JPH0665430A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition good in its surface layer peeling resistance, impact resistance and flowability and useful for injection moldings, etc., by adding glass fibers, talc and a specific compatibilizing agent to resins comprising a modified vinyl chloride resin or its mixture with a modified styrenic resin and an olefinic resin. CONSTITUTION:This resin composition excellent in its elastic modulus, heat resistance and appearance comprises 100 pts.wt. of resins comprising 1-99 pts.wt. of (A) a modified vinyl chloride resin and (or) (B) a modified styrenic resin and (C) 99-1 pts.wt. of an olefinic resin, 1-50 pts.wt. of (D) glass fibers and (or) (E) talc, and (F) 0.1-50 pts.wt. of a compatibilizing agent comprising a polymer produced by adding 150 pts.wt. of a functional group-containing rubbery polymer and (or) an olefinic polymer or by grafting 5-200 pts.wt. of a monomer group to 25-70 pts.wt. of an ethylene-propylene-dienic rubber, 25-70 pts.wt. of ethylene-vinyl acetate copolymer, 0-25 pts.wt. of a rubbery polymer and (or) an olefinic polymer, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent appearance, and more particularly to a resin composition having excellent elastic modulus, heat resistance and appearance.

[0002]

2. Description of the Related Art Recently, alloying polymers having different characteristics to modify a resin has been extensively studied. For example, the following reports have been made on alloying of an olefin resin with a styrene resin or a vinyl chloride resin. That is, a method of alloying with an ethylene-vinyl acetate copolymer (Japanese Patent Publication Sho 60)
-36178), a method of alloying with a polyethylene-EPDM modified product (JP-A-63-340039, JP-A-1-165640), and a method of alloying with a block of polypropylene and a styrene resin (JP-A-2-19).
9127, JP-A-2-199128, JP-A-2-199
129) and so on.

The alloy of the olefin resin and the styrene resin or the vinyl chloride resin has attracted attention in the complicated applications, but since the olefin resin is used, the elastic modulus and heat resistance are high. Shortage is a problem.

As a means for increasing elastic modulus and heat resistance, a method of adding an inorganic substance such as talc or an inorganic filler such as glass fiber is generally practiced.

[0005]

SUMMARY OF THE INVENTION In the above conventional method,
Insufficient improvement in elastic modulus and heat resistance, surface peeling phenomenon where the surface layer of the molded product separates from the molded product with a slight force after molding under high shear such as injection molding, or the filler There was a problem that the appearance was deteriorated due to the surface irregularities and uneven surface gloss due to the addition.

An object of the present invention is to solve the above problems and to provide a resin composition excellent in elastic modulus, heat resistance and appearance.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that modified vinyl chloride resin and / or modified styrene resin and olefin resin have glass fiber and (or ) For talc blended systems, one or more ethylene-propylene-diene rubbers, one or more ethylene-vinyl acetate copolymers, one or more rubbery polymers and / or olefinic polymers and one or more A compatibilizing agent, which is a composition composed of a functional group-containing rubber-like polymer and / or an olefin-based polymer and at least partially reacted with each other,
At least one ethylene-propylene-diene rubber, at least one ethylene-vinyl acetate copolymer and 1
Compatibilizer, which is a graft polymer obtained by impregnating and polymerizing a monomer group containing a functional group into a polymer mixture composed of one or more rubber-like polymers and / or olefin polymers, containing a functional group A compatibilizer which is a graft copolymer composed of a styrene polymer part and a polymer part composed of a styrene polymer, an alkyl (meth) acrylate polymer and / or a vinyl chloride polymer, and an olefin polymer. It contains a compatibilizer, which is a block copolymer composed of a block of a polymer and a block of a styrene polymer, an olefin polymer modified with a special compound, and functional groups that react with the special compound, respectively. , At least one of a compatibilizing agent comprising a modified styrene-based polymer, a modified methacrylate-based polymer or a modified vinyl chloride-based polymer is used. If, interestingly, elastic modulus, and improved heat resistance, and mar layer peelable, the surface irregularities, surface gloss unevenness are improved, we have found that the surface appearance is good.

That is, according to the present invention, (A) modified vinyl chloride resin and / or (B) modified styrene resin 1 to
(D) glass fiber and / or (F) talc 1 to 50 parts by weight, and (F) to 100 parts by weight of a total of 100 parts by weight of 99 parts by weight and 99 to 1 parts by weight of (C) olefin resin. -1): (f1) 25 to 70 parts by weight of one or more ethylene-propylene-diene rubbers, (f2) 25 to 70 parts by weight of one or more ethylene-vinyl acetate copolymers, (f
3) 0 to 25 parts by weight of one or more rubber-like polymers and / or olefin polymers and (f4) 1 to 50 parts by weight of one or more functional group-containing rubber-like polymers and / or olefin polymers Parts, at least one ethylene-propylene-diene rubber (f1), at least one ethylene-vinyl acetate copolymer (f2), at least one rubber-like polymer and / or olefin polymer (f3), and A compatibilizing agent in which the total amount of the one or more functional group-containing rubber-like polymer and / or the olefin polymer (f4) is 100 parts by weight, (F-2): (f1) one or more ethylene-propylene. 25-70 parts by weight of diene rubber, (f2) 25-70 parts by weight of one or more ethylene-vinyl acetate copolymers and (f3) one or more rubbery polymers and / or olefins From 0 to 25 parts by weight of polymer, one or more ethylene-propylene-diene rubber (f1), one or more ethylene-vinyl acetate copolymer (f2) and one or more rubbery polymer and / or olefin system A polymer mixture in which the total amount of the polymer (f3) is 100 parts by weight, and 0.05 to 50% by weight of a monomer group containing the (f5) functional group.
And 50 to 99.95% by weight of monomers that can be copolymerized with these
A compatibilizer which is a graft polymer composed of 5 to 200 parts by weight of a monomer group consisting of (F-3): (f6) functional group-containing styrene polymer part 5
To 95% by weight and (f7) a styrene polymer, an alkyl (meth) acrylate polymer and / or a vinyl chloride polymer in a polymer portion of 95 to 5% by weight. Compatibilizer, (F-4): Block 5 of (f8) olefin polymer
~ 95% by weight and (f9) styrene polymer block 95 ~
The amount of the compatibilizing agent which is a block copolymer composed of 5% by weight and (F-5): (f10) a functional group-containing monomer is 0.05.
To 95% by weight of a modified olefin polymer polymerized to contain 50% by weight to 0.05% of a monomer having a functional group reactive with the functional group of the monomer having the functional group.
To 50% by weight of (f11) modified styrene polymer, (f12) modified methacrylate polymer or (f13) modified vinyl chloride polymer
1 selected from the group consisting of compatibilizing agents consisting of 5% by weight
It relates to a resin composition containing 0.1 to 50 parts by weight of one or more compatibilizers.

[0009]

EXAMPLES Compatibilizer (F-1) used in the present invention
(F-5) is the elastic modulus, heat resistance, and
It is an essential component for improving the appearance and not reducing the impact resistance and fluidity. That is, the compatibilizers (F-1) to (F-5) of the present invention originally do not have compatibility, unlike the modified vinyl chloride resin and / or the modified styrene resin and the olefin resin. Alternatively, it has an effect of improving the compatibility between resins having poor compatibility and further improving the dispersibility of glass fiber and / or talc.

The compatibilizer (F-1) is (f1) 25 to 70 parts by weight of at least one ethylene-propylene-diene rubber,
25 to 70 parts by weight of (f2) one or more ethylene-vinyl acetate copolymers, 0 to 25 parts by weight of (f3) one or more rubbery polymers and / or olefinic polymers and (f4) one or more The composition comprises 1 to 50 parts by weight of a functional group-containing rubbery polymer and / or an olefin-based polymer in a total of 100 parts by weight.

As the component (f1) in the compatibilizer (F-1) used in the present invention, ethylene content, propylene content, diene content, type of diene, Mooney viscosity of rubber, in rubber Although it does not particularly define the monomer distribution state of the above, it is composed of two different ethylene-propylene-diene rubbers in order to improve the elastic modulus of the obtained resin composition and not reduce the impact resistance. At least one rubber has an ethylene content of 60% or more, a glass transition point of −55 ° C. or less, and a Mooney viscosity ML _{1 + 4} (100 ° C.): 75 or more, and it is preferable that the rubber has an appropriate strength.

It is considered that the use of two kinds of rubber causes the viscosity to be distributed and the width of the distribution to be increased, so that the strength is increased.

The method for producing this rubber is known, and the degree of unsaturation can be adjusted by adjusting the diene content using a vanadium type catalyst. The standard value is 3-20 double bonds per 1000 C atoms. Mooney viscosity is generally
30 to 125, the ethylene content is 45 to 80% by weight, the propylene content is 20 to 50% by weight, and the monomer distribution state of the rubber is random.

The component (f2) is preferably an ethylene-vinyl acetate copolymer having a vinyl acetate content of 25 to 30% by weight. If the vinyl acetate content is outside this range, the elastic modulus, the appearance (including the peeling resistance to the surface layer) and the impact resistance are deteriorated, which is not preferable.

A more preferred ethylene-vinyl acetate copolymer has a melt flow index of 0.5 to 25 dg.
/ Min (230 ℃, 2.16kg / cm ² ).

The component (f3) is styrene-butadiene rubber, styrene-butadiene-block copolymer, acrylonitrile-butadiene rubber in order to improve the elastic modulus of the resin composition of the present invention and not reduce the impact resistance or fluidity. , At least one selected from the group consisting of polybutadiene rubber, isobutylene rubber, butyl rubber, and polyolefin is preferable. For the resin composition of the present invention, styrene-based resin is used in terms of elastic modulus and impact resistance.
More preferred are butadiene rubber, styrene-butadiene-block copolymers and polybutadiene rubber. Further, in order to improve the compatibility between the resin compositions of the present invention, the component (f3) is a polymethylmethacrylate ester having an affinity with the modified vinyl chloride resin and / or the modified styrene resin, respectively. At least one selected from the group consisting of styrene-butadiene rubber grafted with styrene-acrylonitrile copolymer or styrene-methyl methacrylate copolymer, styrene-butadiene block copolymer, acrylonitrile-butadiene rubber, polybutadiene rubber, isobutylene rubber, butyl rubber and polyolefin. It is preferably a seed. Further, from the viewpoint of elastic modulus and impact resistance, polymethylmethacrylate ester, styrene-acrylonitrile copolymer or styrene-methylmethacrylate ester copolymer, which has affinity with the modified vinyl chloride resin and / or modified styrene resin, respectively. More preferred are styrene-butadiene rubbers, styrene-butadiene-block copolymers and polybutadiene rubbers grafted with.

As the component (f4), modified styrene-butadiene rubber, modified styrene-butadiene-block copolymer, modified acrylonitrile-butadiene rubber, modified polybutadiene rubber, modified isobutylene rubber, modified butyl rubber and modified polyolefin each containing a functional group. At least one selected from the group consisting of: a modified styrene-butadiene rubber, a modified styrene-butadiene-block copolymer, a modified acrylonitrile-butadiene rubber, each grafted with a functional group-containing compound and / or a functional group-containing polymer. At least one selected from the group consisting of modified polybutadiene rubber, modified isobutylene rubber, modified butyl rubber and modified polyolefin is more preferred.

As the functional group, for example, an epoxy group,
Examples thereof include a primary, secondary or tertiary amino group, an amide group, a carboxyl group, an acid anhydride group and a hydroxyl group, which may be used alone or in combination of two or more. In order to further improve the compatibility between the resin compositions of the present invention,
Epoxy groups are preferred.

Examples of the monomer capable of introducing a functional group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinyl pyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylamide, maleimide, acrylic acid, Methacrylic acid, maleic acid, maleic anhydride, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-
Examples include hydroxypropyl acrylate.

Component (f4) (total 100% by weight)
The amount of the functional group to be introduced is preferably 0.01 to 50% by weight, and more preferably 0.1 to 10% by weight, as a monomer.

If the total amount of the compatibilizer (F-1) is 100 parts by weight, (f1) one or more kinds of ethylene-propylene-diene rubber is 25 to 70 parts by weight, and (f2) one or more kinds of ethylene-. 25 to 70 parts by weight of vinyl acetate copolymer, (f
3) 0 to 25 parts by weight of one or more rubber-like polymers and / or olefin polymers and (f4) 1 to 50 parts by weight of one or more functional group-containing rubber-like polymers and / or olefin polymers It is often part, and the (f1) component 35-
65 parts by weight, (f2) component 35 to 65 parts by weight, (f3) component 1
To 20 parts by weight and 1 to 30 parts by weight of component (f4), more preferably 35 to 65 parts by weight of component (f1), 35 to 65 parts by weight of component (f2), and 0 parts by weight of component (f3). And 1 to 30 parts by weight of the component (f4).

The ratio of the (f1) component to the (f2) component is preferably as close to 1 as possible in order to improve the compatibility of the modified vinyl chloride resin and / or the modified styrene resin with the olefin resin. .

When the amount of the component (f1) is less than 25 parts by weight, the elastic modulus is lowered, and when it exceeds 70 parts by weight, the appearance is deteriorated.
If the amount of the component (2) is less than 25 parts by weight, the appearance is deteriorated, and if it exceeds 70 parts by weight, the elastic modulus is lowered. If the component (f3) or the component (f4) is out of the applicable range, the appearance is deteriorated.

The component (f3) does not necessarily have to be contained, and even if it is not contained, the appearance is improved.

The method for producing the compatibilizer (F-1) is not particularly limited, but the following method can be exemplified. A mixture of the components (f1), (f2), (f3) and (f4) is melt-kneaded at a high temperature (300 ° C. or less) in an extruder to react. The lower limit of melting temperature is determined by the melting range of the component with the highest melting point. The melting range of the compatibilizer (F-1) of the present invention is 40 to 150 ° C, especially 50 to
It can be 100 ° C. One important condition in the preparation of compatibilizer (F-1) is that the components are at least partially interacted.

The compatibilizer (F-2) is (f1) 25 to 70 parts by weight of at least one ethylene-propylene-diene rubber,
(F2) 25 to 70 parts by weight of one or more ethylene-vinyl acetate copolymer, and (f3) 0 to 25 parts by weight of one or more rubber-like polymer and / or olefin polymer, each component (f1) , (F2) and (f3) total 100 parts by weight of a polymer mixture are suspended in water, and (f5) functional group-containing monomer group 0.05 to 50% by weight
And 50 to 99.95% by weight of monomers that can be copolymerized with these
It is a compatibilizer obtained by impregnating the above-mentioned polymer mixture with 5 to 200 parts by weight of the monomer group consisting of and polymerizing.

In this graft polymer, the component (f
1), (f2) and (f3) are the trunk polymers.

Components (f1), (f2) and (f3)
Is the same as in the compatibilizer (F-1).

The monomer group (f5) to be impregnated in the polymer mixture and polymerized is composed of 0.05 to 50% by weight of a functional group-containing monomer group and 50 to 99.95% by weight of a copolymerizable monomer group. % Is a monomer group. Preferably, it is composed of 0.1 to 30% by weight of a functional group-containing monomer group and 70 to 99.9% by weight of a copolymerizable monomer group.

If the monomer group containing a functional group is less than 0.05% by weight, the appearance (surface layer peeling resistance) will be deteriorated, and if it exceeds 50% by weight, the fluidity will be greatly reduced and the molded article will have surface irregularities. Surface gloss unevenness occurs and the appearance is deteriorated.

As the functional group, for example, an epoxy group,
Examples thereof include a primary, secondary or tertiary amino group, an amide group, a carboxyl group, an acid anhydride group and a hydroxyl group, which may be used alone or in combination of two or more. In order to further improve the compatibility between the resin compositions of the present invention,
Epoxy groups are preferred.

Examples of the monomer capable of introducing a functional group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinyl pyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylamide, maleimide, acrylic acid, Methacrylic acid, maleic acid, maleic anhydride, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-
Examples include hydroxypropyl acrylate. The above compounds are used alone or in combination of two or more.

Examples of the copolymerizable monomer include aromatic vinyl compounds, vinyl cyanide compounds, alkyl (meth) acrylate compounds, halogenated vinyl compounds, olefin compounds and other vinyl compounds copolymerizable therewith. preferable.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and examples of the aromatic vinyl compound include styrene, methylstyrene, chlorostyrene and α-methylstyrene, and alkyl (meth) ) Examples of the acrylate compound include methyl methacrylate, ethyl methacrylate, butyl acrylate and the like. Examples of vinyl halide compounds include vinyl chloride and vinylidene chloride, and examples of olefin compounds include ethylene,
Examples include propylene and butadiene. Any of the above compounds may be used alone or in combination of two or more.

The compatibilizer (F-2) is (f1) 25 to 70 parts by weight of one or more ethylene-propylene-diene rubber (f).
2) Use of a polymer mixture comprising 25 to 70 parts by weight of one or more ethylene-vinyl acetate copolymers and (f3) 0 to 25 parts by weight of one or more rubbery polymers and / or olefinic polymers. Good, (f1) component
35-65 parts by weight, (f2) component 35-65 parts by weight and (f
3) The component is preferably 1 to 20 parts by weight, more preferably (f
1) Component 35 to 65 parts by weight, component (f2) component 35 to 65 parts by weight and component (f3) component 0 parts by weight.

The ratio of the (f1) component to the (f2) component should be as close to 1 as possible in order to improve the compatibility of the modified vinyl chloride resin and / or the modified styrene resin with the olefin resin. preferable.

When the amount of the component (f1) is less than 25 parts by weight, the elastic modulus is lowered, and when it exceeds 70 parts by weight, the appearance is deteriorated.
If the amount of the component (2) is less than 25 parts by weight, the appearance is deteriorated, and if it exceeds 70 parts by weight, the elastic modulus is lowered. If the component (f3) is out of the applicable range, the appearance is deteriorated.

The component (f3) does not necessarily have to be contained, and even if it is not contained, the appearance is improved.

The method for producing the compatibilizer (F-2) is not particularly limited, but the following method can be exemplified. To the polymer mixture of each component (f1), (f2) and (f3),
A monomer group (f5) consisting of a functional group-containing monomer group and a monomer group copolymerizable with these is impregnated and polymerized. The compatibilizer (F-2) of the present invention includes, for example, 300 to 500 parts by weight of a polymer mixture of each component (f1), (f2) and (f3) and 100 parts by weight of the mixture and a dispersant. In a nitrogen atmosphere, 0.01 to 5 parts by weight of a radical polymerization initiator (decomposition temperature at which the half-life is 10 hours is 80 to 180 ° C.) is added to 100 parts by weight of the monomer group in a nitrogen atmosphere. About 1 to 5 after heating (about 50 to 100 ° C) under the condition that decomposition does not substantially occur and the monomer group does not start polymerization.
After impregnating the mixture with 70% by weight or more of the monomer for an hour, the temperature of the suspension is raised to 100 to 150 ° C. to polymerize the mixture,
It is manufactured by completing the polymerization in about 3 to 10 hours. As the radical polymerization initiator, for example, di-t-butyl peroxide, di-cumyl peroxide, t-butyl peroxybenzoate or the like is used.

The compatibilizers (F-1) and (F- of the present invention
The preferable melt flow index of 2) is 0.25 to 1.
It is 5 dg / min (230 ° C, 2.16 kg / cm ² ). This melt flow index depends on the reaction between the components, and if the reaction proceeds too much, separation occurs and the melt flow index increases. Therefore, it is preferable that the melt flow index is 1.5 dg / min or less.

The compatibilizer (F-3) of the present invention is (f6).
Functional group-containing styrene polymer part 5 to 95% by weight (f7)
It is a graft copolymer composed of a polymer portion consisting of a styrene polymer, an alkyl (meth) acrylate polymer and / or a vinyl chloride polymer in an amount of 95 to 5% by weight.

In this graft copolymer, usually (f
6) The component is the trunk, but it can be reversed.

Functional group-containing styrene polymer part (f6)
Is preferably a styrene polymer containing an epoxy group and obtained by polymerizing 50% by weight or more of an aromatic vinyl compound.

As the aromatic vinyl compound, styrene,
Examples include methylstyrene, α-methylstyrene, chlorostyrene, β-isopropylnaphthalene, and the like. 80% by weight or more of the aromatic vinyl compound is styrene, methylstyrene, α-methylstyrene, and / or β-isopropylnaphthalene. It is preferable.

Polymer part (f7) of compatibilizer (F-3)
Consists of a styrene polymer, an alkyl (meth) acrylate polymer and / or a vinyl chloride polymer.
The styrene-based polymer is preferably a copolymer of 15 to 40% by weight of a vinyl cyanide compound, 50 to 85% by weight of an aromatic vinyl compound, and 0 to 20% by weight of another vinyl compound which can be copolymerized with these. The (meth) acrylate-based polymer contains 60% by weight of methyl methacrylate as a constituent component.
It is preferable to contain the above.

The epoxy group in the compatibilizer (F-3) is preferably contained in an oxygen content of 0.03 to 5% by weight.
When the epoxy oxygen content is 0.03% by weight or less, the appearance properties (surface layer peeling resistance) are deteriorated, and when the epoxy oxygen content is 5% by weight or more, surface irregularities and uneven surface gloss are generated due to deterioration of fluidity, and the appearance properties are deteriorated.

The compatibilizer (F-3) is a functional group-containing styrene polymer part (f6) of 5 to 95% by weight, a styrene polymer, an alkyl (meth) acrylate polymer and / or a vinyl chloride polymer. Polymer part composed of coalescence (f7)
95 to 5% by weight, preferably 25 to 75% by weight of the functional group-containing styrene polymer part (f6) and 75 to 25% by weight of the polymer part (f7). (F6) component is 5
If it is less than 95% by weight, the appearance (resistance to peeling off the surface layer) is deteriorated. When the content of the component (f7) is less than 5% by weight, surface irregularities and uneven gloss are generated to deteriorate the appearance, and when it exceeds 95% by weight, surface layer peeling occurs and the appearance is deteriorated.

As the method for producing the compatibilizing agent (F-3), a known production method can be used, and the kind and operation thereof are not particularly limited. For example, there are the following two methods.

The first method is to obtain a graft polymer by polymerizing the macromonomer of the polymer part (f7) and the monomer of the polymer part (f6). Polymerization is carried out, for example, in a solvent such as toluene, xylene, benzene or chlorobenzene under a nitrogen atmosphere at 30 to 100 ° C., preferably 40 to 80 ° C., cumene hydroperoxide, di-cumyl peroxide, t-butyl cumyl peroxide. And the like using a polymerization initiator.

In the second method, in the presence of the polymer part (f6), in a solvent such as toluene, xylene or benzene, at a high temperature of 150 to 250 ° C., preferably 160 to 230 ° C., benzyl peroxide or di- In this method, a radical initiator such as cumyl peroxide is used to graft the monomer of the polymer part (f7).

The compatibilizer (F-4) is a block copolymer composed of 5 to 95% by weight of an olefin polymer block (f8) and 95 to 5% by weight of a styrene polymer block (f9). Is.

The olefin polymer block (f8) is, for example, a homopolymer of various olefin monomers, a random copolymer thereof, a block copolymer or a graft copolymer thereof, or a homopolymer or copolymer thereof. Examples include a mixture of coalescence. For example,
High density polyethylene, medium density polyethylene, low density polyethylene, copolymer of ethylene and other α-olefin, polypropylene, copolymer of propylene and other α-olefin, polybutene, poly-4-methylpentene-1 Such as polyolefins or oligomers, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer, butyl rubber, butadiene rubber, propylene-butene copolymer,
Examples thereof include polyolefin-based elastomers such as ethylene-acrylic acid ester copolymers, which may be used alone or in combination of two or more kinds. Among these, low modulus polyethylene, polypropylene, copolymers of propylene and other α-olefins and oligomers thereof are preferable from the viewpoint of elastic modulus and heat resistance, and polypropylene, propylene and other α-olefins are preferable. Particularly preferred are the copolymers and oligomers thereof.

The three-dimensional structure of this olefin polymer is not particularly limited, but from the viewpoint of heat resistance, the isotactic content is preferably 60% by weight or more, more preferably 70% by weight.
That is all. The number average molecular weight of the olefin polymer is preferably from 500 to 60,000, more preferably from 1,000 to 50,000 from the viewpoint of elastic modulus and appearance. The number average molecular weight is G
It can be measured by PC (gel permeation chromatography).

The block (f9) of the styrene polymer is
It is preferably a block obtained by polymerizing 3 to 40% by weight of a vinyl cyanide compound, 35 to 85% by weight of an aromatic vinyl compound and 50 to 0% by weight of an alkyl (meth) acrylate compound.

When the composition within these ranges is used, the compatibility with the modified styrene resin is improved.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and examples of the aromatic vinyl compound include styrene, methylstyrene, chlorostyrene, α-methylstyrene and β-isopropenylnaphthalene. Examples of the alkyl (meth) acrylate compound include methyl methacrylate, ethyl methacrylate and butyl acrylate. Any of the above compounds may be used alone or in combination of two or more.

The block (f9) of the styrene polymer is
In addition to the vinyl cyanide compound, the aromatic vinyl compound and the alkyl (meth) acrylate compound, 20% by weight or less of another vinyl compound copolymerizable therewith may be copolymerized. Examples of other copolymerizable vinyl compounds include maleimide, N-substituted maleimide, and (meth) acrylic acid.

Further, the block (f9) of the stinylene polymer preferably has a reduced viscosity of 0.2 to 0.9 dl / g (dimethylformamide solution, 30 ° C., concentration 0.3 g / dl),
Within the range other than this range, the elastic modulus and the appearance of the resin composition of the present invention tend to be lowered.

The compatibilizer (F-4) is composed of 5 to 95% by weight of a block of (f8) olefin polymer and 95 to 5% of a block of (f9) styrene polymer. 25 to 75% by weight of the block (f8) and 75 to 25% by weight of the styrene copolymer block (f9). When the content of the component (f8) is less than 5% by weight, the compatibility with the olefin resin is lowered, and 95% by weight
If it exceeds, the compatibility with the modified styrenic resin is lowered and the appearance is deteriorated. When the content of the component (f9) is less than 5% by weight, the compatibility with the modified styrene resin is lowered, and when it exceeds 95% by weight, the compatibility with the olefin resin is lowered and the surface layer is peeled off to deteriorate the appearance.

The method for producing the compatibilizer (F-4) is not particularly limited. For example, the following methods can be given.

There is a method in which the olefin polymer block (f8) is polymerized by living polymerization and then the styrene polymer block (f9) is polymerized.

Further, a hydroxyl group or a carboxyl group is introduced at the terminal of the olefin polymer by living polymerization, radiation modification, or acid anhydride modification, while β-mercaptopropionic acid or 2-mercaptoethanol is used as a chain transfer agent. For example, in a solvent such as xylene, a hydroxyl group or a carboxyl group is introduced at the terminal of the styrenic polymer, and a non-aqueous solvent such as xylene, decalin or tetralin is used at 100 to 200 ° C. for 2 to 10 ° C.
There is a method of producing by dehydration reaction for a period of time.

The compatibilizer (F-5) is a modified olefin polymer obtained by polymerizing a monomer having a functional group (f10), and a monomer having a functional group capable of reacting with the functional group of the monomer having the functional group. Was polymerized, (f11)
It is a compatibilizer composed of a modified styrene polymer, a (f12) modified methacrylate polymer or a (f13) modified vinyl chloride polymer.

As the functional group that can be introduced into (f10),
For example, an epoxy group, a primary, secondary or tertiary amino group, an amide group, a carboxyl group, an acid anhydride group, a hydroxyl group and the like are exemplified, and these are used alone or in combination of two or more kinds.

Examples of the compound capable of introducing a functional group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinyl pyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylamide, maleimide, acrylic acid and methacrylic acid. , Maleic acid, maleic anhydride, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-
Examples include hydroxypropyl acrylate.

Among them, the reaction with the functional group introduced into the modified styrene polymer (f11), modified methacrylate polymer (f12) or modified vinyl chloride polymer (f13) in the present invention is made more effective. In order to do so, the modified olefin polymer (f) of the compatibilizer (F-5) is used.
10) is a modified olefin system having one structural unit having at least one amide group and at least one functional group selected from the group consisting of a glycidyloxy group and a glycidyl group per 2-1000 repeating units of olefin. It is preferably a polymer. Such a modified olefin polymer is a compound having a functional group capable of polymerizing with an olefin, for example, a vinyl group, and has one or more amide groups, and one or more glycidyloxy groups and / or glycidyl groups. A compound having a group or a compound having one or more amide groups and one or more glycidyloxy groups and / or glycidyl groups and other functional groups can also be produced by copolymerization with an olefin. it can. In addition, after producing a polyolefin by a usual polymerization method, a compound having a functional group capable of polymerizing with the above-mentioned olefin in the polyolefin chain, for example, a vinyl group, and one or more amide groups, and one or more A compound having both a glycidyloxy group and / or a glycidyl group, or a compound having at least one amide group and one or more glycidyloxy group and / or a glycidyl group, and other functional groups as well. You may introduce | transduce by graft-polymerizing by the method of. When copolymerized or graft-polymerized with an olefin, the compound represented by the general formula (I):

[0067]

[Chemical 2]

It is also possible to copolymerize a polymerizable vinyl monomer other than the compound represented by or the compound having a functional group.

Further, the modified styrenic polymer (f
11) or modified methacrylate-based polymer (f12) or modified vinyl chloride-based polymer (f13) In order to make the reaction with the functional group more effective, it is introduced into modified olefin-based polymer (f10). As the functional group, a carboxyl group and an acid anhydride group are also preferable, and an acid anhydride group is particularly preferable.

The functional group is a modified styrene polymer (f1
1) or a modified methacrylate-based polymer (f12) or a modified vinyl chloride-based polymer (f13) may be reacted to produce a compatibilizing agent, preferably a functional group in the modified olefin-based polymer (f10). Containing 0.05 to 50% by weight of the monomer portion containing a group, more preferably 0.
Contains 1 to 30% by weight. If it is less than 0.05% by weight, the external appearance (surface layer peeling resistance) will not be improved, and if it exceeds 50% by weight, the fluidity tends to decrease significantly, and the surface properties (surface irregularities, uneven gloss) will deteriorate, and the external appearance will deteriorate. Is damaged.

An example of such a modified olefin polymer is shown below.

As the modified olefin polymer, for example, the following general formula (I):

[0073]

[Chemical 3]

(In the formula, Ar represents an aromatic hydrocarbon group having 9 to 23 carbon atoms and having at least one functional group selected from the group consisting of a glycidyloxy group and a glycidyl group,
R represents a hydrogen atom or a methyl group) and an olefin polymer modified with a compound represented by

More specifically, the modified olefin polymer used in the present invention is obtained by copolymerization of the compound represented by the general formula (I) and the olefin polymer, and the obtained modified olefin polymer is obtained. As per 2 to 1000 repeating units of olefin, the following general formula (II):

[0076]

[Chemical 4]

(In the formula, Ar represents an aromatic hydrocarbon group having 9 to 23 carbon atoms and having at least one functional group selected from the group consisting of a glycidyloxy group and a glycidyl group,
R represents a hydrogen atom or a methyl group) and a modified olefin polymer having one structural unit having a glycidyloxy group and / or a glycidyl group.

The compound represented by the general formula (I) can be produced by the method described in JP-A-60-130580.

That is, the following general formula (III):

[0080]

[Chemical 5]

(Wherein Ar 'represents an aromatic hydrocarbon group having at least one hydroxyl group and having 9 to 23 carbon atoms and R represents a hydrogen atom or a methyl group) and epihalohydrin were added. Then, it can be produced by carrying out a dehydrohalogenation reaction with an alkali.

For example, when 2,6-xylenol N-methylolacrylamide is used as the starting material, the following structural formula (IV):

[0083]

[Chemical 6]

A compound represented by the following formula can be obtained.

The general formula (I) for the above olefin-based polymer
The modified olefin-based polymer produced by radical addition of the compound represented by or copolymerization of the olefin monomer and the compound of the general formula (I) may be a graft copolymer or a block copolymer. Even if it is a combination, it is preferable to have one structural unit having a glycidyloxy group and / or a glycidyl group represented by the general formula (II) per 2 to 1000 repeating units of olefin.

The proportion of general formula (II) that is randomly or graft-copolymerized is such that the number of olefin repeating units is 10
If the number of structural units per 00 is 1 or less, the modification of the olefin polymer is insufficient, and the appearance of the modified vinyl chloride resin and / or modified styrene resin and the olefin resin is improved. The effect is not fully exerted.

The method for producing the copolymer of the olefin polymer and the compound of formula (I) or the compound capable of introducing the selected functional group is not particularly limited, but the following two methods are preferable. Available for

The first production method is a graft modification method of an olefin polymer, and the second production method is a compound having an olefin monomer and a glycidyl group represented by the above general formula (I), or selected. It is a method of copolymerizing a compound capable of introducing a functional group.

The first production method is an olefin polymer and a compound having a glycidyl group represented by the above general formula (I),
Alternatively, a composition composed of two components capable of introducing a selected functional group is prepared by using a radical initiator such as α, α ′-(t-butylperoxy-m-isopropyl) benzene or t-butylperoxybenzoate. To add radicals.

At this time, a solvent which dissolves or swells the olefin polymer, for example, tetralin, decalin, toluene, xylene or chlorobenzene may be used.

Specifically, the olefin polymer and the compound represented by the general formula (I) or the compound capable of introducing a selected functional group are conventionally used in, for example, an extruder, a heating roll, a Brabender, a Banbury mixer and the like. There is a method of melt-kneading using various known blenders.

The second production method is a compound having an olefin monomer and a glycidyl group represented by the above general formula (I),
Alternatively, it is a method of copolymerizing a compound capable of introducing a selected functional group.

The copolymerization method is not particularly limited, but a general radical polymerization method, cationic polymerization method, anion polymerization method, or coordination polymerization method using a transition metal can be used.

The modified olefin polymer produced by radical addition of a compound capable of introducing a functional group to the olefin polymer or copolymerization of an olefin monomer with a compound capable of introducing a functional group is a graft copolymer or block. It may be a copolymer or the like.

Examples of the olefin polymer as a raw material of the modified olefin polymer used in the present invention include homopolymers of various olefin monomers, random copolymers thereof, block copolymers or graft copolymers thereof,
Alternatively, a mixture of these homopolymers or copolymers can be used. For example, high-density polyethylene, medium-density polyethylene, low-density polyethylene, copolymers of ethylene and other α-olefins, polypropylene, copolymers of propylene and other α-olefins, polybutene, poly-4-methylpentene. -1, such as polyolefins or oligomers, ethylene-propylene rubber,
Examples thereof include polyolefin elastomers such as ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer, butyl rubber, butadiene rubber, propylene-butene copolymer, ethylene-acrylic acid ester copolymer, and these alone or in combination. Used in the above combination. Among these, low density polyethylene, polypropylene, propylene and other α
-Copolymers with olefins and their oligomers are preferred, polypropylene, propylene and other α
Copolymers with olefins and their oligomers are particularly preferred.

The three-dimensional structure of this olefin polymer is not particularly limited, but from the viewpoint of heat resistance, the isotactic content is preferably 60% by weight or more, more preferably 70% by weight.
That is all. The number average molecular weight of the olefin polymer is preferably from 500 to 60,000, more preferably from 1,000 to 50,000 from the viewpoint of elastic modulus and appearance. The number average molecular weight is G
It can be measured by PC (gel permeation chromatography).

The modified styrene-based polymer (f11) or modified methacrylate-based polymer (f12) obtained by polymerizing a compound having a functional group reactive with the functional group selected from the modified olefin-based polymer (f10) is A polymer obtained by polymerizing a vinyl compound having a functional group with an aromatic vinyl compound, a vinyl cyanide compound, an alkyl (meth) acrylate compound and / or another vinyl compound copolymerizable therewith. It may be a random copolymer, a block copolymer or a graft copolymer, or a mixture of these copolymers.

The copolymerization method is not particularly limited, but a general radical polymerization method, a cationic polymerization method, an anionic polymerization method, or a coordination polymerization method using a transition metal can be used.

The modified styrene polymer (f11) is a polymer containing an aromatic vinyl compound as a main component (50% by weight or more), and the modified methacrylate polymer (f12) is an alkyl (meth) acrylate compound. Main component (50% by weight
And above).

As the functional group, for example, an epoxy group,
Examples include primary, secondary or tertiary amino group, dimethylamino group, amide group, carboxyl group, acid anhydride group, hydroxyl group and the like, and these are used alone or in combination of two or more kinds. For example, modified olefin polymer (f10)
In order to make the reaction with the glycidyl group introduced in the above more effective, an amino group, a carboxyl group and a hydroxyl group are preferable, and a carboxyl group is particularly preferable.

The modified olefin polymer (f10)
When a carboxyl group and / or an acid anhydride group is introduced into, it is preferably an epoxy group, an amino group, a dimethylamino group and / or a hydroxyl group.

Examples of the compound capable of introducing a functional group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinyl pyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylamide, maleimide, acrylic acid and methacrylic acid. , Maleic acid, maleic anhydride, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-
Examples include hydroxypropyl acrylate.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and examples of the aromatic vinyl compound include styrene, methylstyrene, chlorostyrene and α-methylstyrene, and alkyl (meth) ) Examples of the acrylate compound include methyl methacrylate, ethyl methacrylate, butyl acrylate and the like. The above compounds are used alone or in combination of two or more.

The functional group is a modified olefin polymer (f1
It is sufficient that a compatibilizer can be produced by a reaction with 0),
Preferably, the modified styrene-based polymer (f11) or the modified methacrylate-based polymer (f12) contains 0.05 to 50% by weight of a monomer as a constituent containing a functional group, and more preferably 0.1 to 30% by weight. contains. If it is less than 0.05% by weight, the external appearance (surface layer peeling resistance) is not improved and
If the content is more than wt%, the fluidity tends to be greatly reduced, the surface properties are deteriorated (irregularities on the surface and uneven gloss are generated), and the appearance properties are deteriorated.

Furthermore, the modified styrene polymer (f11)
And the modified methacrylate polymer (f12) has a reduced viscosity of 0.2 to 0.9 dl / g (dimethylformamide solution,
The temperature is preferably 30 ° C. and the concentration is 0.3 g / dl). Within this range, the elastic modulus and appearance of the resin composition of the present invention are improved.

The modified vinyl chloride polymer (f13) obtained by polymerizing a compound having a functional group reactive with the functional group selected in the modified olefin polymer (f10) is a vinyl compound having a functional group and a chloride. A polymer obtained by polymerizing a vinyl compound and / or another vinyl compound copolymerizable therewith, which is a random copolymer, a block copolymer or a graft copolymer of the above vinyl compound, or a copolymer thereof. It can be a mixture of coalesces.

The copolymerization method is not particularly limited, but a general radical polymerization method, a cationic polymerization method, an anionic polymerization method, or a coordination polymerization method using a transition metal can be used.

The modified vinyl chloride polymer (f13) is a polymer containing a vinyl chloride compound as a main component (50% by weight or more).

As the functional group, for example, an epoxy group,
Examples include primary, secondary or tertiary amino group, dimethylamino group, amide group, carboxyl group, acid anhydride group, hydroxyl group and the like, and these are used alone or in combination of two or more kinds. For example, in order to make the reaction with the glycidyl group introduced into the modified olefin polymer (f10) of the present invention more effective, an amino group, a carboxyl group and a hydroxyl group are preferable, and a carboxyl group is particularly preferable. Further, when a carboxyl group and / or an acid anhydride group is introduced into the modified olefin polymer (f10), it is preferably an epoxy group, an amino group, a dimethylamino group and / or a hydroxyl group. .

Examples of the compound capable of introducing a functional group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinyl pyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylamide, maleimide, acrylic acid and methacrylic acid. , Maleic acid, maleic anhydride, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-
Examples include hydroxypropyl acrylate.

The functional group is a modified olefin polymer (f1
It is sufficient that a compatibilizer can be produced by a reaction with 0),
Preferably, the modified vinyl chloride polymer (f13) contains 0.05 to 50% by weight, and more preferably 0.1 to 30% by weight of a functional group-containing monomer as a constituent component. If it is less than 0.05% by weight, the appearance will not be improved and 50% by weight
If it exceeds, the fluidity tends to be greatly reduced, and surface irregularities and uneven surface gloss are generated, and the appearance tends to be degraded.

The modified vinyl chloride polymer (f13) preferably has an average degree of polymerization of 400 to 1500, more preferably 450 to 1500.
1000 is more preferable. When the average degree of polymerization is 400 or more, the elastic modulus and impact resistance are improved, and when it is 1500 or less, the appearance tends to be improved. Modified vinyl chloride polymer (f1
3) comprises a copolymer in which 80% by weight or more of the constituents are modified vinyl chloride, a graft copolymer in which 80% by weight or more of the constituents is modified vinyl chloride, and a modified chlorinated vinyl chloride afterwards. A copolymer as a component is included, and these are used alone or in combination of two or more kinds. Copolymers include ethylene, vinyl acetate, methyl methacrylate,
20% or less of a monovinylidene compound such as butyl acrylate may be contained.

The compatibilizer (F-5) is a modified olefin polymer (f1) obtained by polymerizing a monomer having a functional group.
0) A modified styrene polymer (f11) or a modified methacrylate polymer (f12) obtained by polymerizing 5 to 95% by weight of a monomer having a functional group reactive with the functional group of the monomer having the functional group, or It is a compatibilizer obtained by reacting 95 to 5% by weight of a modified vinyl chloride polymer (f13). Modified olefin polymer (f10) 15 to 85% by weight, modified styrene polymer (f11) or modified methacrylate polymer (f12) or modified vinyl chloride polymer (f13) 85 to 15% by weight, preferably modified Olefin polymer (f10) 25 to 75% by weight, modified styrene polymer (f11) or modified methacrylate polymer (f12) or modified vinyl chloride polymer (f13) 75
-25% by weight is particularly preferred. When the modified olefin polymer (f10) is less than 5% by weight or more than 95% by weight,
The compatibility between the resin compositions of the present invention cannot be improved, and the appearance is significantly deteriorated.

The method for producing the compatibilizer (F-5) is not particularly limited, but the following two methods can be preferably used.

The first production method is a melt-kneading method of the modified olefin polymer (f10) and the modified styrene polymer (f11) or the modified methacrylate polymer (f12) or the modified vinyl chloride polymer (f13). In the second production method, the modified olefin polymer (f10) is added to the modified styrene polymer (f11), the modified methacrylate polymer (f12), or the modified vinyl chloride polymer (f1).
It is a method of graft polymerizing the vinyl compound group constituting 3).

The first production method is, for example, the glycidyl group in the structural unit represented by the general formula (II) in the modified olefin polymer (f10) and the modified styrene polymer (f11) or the modified methacrylate polymer. United (f1
2) or the compound having a reactive functional group with the glycidyl group in the modified vinyl chloride polymer (f13).

At this time, a solvent which dissolves or swells the olefin polymer, for example, tetralin, decalin, toluene, xylene, chlorobenzene and the like may be used.

Specifically, the modified olefin polymer (f
10) and the modified styrene-based polymer (f11) or modified methacrylate-based polymer (f12) or modified vinyl chloride-based polymer (f13) are conventionally used, for example, in an extruder, heating roll, Brabender, Banbury mixer, etc. There is a method of melt kneading at 150 to 250 ° C., preferably 180 to 230 ° C. using various known blenders.

In the second production method, the modified olefin-based polymer (f10) is a vinyl which constitutes the modified styrene-based polymer (f11), the modified methacrylate-based polymer (f12) or the modified vinyl chloride-based polymer (f13). It is a method of graft-polymerizing a group of compounds. The graft polymer is not particularly limited, but a general impregnation polymerization method, a polymerization method using a macromonomer, a radical polymerization method or the like can also be used.

The modified vinyl chloride resin (A) used in the present invention preferably has an average degree of polymerization of 400 to 1500, more preferably 450 to 1000. If the average degree of polymerization is less than 400, the elastic modulus and impact resistance will decrease, and if it exceeds 1500, the appearance and fluidity will tend to deteriorate significantly. The modified vinyl chloride resin (A) is a copolymer in which 80% by weight or more is modified vinyl chloride, a graft copolymer in which 80% by weight or more is modified vinyl chloride, and a copolymer of modified vinyl chloride which has been chlorinated later. Which are used alone or in combination of two or more. The copolymer includes
20% by weight or less of a monovinylidene compound such as ethylene, vinyl acetate, methyl methacrylate and butyl methacrylate may be contained.

The functional group introduced into the modified vinyl chloride resin (A) is, for example, an epoxy group, 1, 2 or 3
Primary amino group, amide group, carboxyl group, acid anhydride group,
Examples thereof include a hydroxyl group, and these are used alone or in combination of two or more. An epoxy group is preferable in order to further improve the compatibility with the olefin resin.

Further, as an agent having an effect of improving the compatibility between the compatibilizing agent and the vinyl chloride resin, the compatibilizing agent (F
-1), (F-2), (F-3) or a functional group reactive with the functional group introduced into (F-5), especially a compatibilizer (F-1), (F-2) , (F-3) or (F-5)
When the functional group introduced into is an epoxy group, functional groups reactive with these, such as amino groups, carboxyl groups and / or hydroxyl groups, are the most preferred combinations.

Examples of the monomer capable of introducing a functional group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinyl pyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylamide, maleimide, acrylic acid, Methacrylic acid, maleic acid, maleic anhydride, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-
Examples include hydroxypropyl acrylate and the like.

The introduction of the functional group may be copolymerization or graft copolymerization and is not particularly limited. The amount of functional group introduced is preferably 0.01 to 10% by weight, and 0.1 to 5% by weight, as a monomer.
Is more preferable.

Examples of the modified styrene resin (B) used in the present invention include polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-α-methylstyrene copolymer, acrylonitrile-methylmethacrylate-styrene-α-methyl. Styrene copolymer, ABS resin, AS resin, MABS resin, MBS
Resin, AAS resin, AES resin, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, acrylonitrile-methylmethacrylate-butadiene-
Styrene-α-methylstyrene copolymer, styrene-maleic anhydride copolymer, styrene-maleimide copolymer, styrene-N-substituted maleimide copolymer, acrylonitrile-styrene-N-substituted maleimide copolymer, acrylonitrile- Butadiene-styrene-β-isopropenylnaphthalene copolymer, acrylonitrile-methyl methacrylate-butadiene-styrene-α-methylstyrene-maleimide copolymer is exemplified, and these are used alone or in combination of two or more. To be

When elastic modulus and impact resistance are required, the rubbery polymer 40 is used as the modified styrene resin (B).
To 90% by weight of 60% by weight of a mixture of one or more compounds selected from vinyl cyanide compounds, aromatic vinyl compounds, alkyl (meth) acrylate compounds and monomers copolymerizable therewith. It is preferable to use a modified styrenic resin containing 0 to 70% by weight of the following graft copolymer.

Examples of the rubber-like polymer include polybutadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR) and butyl acrylate rubber. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and examples of the aromatic vinyl compound include styrene and
Examples include methyl styrene, chlorostyrene, α-methyl styrene, and examples of the alkyl methacrylate compound include methyl methacrylate and ethyl methacrylate. The above polymers and compounds are used alone or in combination of two or more.

As the modified styrene resin (B), those having the following composition are particularly preferable. That is, the composition of the methyl ethyl ketone soluble component contains a vinyl cyanide compound and / or an alkyl (meth) acrylate compound as a copolymerization component in an amount of 10 to 60% by weight, preferably 15% by weight or more, and a reduced viscosity of 0.2 to 0.9. dl / g (dimethylformamide solution, 30 ° C., concentration 0.3 g / dl), more preferably 0.25 to 0.8 dl / g. If the vinyl cyanide compound and / or the alkyl methacrylate compound is less than 10% by weight as a copolymerization component, the peeling resistance to the surface layer is deteriorated and the appearance is impaired. There is a tendency. Also, the reduced viscosity is 0.
If it is less than 2 dl / g, the elastic modulus and impact resistance will be reduced to 0.9.
If it exceeds dl / g, the fluidity tends to decrease, the appearance tends to deteriorate, and the thermal stability during molding tends to deteriorate. When heat resistance is required, the modified styrene-based resin having a content of α-methylstyrene of 30% by weight or more in the composition of the methyl ethyl ketone-soluble component is preferable.

Examples of the functional group to be introduced into the modified styrene resin (B) include an epoxy group, an amino group, an amide group, a carboxyl group, an acid anhydride group, a hydroxyl group and the like, and these may be used alone or in combination of two kinds. Used in the above combination. An epoxy group is preferable in order to further improve the compatibility with the olefin resin. In addition, as the effect of improving the compatibility between the compatibilizing agent and the vinyl chloride resin, the compatibilizing agents (F-1), (F-2), (F-3)
Alternatively, a functional group reactive with the functional group introduced into (F-5), particularly compatibilizer (F-1), (F-2), (F-
When the functional group introduced into 3) or (F-5) is an epoxy group, a functional group reactive with them, such as an amino group, a carboxyl group and / or a hydroxyl group, is the most preferable combination.

Examples of the monomer capable of introducing a functional group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinyl pyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylamide, maleimide, acrylic acid, Methacrylic acid, maleic acid, maleic anhydride, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-
Examples include hydroxypropyl acrylate and the like.

The introduction of the functional group may be copolymerization or graft copolymerization and is not particularly limited. The amount of the functional group introduced is preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight, as a monomer.

The modified vinyl chloride resin (A) and the modified styrene resin (B) do not necessarily have to be both modified, and at least one of them may be modified.

Examples of the olefin resin (C) used in the present invention include high density polyethylene, medium density polyethylene, low density polyethylene, copolymers of ethylene with other α-olefins, polypropylene, propylene and other α. -Copolymer with olefin, polybutene, polyolefins or oligomers such as poly-4-methylpentene-1, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer, butyl rubber, butadiene rubber, Examples include polyolefin elastomers such as propylene-butene copolymers and ethylene-acrylic acid ester copolymers, and polyolefins or modified polyolefin elastomers, which may be used alone or in combination of two or more. Can be Among these, from the viewpoint of elastic modulus and heat resistance, low-density polyethylene, polypropylene, a copolymer of propylene and other α-olefins are preferable, and polypropylene, a copolymer of propylene and other α-olefins are preferable. Especially preferred.

The three-dimensional structure of the olefin resin (C) is not particularly limited, but from the viewpoint of heat resistance, the isotactic content is preferably 60% by weight or more, more preferably 70% by weight or more. The molecular weight of the olefin resin (C) is 5,000 to 100,000 in terms of weight average in terms of elastic modulus and appearance.
0 is preferable, and 10000 to 700000 is more preferable.

The olefin resin (C) contains, for example, an epoxy group, a primary, secondary or tertiary amino group, an amide group, a carboxyl group, an acid anhydride group, a hydroxyl group and the like alone or in combination of two or more functional groups. A modified olefin resin may also be used.

The glass fiber (D) has a fiber diameter of 3 to 50 μm.
m, preferably 5 to 30 .mu.m, and the fiber length is 0.1 to 50 mm, preferably 0.5 to 30 mm. Fiber diameter is less than 3 μm,
When the fiber length is less than 0.1 mm, the elastic modulus is not improved, the fiber diameter exceeds 50 μm, and when the fiber length exceeds 50 mm, the appearance is deteriorated.

As the glass component, glass containing 40% by weight or more of silicon oxide is preferable. Also, a silane compound,
It is more preferable to apply a surface treatment agent such as a borane compound, an epoxy compound or a polymer. Furthermore, from the viewpoint of handling, a bundled one is more preferable.

Talc (E) has an oil absorption of 10 to 50 cc / g,
Preferably 15 to 45 cc / g, average particle size 0.5 to 10 μm,
It is preferably 0.7 to 7 μm. Oil absorption is 10cc /
If it is less than g and the particle size is less than 0.5 μm, the elastic modulus decreases,
If the oil absorption exceeds 50 cc / g and the particle size exceeds 10 μm, the appearance is deteriorated.

[0139] Talc is a magnesium silicate main component, and it is not particularly limited as long as it is purified from talc produced in China, Austria, USA, South Korea, the former Soviet Union, Italy, France, India, Japan and the like. Further, it is preferable that a surface treatment agent is applied in the same manner as the glass fiber.

The resin composition of the present invention comprises a modified vinyl chloride resin (A) and / or a modified styrene resin (B).
1 to 99 parts by weight and 99 to 1 parts by weight of the olefin resin (C), a total of 10 components (A), (B) and (C).
0 to 50 parts by weight of glass fiber (D) and / or talc (E) 1 to 50 parts by weight, and further a compatibilizing agent (F-1)
(F-5) at least one or more compatibilizers in an amount of 0.1 to 50 parts by weight. Each component (A),
The ratio of (B) and (C) is preferably 10 to 99 parts by weight of the (A) component and / or (B) component and 90 to 1 parts by weight of the (C) component, and the (A) component and (or) ( B) ingredient 10
˜70 parts by weight and 90 to 30 parts by weight of component (C) are more preferred.
The ratio of the (A) component to the (B) component is 0 to 100 for the (A) component.
It can be applied in an amount of 100% by weight and 100% by weight of the component (B). That is, the modified vinyl chloride resin (A) or the modified styrene resin (B) alone and the olefin resin (C) may be used.

The glass fiber (D) and / or talc (E) comprises a total of 10 components (A), (B) and (C).
It is 1 to 50 parts by weight, preferably 3 to 40 parts by weight, based on 0 parts by weight. If it is less than 1 part by weight, sufficient improvement in elastic modulus and heat resistance will not be exhibited, and if it exceeds 50 parts by weight, the appearance of the molded product will be significantly deteriorated. The ratio of the component (D) and the component (E) is applicable to 0 to 100% by weight of the component (D) and 100 to 0% by weight of the component (E). That is, the glass fiber (D) or the talc (E) alone may be used.

The compatibilizers (F-1) to (F-5) are used in a total amount of 100 parts by weight of the components (A), (B) and (C).
It is 0.1 to 50 parts by weight, preferably 1 to 25 parts by weight. 0.1
If the amount is less than parts by weight, the appearance (surface layer peeling resistance) is not improved, and if it exceeds 50 parts by weight, the elastic modulus and molding processability are impaired (the appearance is impaired due to poor surface properties).

When the modified vinyl chloride resin (A) is the main component as the compatibilizing agent, (F-1), (F-2)
And / or (F-5) are preferable, and when the modified styrene resin (B) is the main component, (F-3) and / or (F-5) are preferable.

For the polymerization of the modified vinyl chloride resin (A), the modified styrene resin (B), and the olefin resin (C), known polymerization methods can be used.
There are no particular restrictions on the type or operation. After completion of the polymerization, the target powder is obtained by a known method.

Further, the resin composition of the present invention is prepared by blending the powders or pellets obtained by the respective methods by a known method, for example, using a Henschel super mixer or the like, and by using a twin-screw extruder or the like at 150 to 250 ° C. The desired product is obtained, for example, by melt-kneading at preferably 180 to 230 ° C. Further, the resin composition of the present invention is a well-known impact resistance improver, processability improver, antioxidant, heat stabilizer, lubricant, and, if necessary, a UV absorber, a pigment, Antistatic agents, flame retardants, flame retardant auxiliaries and the like can be used in combination. In particular, styrene-based resins, phenolic antioxidants used for olefin-based resins, phosphite-based stabilizers, tin-based stabilizers blended with vinyl chloride-based resins and various fatty acid esters, internal and external lubricants such as waxes, etc. Can be used to improve the performance of the resin composition of the present invention as a resin for injection molding.

Hereinafter, the present invention will be described in more detail with reference to specific examples, but these examples do not limit the present invention. In the examples, "part" means part by weight and "%" means% by weight.

Examples 1 to 9 and Comparative Examples 1 to 3 Modified vinyl chloride resins (A-1 to A-2) having the composition shown in Table 1 polymerized by a known suspension polymerization method, and olefins shown in Table 3 Resins (C-1 to C-2), compatibilizers (F-1 to F-5) shown in Table 4, stabilizers (dibutyltin maleate)
Glass fiber (D) with 2 parts and fiber diameter of 13 μm and length of 3 mm
And talc (E) with an oil absorption of 35 cc / g and an average particle size of 3 μm were blended in a composition ratio shown in Table 5 using a Henschel mixer, and these components were melted at 160 to 210 ° C with a twin-screw extruder. The resin composition was pelletized by kneading and pelletizing.

Examples 10 to 12 and Comparative Examples 4 to 6 Modified styrene resins (B-1 to B-2) having the composition shown in Table 2 polymerized by a known emulsion polymerization method, and olefin resins shown in Table 3 (C-2), a compatibilizer (F-3) shown in Table 4, a glass fiber (D) having a fiber diameter of 13 μm and a length of 3 mm, and an oil absorption of 35 cc / g, and a talc (E) having an average particle diameter of 3 μm are shown in the table. Blend with a Henschel mixer at the composition ratio shown in 6,
Using a twin-screw extruder, these components were melt-kneaded at 200 to 250 ° C. and pelletized to obtain resin composition pellets.

Examples 13 to 15 and Comparative Examples 7 to 9 Modified vinyl chloride resins (A-1, A) having the compositions shown in Table 1
-3), the modified styrenic resin (B-1, B shown in Table 2)
-3), modified olefin resin (C-2) shown in Table 3,
Compatibilizer (F-1), stabilizer (dibutyltin malate)
Glass fiber (D) with 2 parts and fiber diameter of 13 μm and length of 3 mm
And talc (E) with an oil absorption of 35 cc / g and an average particle size of 3 μm were blended in a composition ratio shown in Table 7 using a Henschel mixer, and these components were melted at 170 to 220 ° C. with a twin-screw extruder. The resin composition was pelletized by kneading and pelletizing.

The reduced viscosity was measured by the following method.

(Reduced viscosity) A styrene resin was dissolved in N, N-dimethylformamide to a concentration of 0.3 g / dl to give a polymer solution, and a Ubbelohde viscometer (at 30 ° C according to JIS-K6721) was used. The transit time (t) was measured using a capillary viscosity automatic measuring device manufactured by Shibayama Chemical Equipment Co., Ltd. On the other hand, for the solvent N, N-dimethylformamide, the passage time at 30 ° C. (t
_o ) was measured, and the reduced viscosity (η _red ) was calculated by the following formula.

Η _red = (t / t ₀ -1) / C where C means the concentration (g / dl) of the polymer solution.

[0153]

[Table 1]

[0154]

[Table 2]

[0155]

[Table 3]

[0156]

[Table 4]

[0157]

[Table 5]

[0158]

[Table 6]

[0159]

[Table 7]

Next, using the pellets prepared by the above-mentioned method, the nozzle temperature was changed by using a 5 ounce injection molding machine in Examples 1-9, 13-15 and Comparative Examples 1-3, 7-9.
180 ° C., Examples 10 to 12 and Comparative Examples 4 to 6 were set to 230 ° C., and test pieces required for the following tests were molded.

Various physical properties of each test piece were measured according to the methods described below. The results are shown in Table 8.

[0162]

[Table 8]

The appearance of the molded product was evaluated by evaluating a flat plate molded product having a thickness of 2.5 mm. The evaluation was carried out by a visual 5-point method as follows, the highest being 5 points and the lowest being 1 point.

5 points: Non-defective product 4 points: Surface gloss unevenness is a little 3 points: Surface gloss unevenness is a little or surface irregularity is a little 2 points: Surface gloss unevenness is a surface unevenness, or surface peeling is a little 1 point: Surface layer With peeling, that is, the larger the number, the better the appearance.

The flexural modulus was evaluated using an autograph based on the ASTM D-790 standard (23 ° C, unit:
kg / cm ² ).

The heat distortion temperature was evaluated by the HDT test under a load of 18.6 kg / cm ² based on the ASTM D-648 standard (unit: ° C).

..

From the results shown in Table 8, it can be seen that the resin composition of the present invention is excellent in elastic modulus, heat resistance and appearance.

[0169]

INDUSTRIAL APPLICABILITY The resin composition of the present invention has excellent elasticity, heat resistance and appearance, and is extremely useful as a resin composition for injection molding.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Reference number within the agency FI Technical display location C08K 7/14 KFT 7242-4J C08L 23/08 LDJ 7107-4J 23/16 LCY 7107-4J 25/00 LDS 9166 -4J LDW 9166-4J 27/06 LEP 9166-4J LFA 9166-4J 51/06 LLE 7142-4J 53/00 LLY 7142-4J

Claims (39)

[Claims] 1. (A) Modified vinyl chloride resin and / or (B) Modified styrene resin 1 to 99 parts by weight and (C)
(D) glass fiber and / or () for 100 parts by weight of resin consisting of 99 to 1 parts by weight of olefin resin
(E) 1 to 50 parts by weight of talc, (F-1): (f1) 25 to 70 parts by weight of one or more ethylene-propylene-diene rubbers, (f2) one or more kinds of ethylene-vinyl acetate copolymer 25 to 70 parts by weight, (f
3) 0 to 25 parts by weight of one or more rubber-like polymers and / or olefin polymers and (f4) 1 to 50 parts by weight of one or more functional group-containing rubber-like polymers and / or olefin polymers Parts, at least one ethylene-propylene-diene rubber (f1), at least one ethylene-vinyl acetate copolymer (f2), at least one rubber-like polymer and / or olefin polymer (f3), and A compatibilizing agent in which the total amount of the one or more functional group-containing rubber-like polymer and / or the olefin polymer (f4) is 100 parts by weight, (F-2): (f1) one or more ethylene-propylene. 25-70 parts by weight of diene rubber, (f2) 25-70 parts by weight of one or more ethylene-vinyl acetate copolymers and (f3) one or more rubbery polymers and / or olefins From 0 to 25 parts by weight of polymer, one or more ethylene-propylene-diene rubber (f1), one or more ethylene-vinyl acetate copolymer (f2) and one or more rubbery polymer and / or olefin system A polymer mixture in which the total amount of the polymer (f3) is 100 parts by weight, and 0.05 to 50% by weight of a monomer group containing the (f5) functional group.
And 50 to 99.95% by weight of monomers that can be copolymerized with these
A compatibilizer which is a graft polymer composed of 5 to 200 parts by weight of a monomer group consisting of (F-3): (f6) functional group-containing styrene polymer part 5
To 95% by weight and (f7) a styrene polymer, an alkyl (meth) acrylate polymer and / or a vinyl chloride polymer in a polymer portion of 95 to 5% by weight. Compatibilizer, (F-4): Block 5 of (f8) olefin polymer
~ 95% by weight and (f9) styrene polymer block 95 ~
The amount of the compatibilizing agent which is a block copolymer composed of 5% by weight and (F-5): (f10) a functional group-containing monomer is 0.05.
To 95% by weight of a modified olefin polymer polymerized to contain 50% by weight to 0.05% of a monomer having a functional group reactive with the functional group of the monomer having the functional group.
To 50% by weight of (f11) modified styrene polymer, (f12) modified methacrylate polymer or (f13) modified vinyl chloride polymer
1 selected from the group consisting of compatibilizing agents consisting of 5% by weight
A resin composition containing 0.1 to 50 parts by weight of one or more compatibilizers. 2. The resin composition according to claim 1, wherein the modified vinyl chloride resin (A) has an average degree of polymerization of 400 to 1500. 3. The modified vinyl chloride resin (A) is (F-
1) A vinyl chloride resin containing a functional group reactive with a functional group in a compatibilizer selected from the group consisting of (F-2), (F-3) and (F-5). Item 3. The resin composition according to Item 1 or 2. 4. The resin composition according to claim 1 or 2, wherein the modified vinyl chloride resin (A) is a vinyl chloride resin containing a functional group reactive with an epoxy group. 5. The resin composition according to claim 1, wherein the modified vinyl chloride resin (A) is a vinyl chloride resin containing an epoxy group. 6. The resin composition according to claim 1, wherein the modified vinyl chloride resin (A) is a vinyl chloride resin containing a carboxyl group, an amino group or a dimethylamino group. 7. The composition of the modified ethylenic resin (B) soluble in methyl ethyl ketone contains 10 to 60% by weight of a vinyl cyanide compound and / or an alkyl (meth) acrylate compound as a copolymerization component, and has a reduced viscosity. Is 0.2 to 0.
9 dl / g (dimethylformamide solution, 30 ° C, concentration 0.3
g / dl), The resin composition according to claim 1, 2, 3, 4, 5 or 6. 8. The modified styrenic resin (B) is one or more compounds selected from vinyl cyanide compounds, aromatic vinyl compounds and alkyl (meth) acrylate compounds with respect to 40 to 90% by weight of a rubber-like polymer. And 0 to 70% by weight of a graft copolymer obtained by polymerizing 60 to 10% by weight of a mixture of monomers copolymerizable therewith.
The resin composition according to 2, 3, 4, 5, 6 or 7. 9. The composition of the modified styrene resin (B) having a methyl ethyl ketone soluble content, wherein the α-methyl styrene content is 30% by weight or more.
The resin composition according to 6, 7, or 8. 10. The modified styrene resin (B) is (F-
1. A styrene-based resin containing a functional group reactive with a functional group in a compatibilizer selected from the group consisting of 1), (F-2), (F-3) and (F-5). 1,
The resin composition according to 2, 3, 4, 5, 6, 7, 8 or 9. 11. The modified styrenic resin (B) is a styrenic resin containing a functional group reactive with an epoxy group, 1, 2, 3, 4, 5, 6, 7, 8, 9 Or
The resin composition according to 10. 12. The modified styrene-based resin (B) is a styrene-based resin containing an epoxy group,
The resin composition according to 3, 4, 5, 6, 7, 8, 9 or 10. 13. The modified styrene resin (B) is a styrene resin containing a carboxyl group, an amino group or a dimethylamino group, 1, 2, 3, 4, 5,
The resin composition according to 6, 7, 8, 9 or 10. 14. The olefinic resin (C) is a propylene polymer, 1, 2, 3, 4, 5, 6, 7,
The resin composition according to 8, 9, 10, 11, 12 or 13. 15. The weight average molecular weight of the olefin resin (C) is from 5000 to 100,000,
The resin composition according to 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14. 16. One or more functional group-containing rubbery polymers and / or olefinic polymers (f4) are one or more epoxy group-containing rubbery polymers and / or olefinic polymers 1 to 50 parts by weight.
4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15
The resin composition described. 17. One or more rubber-like polymers and / or olefin polymers (f3) are styrene-butadiene rubber, styrene-butadiene-block copolymer, acrylonitrile-butadiene rubber, polybutadiene rubber, isobutylene rubber, butyl rubber. And at least one selected from the group consisting of polyolefins and polyolefins. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 1.
The resin composition according to 2, 13, 14, 15 or 16. 18. A modified styrene-butadiene rubber in which at least one functional group-containing rubber-like polymer and / or olefin polymer (f4) respectively contains a functional group,
6. At least one selected from the group consisting of a modified styrene-butadiene-block copolymer, a modified acrylonitrile-butadiene rubber, a modified polybutadiene rubber, a modified isobutylene rubber, a modified butyl rubber and a modified polyolefin. , 6, 7, 8,
The resin composition according to 9, 10, 11, 12, 13, 14, 15 or 17. 19. A modified styrene-butadiene rubber, a modified styrene-butadiene-block copolymer, wherein one or more functional group-containing rubbery polymers and / or olefinic polymers (f4) each contain an epoxy group.
At least one selected from the group consisting of modified acrylonitrile-butadiene rubber, modified polybutadiene rubber, modified isobutylene rubber, modified butyl rubber, and modified polyolefin, claims 1, 2, 3, 4, 5, 6, 7,
The resin composition according to 8, 9, 10, 11, 12, 13, 14, 15 or 17. 20. Modified styrene-butadiene, wherein one or more functional group-containing rubbery polymer and / or olefin polymer (f4) are grafted with a functional group-containing compound and / or a functional group-containing polymer, respectively. At least one selected from the group consisting of rubber, modified styrene-butadiene-block copolymer, modified acrylonitrile-butadiene rubber, modified polybutadiene rubber, modified isobutylene rubber, modified butyl rubber and modified polyolefin.
The species 1, 2, 3, 4, 5, 6, 7, 8, 9,
The resin composition according to 10, 11, 12, 13, 14, 15 or 17. 21. A modified styrene-butadiene rubber or a modified styrene-butadiene block in which one or more functional group-containing rubber-like polymers and / or olefin-based polymers (f4) are each grafted with an epoxy group-containing polymer. Copolymer, modified acrylonitrile-butadiene rubber, modified polybutadiene rubber, modified isobutylene rubber,
4. At least one selected from the group consisting of modified butyl rubber and modified polyolefin.
The resin composition according to 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 17. 22. One or more rubber-like polymers and / or olefin polymers (f3) have an affinity for the modified vinyl chloride resin (A) and / or the modified styrene resin (B), respectively. Styrene-butadiene rubber, styrene-butadiene-block copolymer, acrylonitrile-butadiene rubber, polybutadiene rubber, isobutylene rubber grafted with polymethylmethacrylate, styrene-acrylonitrile copolymer or styrene-methylmethacrylate copolymer having
At least one selected from the group consisting of butyl rubber and polyolefins, 1, 2, 3, 4, 5,
6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 1
The resin composition according to 8, 19, 20 or 21. 23. The functional group-containing monomer group in the compatibilizer (F-2) is a monomer group containing one or more epoxy groups. 5, 6, 7,
The resin composition according to 8, 9, 10, 11, 12, 13, 14 or 15. 24. The copolymerizable monomer group in the compatibilizer (F-2) is an aromatic vinyl compound, a vinyl cyanide compound, an alkyl (meth) acrylate compound, a halogenated vinyl compound, an olefin compound or the like. At least one selected from the group consisting of other vinyl compounds copolymerizable with
The resin composition according to 7, 8, 9, 10, 11, 12, 13, 14, 15 or 23. 25. A functional group-containing styrene polymer part (f
6) is obtained by polymerizing 50% by weight or more of an aromatic vinyl compound, 1, 2, 3, 4, 5, 6, 7, 8, 9,
The resin composition according to 10, 11, 12, 13, 14 or 15. 26. A functional group-containing styrene polymer part (f6)
80% by weight or more of the aromatic vinyl compound polymerized as a monomer in styrene, methylstyrene, α
-Methylstyrene and / or β-isopropylnaphthalene, 1, 2, 3, 4, 5, 6, 7,
The resin composition according to 8, 9, 10, 11, 12, 13, 14 or 15. 27. The styrene-based polymer of the polymer portion (f7) comprises 15 to 40% by weight of a vinyl cyanide compound, 50 to 85% by weight of an aromatic vinyl compound, and 0 to another vinyl compound copolymerizable therewith. 20% by weight of a copolymerized product, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 1
The resin composition according to 3, 14, 15 or 26. 28. The alkyl (meth) of the polymer part (f7).
The acrylate-based polymer contains 60% by weight or more of methyl methacrylate as a constituent component.
4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15
The resin composition described. 29. The oxygen content of the epoxy group in the compatibilizer (F-3) is 0.03 to 5% by weight.
2,3,4,5,6,7,8,9,10,11,12,13,14
Or the resin composition according to item 15. 30. An olefin polymer block (f
8) has a number average molecular weight of 1,000 to 50,000.
2,3,4,5,6,7,8,9,10,11,12,13,14
Or the resin composition according to item 15. 31. Styrenic polymer block (f9)
Is 3 to 40% by weight of a vinyl cyanide compound, 35 to 85% by weight of an aromatic vinyl compound, and 50 to 0% by weight of an alkyl (meth) acrylate compound as constituent components. 5, 6, 7, 8, 9, 1
The resin composition according to 0, 11, 12, 13, 14, 15 or 30. 32. Styrenic polymer block (f9)
Has a reduced viscosity of 0.2 to 0.9 dl / g (dimethylformamide solution, 30 ° C., concentration of 0.3 g / dl).
3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15
Or the resin composition according to 31. 33. Modified olefin polymer (f10)
Is a modified olefin polymer having one structural unit having at least one amide group and at least one functional group selected from the group consisting of a glycidyloxy group and a glycidyl group per 2-1000 repeating units of olefin. Claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,
The resin composition according to 11, 12, 13, 14 or 15. 34. Modified olefin polymer (f10)
Is represented by the general formula (I): (In the formula, Ar represents an aromatic hydrocarbon group having 9 to 23 carbon atoms and having at least one functional group selected from the group consisting of a glycidyloxy group and a glycidyl group, and R represents a hydrogen atom or a methyl group). An olefin polymer modified with a compound represented by Claims 1, 2, 3, 4, 5,
The resin composition according to 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15. 35. The modified styrene-based polymer (f11), modified methacrylate-based polymer (f12) or modified vinyl chloride-based polymer (f13) is modified with a compound having a carboxyl group. 3, 4, 5,
6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 33 or 34
The resin composition described. 36. The functional group contained in the modified olefin polymer (f10) is a carboxyl group and / or
An acid anhydride group, Claims 1, 2, 3, 4, 5, 6, 7,
The resin composition according to 8, 9, 10, 11, 12, 13, 14 or 15. 37. The functional group contained in the modified styrene polymer (f11), modified methacrylate polymer (f12) or modified vinyl chloride polymer (f13) is an epoxy group, an amino group, a dimethylamino group or (Or) a hydroxyl group, claims 1, 2, 3, 4, 5, 6,
The resin composition according to 7, 8, 9, 10, 11, 12, 13, 14, 15 or 36. 38. The glass fiber (D) has a fiber diameter of 3 to 50.
Glass fiber having a fiber length of 0.1 to 50 mm and a fiber length of 0.1 to 50 mm.
3, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 2
The resin composition according to 5, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36 or 37. 39. Talc (E) has an oil absorption of 10 to 50 cc /
g, talc having an average particle size of 0.5 to 10 μm.
2,3,4,5,6,7,8,9,10,11,12,13,1
4, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 2
The resin composition according to 6, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38.