturated dicarboxylic acid anhydrides include the aforementioned desirable α,β-unsaturated dicarboxylic acid anhydrides, representative examples of which include maleic anhydride and fumaric anhydride. , itaconic anhydride, etc.

The styrenic multi-component copolymer can be produced by any of the commonly used methods such as aqueous suspension polymerization, emulsion polymerization, solution polymerization and bulk polymerization, and these polymerization methods are generally well-known. It is.

The copolymerization ratio of the imide compound in the styrenic multi-component copolymer is 5.0 to 60% by weight, preferably 5.0 to 55% by weight, particularly preferably 5.0 to 50% by weight. be. The copolymerization ratio of the imide compound in the multi-component copolymer is 5
．． If it is less than 0%, heat resistance will be insufficient. On the other hand, if the weight exceeds 60, moldability and mechanical properties are poor.

In addition, unsaturated carboxylic acid and unsaturated dicarboxylic acid anhydride (polymerization ratio is 0.1 to 3 o as their total amount)
! fi=%, preferably 0.1 to 25% by weight,
Particularly suitable is 0.5 to 20% by weight. (I) of α,β-unsaturated carboxylic acid and α,β-unsaturated dicarboxylic acid anhydride of the multi-component copolymer: If the polymerization ratio is less than 0.1% by weight as the total amount of these, the compatibility with the polyamide resin is not good. -h, If it exceeds 30% by weight, moldability decreases. The copolymerization ratio of the styrene compound in this styrenic multi-component copolymer is at least 2.0% by weight, preferably 2% or more of I8W, particularly preferably 15% or more of I8W. If the copolymerization ratio of the styrene compound in this styrenic multi-component copolymer is less than 20% by weight,
Poor formability.

The styrenic multi-component copolymer of the present invention may be a multi-component copolymer consisting of the above-mentioned styrene compound, imide compound, α, β unsaturated carboxylic acid and/or unsaturated dicarboxylic acid anhydride, and furthermore an unsaturated nitrile-based copolymer. Compounds (e.g. acrylonitrile, methacrylonitrile) and ester compounds of (meth)acrylic acid (e.g. methyl acrylate, methyl methacrylate)
A copolymer of at most 30% by weight may be used as a polymerization component.

A styrenic copolymer containing a high proportion of α, β-unsaturated carboxylic acid and/or unsaturated dicarboxylic acid anhydride is produced, and the styrenic copolymer containing α, β-unsaturated carboxylic acid and/or unsaturated dicarboxylic acid anhydride is Alternatively, it may be mixed with a styrenic copolymer containing no unsaturated dicarboxylic acid anhydride in the above ratio when producing the final composition.

The melt index of the styrenic multi-component copolymer of the present invention [measured according to JIS K7210 at a temperature of 250°C and a load of 5.0 kg, hereinafter referred to as rMI(1)J] is usually 0.01 to 100 g/ 10 minutes and 0.0
5-100g/10 minutes is desirable, especially 0.1-100g/10 minutes
50 g/10 minutes is suitable. When a styrenic multi-component Juff composite having M I (1) of less than 0.01 g/10 minutes is used, moldability is not good. On the other hand, 100g/1
If the time exceeds 0 minutes, the resulting composition will have poor mechanical strength.

(B) Polyamide resin The polyamide resin used in the present invention is a linear polymer compound having an acid amide bond (-CONH-), and can be roughly classified into polycondensation of dibasic acid and diamine. Polyamides and polyamides obtained by self-combining cyclic lactams and amino acids are known. A typical example of the former is a polycondensate of hexamethylene and adipic acid (nylon 6-6).
, polycondensate of hexamethylene diamine and sebacic acid (
Nylon 6-1o), polycondensate of hexamethylene diamine and dodecanoic acid (nylon 6-12), polycondensate of hexamethylene diamine and terephthalic acid (nylon 6T)
), polycondensate of xylene diamine and adipic acid (XD
-6 nylon) and a polycondensate of xylene diamine and cepatic acid (XD-10 nylon). Typical examples of the latter include a self-polycondensate of caprolactam (nylon 6), a self-polycondensate of 10-aminoundecanoic acid (nylon 11), and a self-polycondensate of laurinlactam (nylon 12).

Furthermore, the degree of polymerization of polycondensates and mixed polyamide resins mainly composed of these components is not particularly specified, but generally the relative viscosity (measured in concentrated sulfuric acid at 30°C)
is 1.0 to 6.0, particularly preferably 1.5 to 5.5. These polyamide resins are manufactured industrially and used in a wide range of fields, and their manufacturing methods, types, various physical properties, molding methods, etc. are described in "Plastic Handbook 1" edited by Shunsuke Murahashi, Ryohei Oda, and Minoru Imoto. (
Asakura Shoten, published in 1980), pages 521 to 54
This is well known as page 8.

(C) Modified ethylene-propylene rubber Furthermore, the modified ethylene-propylene rubber used in the present invention has α, β
- It can be obtained by modification with at least one of an unsaturated carboxylic acid and an a,β-unsaturated dicarboxylic acid anhydride.

The ethylene-propylene copolymer rubber is a copolymer rubber of at least ethylene and propylene, such as a Ziegler-Natsuta catalyst, especially vanadium oxytrichloride,
A catalyst consisting of a vanadium compound such as vanadium tetrachloride and an organoaluminum compound is used, and 50% or more of ethylene and 50% or less of propylene (preferably 75 to 95% of ethylene and 25 to 5% of propylene) are used in a mold pan. )
Obtained by copolymerization. Furthermore, a multicomponent copolymer obtained by copolymerizing ethylene and propylene with a third component described later can also be used.

The third component is a linear or branched button diolefin containing two double bonds at the end, such as 1,4-pentadiene, 1,5-hexadiene, and 3,3-dimethyl 1,5-hexane diene. , l,4-hexadiene and 6-methyl-1,5-hebutadiene, linear or branched diolefins containing only one terminal double bond or bicyclo(2,2,1)-hebutene- 2(
Norbornene) and its derivatives (eg, ethylidenenorbornene, methylenenorbornene, vinylnorbornene) and other cyclic diene hydrocarbons having a double bond.

The content of the third component in the multicomponent copolymer obtained by copolymerizing the third component is usually 5 to 30 in terms of iodine value.

Mooney viscosity of this ethylene co-ffi combination M L 1
+4 (100°C) is generally 10 to 150, preferably 25 to 100.

The α, β-unsaturated carboxylic acid and α, β-unsaturated dicarboxylic acid anhydride used to modify the ethylene-propylene copolymer rubber are α, β-unsaturated carboxylic acid and α, β-unsaturated dicarboxylic acid anhydride shown as the copolymerization component of the styrenic multi-component copolymer. , β-unsaturated monocarboxylic acids, α, β-unsaturated dicarboxylic acids, and α, β-unsaturated dicarboxylic acid anhydrides.

This modified ethylene-propylene rubber is produced by the production method described below in the presence of a radical initiator.

The decomposition temperature of a radical initiator with a 1-minute half-life is usually 100°C.
or higher, preferably 105°C or higher, particularly 12°C or higher.
A temperature of 0°C or higher is preferable. Representative examples of suitable radical initiators include dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide,
2,5-dimethyl-2,5-di(tertiary-butyl-peroxy)hexane, 2,5-dimethyl-2,5-di(tertiary-butylperoxy)hexane-3, lauroyl peroxide, Examples include H-machine peroxides such as tertiary-butyl peroxybenzoate.

In producing the modified ethylene-propylene rubber, α, β-unsaturated carboxylic acid and/or α, β-
The proportions of the unsaturated dicarboxylic anhydride and the radical initiator used are generally as follows.

The total amount of α, β-unsaturated carboxylic acid and α, β-unsaturated dicarboxylic acid anhydride is 0, O1 to 5.
0 parts by weight, preferably 0.05 to 3.0 parts by weight,
Particularly suitable is a vertical side portion of 0.1 to 2.0.

The proportion of α,β-unsaturated carboxylic acid and α,β-unsaturated dicarboxylic acid anhydride is 0 as the amount of 1′.
．． If the amount is less than 0.01 parts by weight, the resulting modified ethylene-propylene rubber will have insufficient compatibility with the polyamide resin, making it difficult to obtain a uniform composition. On the other hand, if the amount exceeds 5.0 parts by weight, there is a risk that decomposition or crosslinking reactions may occur during production of the modified ethylene-propylene rubber.

In addition, for radical initiators, the amount is 0.001-1.0 parts by weight, and 0.001-1.0 parts by weight. 1 to 1.0 parts by weight of O is preferred, especially 0.01 to 0.5 parts by weight. When the proportion of the radical initiator used is less than 0.001 part by weight, the modification effect is poorly exhibited and it takes a long time to complete the modification.

On the other hand, if it exceeds 1.0 parts by weight, it is not preferable because excessive hydrogen or crosslinking reaction occurs.

The modified ethylene-propylene rubber of the present invention can be produced by known means for producing this type of modified olefin polymer.

A typical production method involves preparing the ethylene-propylene copolymer rubber, α, β-unsaturated carbon, etc. in a solvent such as an aromatic hydrocarbon compound such as xylene or toluene, or an aliphatic hydrogen ash compound such as hexane or heptane. A method for producing an acid and/or an α,β-unsaturated dicarboxylic acid anhydride and a radical initiator, and an ethylene-propylene copolymer rubber, an α,β-unsaturated carboxylic acid and/or an α,β-unsaturated A saturated dicarboxylic anhydride and a radical initiator are mixed in advance under essentially non-crosslinking conditions, and the resulting mixture is passed through a screw extruder,
Production methods include melt mixing using mixers commonly used in the field of synthetic resins, such as Banbury mixers and kneaders, but the latter method is preferred in terms of operation and economy. Adopted.

In the latter case, the temperature conditions for modification include deterioration of the ethylene-propylene copolymer rubber, decomposition of α, β-unsaturated carboxylic acid and α, β-unsaturated dicarboxylic acid anhydride,
It is selected appropriately considering the decomposition temperature of the radical initiator, but generally it is 100 to 350°C, and 150 to 32°C.
A temperature of 0°C is desirable, and a temperature of 150 to 300°C is particularly suitable.

Furthermore, in producing the ethylene-propylene rubber of the present invention, α,β-unsaturated carboxylic acid and unsaturated dicarboxylic acid anhydride are preliminarily grafted with 347 (
A modified ethylene-propylene rubber may be produced, and an unmodified ethylene-propylene polymer rubber may be blended into the final composition of the present invention so as to fall within the above range.

(D) Ethylene-based multi-component (polymer) Also, the ethylene-based multi-component copolymer used in the present invention is a combination of ethylene and α,β-type unsaturated carboxylic acid ester and dibasic unsaturated carboxylic acid or derivative thereof. (multiple elements) (multiple elements).

The number of carbon atoms in the alkyl group of the α, β-ethylenically unsaturated carboxylic acid ester is usually 1 to 10 (preferably 1 to 8), and among this α, β-ethylenically unsaturated carboxylic ester, Representative examples of acrylic acid alkyl esters include methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate.

Furthermore, representative examples of alkyl methacrylates include methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Among these α,β-ethylenically unsaturated carboxylic acid esters, methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate are particularly preferred. Furthermore, among dibasic unsaturated carboxylic acids or derivatives thereof, the number of carbon atoms in dibasic unsaturated carboxylic acids is usually at least 40,
It is preferably 35 or less. Representative examples of the dibasic unsaturated carboxylic acids include maleic acid, itaconic acid, 5-norbornene-2,3-dicarboxylic acid and fumaric acid. Typical examples of derivatives of dibasic unsaturated carboxylic acids include acid anhydrides, esters, and amide compounds of the dicyclic U-based unsaturated acids and their metals (the metals are usually alkali metals and those listed in IIA of the periodic table). and 1st IB
group metals, such as sodium, magnesium, calcium, and zinc) salts. Suitable examples of these dibasic unsaturated carboxylic acids and their derivatives include maleic acid, maleic anhydride, 5-norbornene-2,3
-dicarboxylic acid and 5-norbornene-2,3-dicarboxylic anhydride.

The copolymerization ratio of ethylene in this multi-component copolymer is 30 to 99
．． It is 85% by weight, particularly preferably 40 to 98.5% by weight. Further, the copolymerization ratio of the α,β-type ethylenically unsaturated carboxylic acid ester is 0.1 to 50% by weight, particularly preferably 1.0 to 50% by weight. Further, the copolymerization ratio of the dibasic unsaturated carboxylic acid or its derivative is 0.05 to 20% by weight, particularly preferably 0.5 to 10% by weight.

If the copolymerization ratio of α,β-type unsaturated carboxylic acid ester and dibasic unsaturated carboxylic acid or its derivative in this multi-component copolymer is less than the lower limit, the resulting modified ethylene polymer will improve the physical properties. The effects are not necessarily satisfactory. On the other hand, when the upper limit is exceeded, the softening point of the multi-component copolymer becomes high, fluidity decreases, and the impact resistance of the resulting composition also decreases.

Melt flow index of this multi-component copolymer [JIS
Measured under conditions 4 according to K7210, hereinafter rMF
RJ] is usually 0.01 to 100 g/10 minutes, preferably 0.05 to 100 g/10 minutes, and particularly preferably 0.1 to 50 g/10 minutes. MFR is 0.0
Processability is not good when using a multicomponent copolymer with a weight of less than 1 g and 710 minutes. On the other hand, if it exceeds 100 g/10 minutes, moldability is poor.

This multi-component copolymer is produced by a generally well-known radical high-pressure polymerization method, for example, by subjecting one 41-Ji compound to high pressure (generally 500 to 2.500 kg/cJ) and high temperature (generally 120 to 260°C). It can be easily produced by radical polymerization using a chain transfer agent if necessary.

(E) Composition ratio The composition ratio of the polyamide resin in the composition of the present invention is 30 to 80% by weight, preferably 30 to 75% by weight, and particularly preferably 35 to 75% by weight. If the proportion of the polyamide resin in the composition is less than 30% by weight, the chemical resistance of the composition to be removed is poor. On the other hand, 80
If it exceeds % by weight, the resulting composition will have a poor balance of heat resistance, impact resistance, and rigidity (flexural modulus), and will also have poor water absorption.

Furthermore, the composition of the modified ethylene-propylene rubber, the ethylene multi-component copolymer, and the styrene-based multi-component copolymer in the composition of the present invention is 30 to 90% per child. % by weight, 35-90% by weight
is desirable, particularly 35 to 85% by weight.

If the composition ratio of the styrenic multi-component copolymer in the total amount of the modified ethylene-propylene rubber, the ethylene-based multi-component copolymer, and the styrene-based multi-component copolymer is less than 30% by weight, the heat resistance and Low rigidity. on the other hand,
If the amount exceeds 90ffi, the impact resistance of the composition will be poor.

Furthermore, the proportion of the ethylene multi-component (composition ratio of the polymer is 15 to 8
5% by weight, preferably 15-80% by weight, 15-80% by weight
75% by weight is preferred. Even if the composition ratio of the ethylene-based multi-component copolymer in the total amount of the modified ethylene-propylene-based rubber and the ethylene-based multi-component copolymer is less than the lower limit or exceeds the upper limit, the impact resistance and heat resistance that are the objectives of the present invention will not be achieved. It is not possible to obtain a composition that is balanced in terms of gender.

(P) Production and molding method of resin composition The resin composition of the present invention is produced by uniformly blending the above-mentioned styrene-based multi-component copolymer, polyamide resin, modified ethylene-propylene-based rubber and ethylene-based multi-component copolymer. , the purpose can be achieved.

There are no particular restrictions on the blending method (mixing method).
Any method commonly used in the field of synthetic resins may be applied. Mixing methods include tri-blending using commonly used mixers such as Henschel mixers, tumblers and ribbon blenders, and melting using mixers such as oven rolls, extrusion mixers, kneaders and Banbury mixers. One method is to mix the mixture while Among these mixing methods, two or more of these mixing methods may be used in combination to obtain a footwear composition (for example, triblending is performed in advance, and then the mixture is melt-mixed). Among them, even when tri-blend is used in combination, or when one or more melt-kneading methods are used, when producing a molded product by the molding method described later, it is necessary to produce pellets using a pelletizer. It is preferable to use

Further, in producing the composition, two or a part of these composition components may be pre-mixed, and the resulting mixture and the remaining composition components may be mixed.

In producing the resin composition of the present invention, stabilizers against heat, oxygen and light, which are widely used in the fields of the above-mentioned styrenic multi-component copolymers, polyamide resins, modified ethylene-propylene rubbers and polyethylene resins; Depending on the intended use of the composition, additives such as flame retardants, fillers, colorants, lubricants, plasticizers, and (;) antistatic agents may be added to a range that does not essentially impair the properties of the composition of the present invention. It may be added with

Of the above mixing methods, both melt kneading and molding using the molding method described below must be carried out at a temperature at which the polymeric substance used is melted. but,
If carried out at high temperatures, the polymeric material will undergo thermal decomposition and deterioration. For these reasons, the temperature is generally 180 to 350℃.
(preferably 200 to 320°C).

The composition of the present invention can be formed into a desired shape by quickly using molding methods such as 1-1 extrusion molding, extrusion molding pressure, compression moldability, and blow molding methods that are generally practiced in the field of synthetic resins. It may also be molded. Alternatively, after forming the sheet into a sheet using an extrusion molding machine, this sheet may be formed into a desired shape by a secondary processing method such as a vacuum forming method or a pressure forming method.

[Examples and comparative examples]

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the Examples and Comparative Examples, the Izot impact strength was measured with a notch at a temperature of 23° C. according to ASTM D256. In addition, the flexural modulus is ASTM
Measured according to D790 at a temperature of 23°C.

Furthermore, in the water absorption test, the flexural modulus of elasticity was measured after the test piece was immersed in boiling water at 100°C for 30 minutes.

In addition, the heat distortion temperature is ASTM D (according to i48, 18
, measured at a stress of 6 kg/cd.

In addition, in Examples and Comparative Examples, the manufacturing method, type, physical properties, etc. of the styrene-based multi-component copolymer, polyamide resin, modified ethylene-propylene-based rubber, and ethylene-based multi-component copolymer used are shown below.

[(^) Styrenic multi-component copolymer]

As the styrenic multi-component copolymer, a styrenic multi-component copolymer manufactured as follows was used.

log autocrepe l: [i, 000g water, 2,
400g (7) of styrene (ST), 811Qg of acrylonitrile (AN), BOOg of N-phenylmaleimide (N-PMI) and 120g of methacrylic acid (MAA) were charged, and lauryl peroxide and 9.6 g of tertiary-butyl peroxylaurate, 8 g of tertiary-dodecyl mercaptan as chain transfer agent and 60 g as suspension stabilizer
of tricalcium phosphate and 0.9 g of sodium dodecylbenzenesulfonate were added, and polymerization was carried out at a temperature of 80° C. for 2 hours with stirring. Then, the polymerization system was
After raising the temperature to 20° C. and carrying out polymerization at this temperature for 3 hours, the polymerization system was allowed to cool to room temperature. As a result, about 3
．． 500 g of pale bitter powder was obtained. When the obtained powder was determined by infrared absorption spectroscopy (solution method),
Weight ratio ST: AN: N-PM I:
It was a terpolymer (hereinafter referred to as "copolymer (1)") having a ratio of MAA-80:17:20:3. The heat distortion temperature of the obtained copolymer (1) was 115.0°C, and the M I (+) was 18.2 g/! It was 0 minutes.

In addition, the MA used in producing the copolymer (1)
Polymerization was carried out in the same manner as for copolymer (1) except that the entire amount of A was changed to AN. Approximately 3.500g obtained
When the powder was analyzed in the same manner as copolymer (1), it was found that ff
i amount ratio ST:AN:N-PMI-60: 20:
20 [hereinafter referred to as "copolymer (2)"]. The heat distortion temperature of the obtained copolymer (2) was 114.2°C, and M l (1) was 17.8 s
r/10 minutes.

[<B> Polyamide resin]

In addition, as a polyamide resin, a condensation product of hexamethylene diamine and adipic acid whose η (1) is 266 (nylon 6-6, hereinafter referred to as rP A (a) J) and a polyamide resin whose η (1) is 2.7 are used. Polycaprolactam (nylon 6, hereinafter referred to as rPA(b)J) was used.

[(C) Modified ethylene-propylene rubber] Further, as a modified ethylene-propylene rubber, ethylene-propylene having a copolymerization ratio of propylene of 26.5ffij1% and a Mooney viscosity (MLl+4.100°C) of 60 is used.
Propylene copolymer rubber (hereinafter referred to as "EP RJ") 1
00 parts by weight, 2.0 parts by weight of maleic anhydride and 0.00 parts by weight.
015 parts by weight of 2.5-dimethyl-2,5-di(tertiary-butyl-peroxy)hexane was charged into a Henschel mixer, and triblended for 5 minutes. The resulting mixture was kneaded using a solvent extruder (diameter 40 mm) at a resin temperature in the range of 220 to 240°C to obtain a modified ethylene-propylene copolymer rubber (hereinafter referred to as "modified product (I)").
) was manufactured. The modified amount of maleic anhydride in the obtained modified product (1) was 1.8% by weight.

[(D) Ethylene-based multi-component copolymer]

In addition, as an ethylene-based multi-component copolymer, ethylene-methyl methacrylate-- which has a methyl methacrylate I Maleic anhydride terpolymer (MFR, 3.5 g/10 min, hereinafter rEMM)
HJ] was used.

Examples 1-9. Comparative Examples 1 to 11 Each component whose distribution is shown in Table 1 was charged into a Henschel mixer, and triblended for 5 minutes. Each of the obtained mixtures was kneaded using a twin-screw extruder (diameter: 40 mm) set at 270°C to form pellets (
composition) was produced. Each of the obtained pellets was vacuum dried at a temperature of 80°C for 48 hours, and then injection molded using an injection molding machine set at 270°C to prepare test pieces for measurement.

Each test piece was subjected to a heat resistance test, a water absorption test, and measurements of Izot impact strength and flexural modulus. The results are shown in Table 2.

No. 2 table (Part 1) l) kg・cIII/cI11 〔Effect of the invention〕 The resin composition of the present invention exhibits the following effects.

(1) Excellent heat resistance.

(2>　Deterioration of physical properties due to water absorption is small.

(3) Excellent impact resistance.

(4) Good rigidity (early bending and elevation).

The resin composition of the present invention can be used in a wide variety of ways to achieve the effects described above. Typical uses are shown below.

(1) Fenders, rear quarter panels, etc.
Vehicle outer panel.

(2) Automotive parts such as oil covers and radiator grills.

(3) Mechanical and electrical parts such as connectors and transformer cases.

Claims (1)

[Scope of Claims] (A) A styrenic multi-component copolymer comprising at least a styrene compound, an imide compound of an α,β-unsaturated dicarboxylic acid, and an unsaturated carboxylic acid and/or an unsaturated dicarboxylic acid anhydride; (B) Polyamide resin (C) Ethylene-propylene copolymer rubber modified with α,β-unsaturated carboxylic acid and/or unsaturated dicarboxylic acid anhydride, and (D) α,β-type unsaturated carboxylic acid ester The copolymerization ratio of dibasic unsaturated carboxylic acid or its derivative is 0.1 to 50% by weight, and the copolymerization ratio of dibasic unsaturated carboxylic acid or its derivative is 0.1 to 50% by weight.
05 to 20% by weight of an ethylene-based multicomponent copolymer, the composition ratio of polyamide resin in the composition is 30 to 80% by weight, modified ethylene-propylene copolymer rubber, The composition ratio of the styrene-based multi-component copolymer in the total amount of the ethylene-based multi-component copolymer and the styrene-based multi-component copolymer is 30 to 90% by weight. The composition ratio of the ethylene multi-component copolymer in the total amount with the copolymer is 15 to 85% by weight, and the unsaturated carboxylic acid and unsaturated dicarboxylic acid anhydride in the styrene multi-component copolymer are The copolymerization ratio is 0.1 to 30% by weight as their total amount, and the copolymerization ratio of the imide compound is 5.0 to 60% by weight, but the copolymerization ratio of the styrene compound is at least 20% by weight. % resin composition.