JPH0737554B2 - Impact resistant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION “Industrial field of application” The present invention relates to an impact resistant resin composition. More specifically, a thermoplastic resin (AAS resin) obtained by graft-polymerizing an aromatic vinyl monomer or the like on an acrylic rubber produced by adjusting the refractive index by the seeded emulsion polymerization method,
The present invention relates to an impact resistant resin composition containing an ethylene / propylene / non-conjugated diene / styrene copolymer (AES resin) and having excellent colorability and surface gloss.

"Prior Art" Conventionally, it is well known that a hard resin is mixed with rubber to obtain an impact resistant resin reinforced by the rubber. ABS resin is a typical one of this type, but a diene rubber is mainly used as a rubber component of a base. Due to the poor weather resistance of this base rubber, ABS resin based on diene rubber is restricted in outdoor use,
This is the biggest drawback of this resin.

From such a point of view, use of a base rubber other than a diene rubber has been considered, and various examples of using a saturated rubber having good weather resistance have been proposed. Acrylate rubber-like polymers (hereinafter referred to as acrylic rubbers) and ethylene / propylene / non-conjugated diene copolymer rubbers (hereinafter referred to as EPDM) are often used as these examples.

However, a resin having satisfactory properties cannot be obtained by simply substituting an acrylic rubber as a base rubber for a diene rubber of an ABS resin as a base rubber and performing graft polymerization.
Certainly, compared with ABS resin based on diene rubber, it is greatly improved in terms of weather resistance, but there are problems with resin colorability, surface gloss of molded products and impact strength, It is hard to say that it is satisfactory.

A rubber-resin two-component resin reinforced with an acrylic rubber or the like is usually produced by graft-polymerizing a latex-like rubber component with a monomer mixture forming a branch component of a graft copolymer. Compared with diene rubber, acrylic rubber used as a rubber component with good weather resistance has a small optical refractive index, is softer and has a low elastic modulus, and has a drawback of slow elastic recovery and easy plastic deformation. have. When such a soft acrylic rubber having a small refractive index is used to produce a rubber-resin two-component resin and a molding material such as injection molding is carried out, the base rubber and the branch component of the graft copolymer are produced. The difference in the refractive index between the resin and the diluent resin used in the graft copolymer is large, and the deformation and orientation of the rubber particles are significant. Is diffusely reflected and the appearance becomes whitish, and it becomes difficult to express the depth of color (saturation), especially when coloring, so that the commercial value tends to decrease.

In such molded products, the color of the molding surface and the mechanical strength such as impact strength greatly differ depending on the flow direction at the time of molding and the location of the molded product. It has the drawback of causing defects.

Further, EDPM cannot be usually produced by an emulsion radical polymerization method and is produced by a solution-type coordinated anionic polymerization method. Therefore, it is a technical idea to obtain a latex-like water-dispersed rubber having a rubber particle diameter of about 0.5 μm or less. Extremely economically and economically For this reason, it is difficult to carry out the graft polymerization reaction by using the emulsion polymerization method, and as a rubber-resin two-component resin, a material having a rubber particle distribution suitable for impact resistance and a rubber component content cannot be obtained. However, it was a drawback of AES resin.

“Problems to be Solved by the Invention” The present inventors have solved the above-mentioned various drawbacks existing in a conventional rubber-resin two-component resin using an acrylic rubber or EPDM as a base rubber. As a result of intensive studies, the present invention has been achieved. That is, first, a two-step polymerization reaction is carried out by the seeded emulsion polymerization method to change the refractive index to produce an acrylic rubber,
Further, by a two-step graft polymerization reaction, an acrylonitrile / acrylic rubber / styrene copolymer (AAS resin) in which the refractive index and the rubber particle diameter are adjusted to specific ranges is produced,
Next, this resin was added to acrylonitrile / EPDM / styrene copolymer (AES resin) and acrylonitrile / styrene copolymer (AS resin) with rubber particle diameter adjusted to a specific range.
It is intended to provide an impact-resistant resin composition having good molding processability and weather resistance, and having excellent colorability and surface gloss, by blending and with a specific proportion.

"Means for Solving Problems" The gist of the present invention is that the alkyl group has 1 to 1 carbon atoms.
8 to 100% by weight of alkyl acrylate monomer, vinyl monomer 0 to 0
A monomer mixture consisting of 30% by weight and 0 to 5% by weight of a polyfunctional vinyl monomer (however, the total amount of the monomer mixture is 100% by weight) is emulsion-polymerized to give a rubber particle diameter of 0.03. μ
a first step of producing acrylic seed rubber particles having a size of m to less than 0.15 μm, 1 part by weight of the acrylic seed rubber particles obtained in the first step as a seed, and an alkyl acrylate having 1 to 8 carbon atoms of an alkyl group Monomer 20 to 94.9% by weight, the refractive index of a single polymer
A monomer mixture consisting of 5 to 79.9% by weight of a vinyl monomer copolymerizable with the above-mentioned alkyl acrylate of 1.50 or more and 0.1 to 5% by weight of a polyfunctional vinyl monomer (however, the monomer mixture is 100% by weight in total). 2.5 to 125 parts by weight is added, and the rubber particle diameter is 0.15 to 0.5 by the seed emulsion polymerization method.
Second step of producing an acrylic rubber having a thickness of μm, 100 parts by weight of the acrylic rubber obtained in the second step,
Aromatic vinyl monomer 0 to 80% by weight, vinyl cyanide monomer 0 to 40% by weight, vinyl monomer copolymerizable with the above aromatic vinyl monomer whose refractive index of a single polymer is less than 1.50 Body 0
A monomer mixture consisting of 99.9% by weight and 0.1 to 5% by weight of a polyfunctional vinyl monomer (however, the total amount of the monomer mixture is 10%).
It is 0% by weight. ) Addition of 10 to 100 parts by weight and a cross-linking graft reaction by a seeded emulsion polymerization method, a third step, a polymerization system after the third step is further added, 10 to 90% by weight of an aromatic vinyl monomer, and cyan. Grafting is performed by adding 55 to 185 parts by weight of a monomer mixture consisting of 10 to 40% by weight of vinyl chloride monomer and 0 to 80% by weight of methyl methacrylate (however, the total amount of the monomer mixture is 100% by weight). Fourth step of polymerization, graft copolymer resin (A) obtained by, ethylene / propylene, non-conjugated diene copolymer rubber (EP
DM) 100 parts by weight, aromatic vinyl monomer 10 to 90% by weight,
20 to 2000 parts by weight of a monomer mixture consisting of 10 to 40% by weight of vinyl cyanide monomer and 0 to 80% by weight of methyl methacrylate (however, the total amount of the monomer mixture is 100% by weight) is added, The rubber particle size obtained by graft polymerization is 0.5 to
Graft copolymer resin (B) having a thickness of 5 μm, aromatic vinyl monomer 10 to 90% by weight, vinyl cyanide monomer
Monomer mixture consisting of 10 to 40% by weight and methyl methacrylate 0 to 80% by weight (however, the total monomer mixture is
100% by weight. And a copolymer resin (C) obtained by polymerizing the above), and an impact-resistant resin composition.

Hereinafter, the present invention will be described in detail.

The graft copolymer resin (A) constituting the resin composition according to the present invention is produced through the first step, the second step, the third step and the fourth step described below. The graft copolymer resin (A) is a kind of acrylonitrile / acrylic rubber / styrene copolymer (AAS resin), and is a weather resistant and impact resistant resin having excellent coloring properties and surface gloss.

The first step for producing the graft copolymer (A) in the present invention is a step for producing acrylic seed rubber particles in the seed emulsion polymerization. The acrylic seed rubber particles produced in the first step are first added to the emulsion polymerization system during the production of the acrylic rubber and serve as seeds for producing an acrylic rubber having a large rubber particle diameter.

The acrylic seed rubber particle in the present invention means an alkyl acrylate monomer having an alkyl group having 1 to 8 carbon atoms 70 to 100
% By weight, 0 to 30% by weight of a vinyl monomer copolymerizable with the above alkyl acrylate, and 0 a multifunctional vinyl monomer.
˜5% by weight of the monomer mixture (however, the total amount of the monomer mixture is 100% by weight; the same applies hereinafter) (I) is produced by emulsion polymerization and has a rubber particle size of 0.03 μm to 0.15 μm.
Less than.

The alkyl acrylate monomer, which is a constituent of the acrylic seed rubber particles, refers to an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group. Specific examples thereof include alkyl acrylates such as ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. These may be one kind or a mixture of two or more kinds.

The monomer mixture (I) used for the production of the acrylic seed rubber particles contains the alkyl acrylate monomer in an amount of 70 to 100.
Must be contained in the range of wt%. When the content is less than 70% by weight, the rubber elasticity of the seed rubber particles becomes small, and the affinity with the acrylic rubber layer formed on the outer layer of the seed rubber particles decreases, which is not preferable.

Examples of the vinyl monomer copolymerizable with the alkyl acrylate include aromatic vinyl monomers described below, vinyl cyanide monomers described below, acrylamide, methacrylamide, vinylidene chloride, alkyl vinyl ethers, alkyl vinyl esters, and alkyl methacrylates. And halogen-substituted compounds thereof. These may be one kind or a mixture of two or more kinds.

The amount of the copolymerizable vinyl monomer contained in the monomer mixture (I) must be selected in the range of 0 to 3% by weight. If the copolymerizable vinyl monomer exceeds 30% by weight, it is not preferable that the properties of the seed rubber particles deteriorate.

The polyfunctional vinyl monomer in the present invention refers to a vinyl monomer containing two or more vinyl groups in one molecule of the monomer in order to crosslink the acrylic seed rubber particles. Specific examples of the polyfunctional vinyl monomer include divinylbenzene,
Aromatic polyfunctional vinyl monomers such as divinyltoluene, methacrylates and acrylates of polyhydric alcohols such as ethylene glycol dimethacrylate, trimethylolpropane triacrylate, diallylmaleate, triallyl isocyanurate, diallyl phthalate, and allyl methacrylate. can give. These are 1 or 2
It may be a mixture of two or more species.

The amount of the polyfunctional vinyl monomer contained in the monomer mixture (I) must be selected in the range of 0 to 5% by weight. If this polyfunctional vinyl monomer exceeds 5% by weight,
It is not preferable because the compatibility and affinity with the acrylic rubber layer formed in the outer layer becomes poor and the various properties of the seed rubber particles deteriorate.

Acrylic seed rubber particles in the present invention, in the known emulsion polymerization using water as a medium, appropriately combine various kinds of known conditions such as the type and amount of the emulsifier and the polymerization catalyst, the addition method thereof, and the addition method of the monomer. Can be manufactured.

The acrylic seed rubber particles should have a rubber particle size of 0.03 μm to less than 0.15 μm. Rubber particle size is 0.
If it is smaller than 03 μm, it cannot be produced by the usual emulsion polymerization method, and the emulsifier concentration becomes high, which is not economical. If the rubber particle size is 0.15 μm or more, the composition and refractive index of the acrylic rubber produced in the second step cannot be optimized, and an impact resistant resin having excellent coloring properties and surface gloss can be obtained. It cannot be manufactured.

Rubber particles such as acrylic rubber dispersed in water in the present invention
The diameter is the Coulter Electronic Co.
s Ltd. Nanosizer (Coulter  Nano-Sizer^TM) To
Measured with a system in which latex was dispersed in water at 23 ° C.
It also means the weight average rubber particle size.

In the second step for producing the graft copolymer resin (A) in the present invention, an acrylic rubber is produced by the seed emulsion polymerization method. In the second step, an acrylic rubber having a higher refractive index than that of a conventional acrylic rubber can be obtained by copolymerizing a monomer having a high refractive index.

The acrylic rubber in the present invention is obtained by using 1 part by weight of the acrylic seed rubber particles obtained in the first step as a seed, and an alkyl acrylate monomer having an alkyl group having 1 to 8 carbon atoms.
94.9% by weight, a vinyl monomer 5 to 7 copolymerizable with the above alkyl acrylate having a refractive index of 1.50 or more as a single polymer
9.9% by weight, and 0.1-5% by weight of multifunctional vinyl monomer
2.5 to 125 parts by weight of a monomer mixture (II) consisting of
Produced by the seeded emulsion polymerization method, the rubber particle size is 0.15 to 0.
It means that it is 5 μm.

Examples of the alkyl acrylate monomer which is a constituent component of the acrylic rubber include the alkyl acrylate monomers exemplified above as the constituent component of the acrylic seed rubber particles. These may be one kind or a mixture of two or more kinds. The monomer mixture (II) used for the acrylic rubber contains 20 to 94.9% of the alkyl acrylate monomer.
It is contained in the range of% by weight. When the content is less than 20% by weight, the rubber elasticity of the acrylic rubber becomes small, which is not preferable. Further, the content of the alkyl acrylate monomer does not exceed 94.9% by weight because the monomer mixture (II) contains other components.

A vinyl monomer that is a constituent of this acrylic rubber and has a refractive index of a single polymer that is copolymerizable with the above alkyl acrylate having a refractive index of 1.50 or higher is a polymer obtained by homopolymerizing this vinyl monomer. Having a refractive index of 1.50 or more. As the vinyl monomer copolymerizable with the alkyl acrylate having a refractive index of 1.50 or more of the single polymer,
Examples thereof include butadiene, vinyl chloride, vinylidene chloride, acrylonitrile, vinylnaphthalene, vinylcarbazole, styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, dichlorostyrene, cyclohexyl methacrylate and benzyl methacrylate. These may be one kind or a mixture of two or more kinds.

The amount of the vinyl monomer component copolymerizable with the alkyl acrylate having a refractive index of the homopolymer of 1.50 or more to be contained in the monomer mixture (II) should be selected in the range of 5 to 79.9% by weight. I have to. If the amount of the copolymerizable vinyl monomer component is less than 5% by weight, the refractive index of the resulting acrylic rubber becomes small and the difference in the refractive index between the branch component of the graft copolymer and the diluting resin is small. It becomes large, which is not preferable. The copolymerizable vinyl monomer component does not exceed 79.9% by weight because the monomer mixture (II) contains other components.

In the present invention, the refractive index means that measured according to JIS K 7105-1981 using an Abbe refractometer at a D line of 23 ° C. Na.

The acrylic rubber in the present invention contains the polyfunctional vinyl monomer component exemplified above as the constituent component of the acrylic seed rubber particles. This polyfunctional vinyl monomer is used in the monomer mixture (II) used in the seed emulsion polymerization of acrylic rubber.
It must be contained in the range of 1 to 5% by weight. When the content is less than 0.1% by weight, the acrylic rubber becomes soft and has fluidity, which is not preferable. When the content of the polyfunctional vinyl monomer exceeds 5% by weight, the rubber elasticity is lost,
It becomes hard, which is not preferable.

The acrylic rubber in the present invention is produced by adding the monomer mixture (II) in an amount of 2.5 to 125 parts by weight to 1 part by weight of the acrylic seed rubber particles and by a seed emulsion polymerization method. If the amount of the monomer mixture (II) is less than 2.5 parts by weight, the rubber particle size of the acrylic rubber does not increase to the target rubber particle size and a layer having a sufficient thickness cannot be formed, which is not preferable. When the amount of the monomer mixture (II) is more than 125 parts by weight, it takes time to polymerize by the seed emulsion polymerization method, which is not economical.

In this seed emulsion polymerization of acrylic rubber, polymerization is initiated by adding the monomer mixture (II), a polymerization initiator and the like to a seed polymerization system containing latex-like acrylic seed rubber particles. At this time, it is preferable to appropriately divide the monomer mixture (II), the emulsifier, the polymerization initiator and the like according to the polymerization rate of the seeding polymerization, and add them over time. Further, the additive composition of the monomer mixture (II) can be appropriately changed, for example, from the initial stage to the latter stage of the polymerization reaction to increase the refractive index sequentially from the inner layer to the outer layer of the acrylic rubber, thereby increasing the acrylic rubber. It is possible to improve the appearance of the molded product by making the refractive index of the rubber base and the graft copolymer branch component approximate to each other without lowering the reinforcing effect.

The rubber particle diameter of the acrylic rubber in the present invention is 0.15 to
Adjust within the range of 0.5 μm. If the rubber particle size of the acrylic rubber is smaller than 0.15 μm, the impact resistance of the graft copolymer cannot be improved, which is not preferable. 0.5μ
If it is larger than m, the polymerization takes too long and is not economical.

In the third step for producing the graft copolymer resin (A) in the present invention, the acrylic rubber is subjected to a cross-linking graft reaction by a seed emulsion polymerization method. The hard cross-linked graft copolymer formed in the third step covers the acrylic rubber produced in the second step and is between the acrylic rubber and the diluting resin and has a low refractive index. Approximate the refractive index with a diluting resin having a high refractive index.
As a result, it is possible to reduce defective phenomena such as pearly luster and defective coloring that appear in the appearance of the molded product of the graft copolymer.

In the cross-linking graft reaction in the third step of the present invention, 100 parts by weight of the acrylic rubber obtained in the second step is added to 0 to 80% by weight of an aromatic vinyl monomer and 0 to 40% of a vinyl cyanide monomer. 0 to 9% by weight of a vinyl monomer copolymerizable with the above-mentioned aromatic vinyl monomer having a refractive index of a single polymer of less than 1.50.
9.9% by weight, and 0.1-5% by weight of multifunctional vinyl monomer
10 to 100 parts by weight of a monomer mixture (III) consisting of
Seeding emulsion polymerization.

Specific examples of the aromatic vinyl monomer used in the cross-linking graft reaction include styrene, α-methylstyrene, and other α-
Examples include nuclear substituted alkylstyrenes such as alkylstyrene and p-methylstyrene, vinylnaphthalene and the like. These may be one kind or a mixture of two or more kinds.

The proportion of the aromatic vinyl monomer in the monomer mixture (III) must be 0 to 80% by weight. If this ratio is more than 80% by weight, the refractive index becomes large and the miscibility becomes poor when the resin produced is mixed with other hard resin.

Specific examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. They are,
It may be one kind or a mixture of two or more kinds. The proportion of vinyl cyanide monomer in the monomer mixture (III) should be 0 to 40% by weight. If it exceeds 40% by weight, the dispersibility of the cross-linked and graft-polymerized resin with other resins is deteriorated, and the moldability becomes poor, which is not preferable.

The refractive index of the homopolymer is a vinyl monomer copolymerizable with the aromatic vinyl monomer of less than 1.50, the refractive index of the polymer obtained by homopolymerizing this vinyl monomer is less than 1.50. What is. Specific examples of the vinyl monomer copolymerizable with the aromatic vinyl monomer include methyl acrylate, t-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, n-butyl methacrylate and methyl methacrylate. These may be one kind or a mixture of two or more kinds.

The proportion of the vinyl monomer copolymerizable with the aromatic vinyl monomer having a refractive index of less than 1.50 in the monomer mixture (III) in the monomer mixture (III) is 0 to 99.9% by weight. Since the monomer mixture (III) contains other components, it is 99.9% by weight.
Never exceeds.

The monomer mixture (III) contains the polyfunctional vinyl monomer exemplified above as the constituent component of the acrylic seed rubber particles. Monomer mixture of this polyfunctional vinyl monomer (III)
The ratio in the inside is 0.1 to 5% by weight. If it is less than 0.1% by weight, it becomes difficult to wrap the rubber particles of the acrylic rubber by a cross-linking graft reaction to form a layered structure. When the polyfunctional vinyl monomer exceeds 5% by weight, the crosslinking density becomes high and the graft polymerization in the next fourth step becomes difficult, which is not preferable.

In the cross-linking graft reaction in the present invention, the monomer mixture (III) is added to 100 parts by weight of the acrylic rubber obtained in the second step.
Is added in the range of 10 to 100 parts by weight and polymerized by the seeded emulsion polymerization method. When the addition amount of the monomer mixture (III) is less than 10 parts by weight, the crosslinked graft copolymer only covers a part of the rubber particle surface of the acrylic rubber,
Not preferable. If the amount of the monomer mixture (III) exceeds 100% by weight, the amount of acrylic rubber in the crosslinked graft particles will be small, which is not preferable.

This cross-linking graft reaction can be carried out by a usual emulsion polymerization method using water as a medium, similar to the one used in the second step. At this time, it is preferable to appropriately divide the monomer mixture (III), the emulsifier, the polymerization initiator and the like in accordance with the polymerization rate of the seed emulsion polymerization and add them over time.

In the fourth step for producing the graft copolymer resin (A) in the present invention, 10-90% by weight of an aromatic vinyl monomer and a vinyl cyanide monomer are added to the polymerization system obtained after the third step. Body 10-40% by weight, and methyl methacrylate 0
Graft polymerization is carried out by adding 55 to 185 parts by weight of a monomer mixture (IV) of -80% by weight. The above monomer mixture (I
The aromatic vinyl monomer and the vinyl cyanide monomer which are the components of V) are the respective vinyl monomers exemplified as the components used in the crosslinking graft reaction in the third step.
The above-mentioned monomer mixture (IV) contains 10 to 90 aromatic vinyl monomers.
In the range of 10% to 40% by weight of vinyl cyanide monomer and 0 to 80% by weight of methyl methacrylate. If it is out of this range, not only the graft polymerizability changes, it is necessary to change the polymerization conditions, but also the characteristics of the graft polymerized resin change and the types of other resins to be mixed are limited, which is not preferable.

In the fourth step, the monomer mixture (IV) was added in an amount of 55 to 185 parts by weight to the polymerization system in which 100 parts by weight of the acrylic rubber in the third step was subjected to the cross-linking graft reaction, and graft polymerization was performed. Do. Monomer mixture IV added at this time)
If the amount is less than 55 parts by weight, a sufficient amount of resin to cover the surface of the rubber particles of the acrylic rubber latex cannot be generated by graft polymerization, and the graft ratio becomes small, resulting in a decrease in graft copolymer resistance. It is not preferable because it lowers impact resistance and dispersibility. If the amount added exceeds 185 parts by weight, the graft ratio will be saturated and constant, only the resin not graft-polymerized will increase, and the concentration of acrylic rubber in the resin will decrease, which is not preferable.

The graft polymerization in the fourth step can be performed by an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, or the like. When the emulsion polymerization method is used, the usual emulsion polymerization method using water as the medium described in the seeded emulsion polymerization method can be used.

In carrying out the graft polymerization other than the emulsion polymerization method in the fourth step, first, when the surface of the acrylic rubber particles is coated with a hard resin and the dispersion by the rubber particles alone becomes possible, It is advisable to adopt a method in which the graft polymerization is continued by shifting from the suspension system, the solution system or the bulk polymerization system.

For the polymerization system that has completed the fourth step, a known appropriate post-treatment,
For example, the graft copolymer resin (A) can be obtained by appropriately combining steps such as salting out, separation, washing, drying, mixing, and pelletizing.

The graft copolymer resin (B) constituting the composition of the present invention means 100 parts by weight of EPDM, 10 to 90% by weight of an aromatic vinyl monomer, 10 to 40% by weight of a vinyl cyanide monomer, and 0% of methyl methacrylate. ~ 80% by weight of monomer mixture (V) 20 ~
A rubber particle having a particle size of 0.5 to 5 μm, which is obtained by adding 2000 parts by weight and graft-polymerizing it. The graft copolymer resin (B) is a kind of acrylonitrile / EPDM / styrene copolymer (AES resin) and is an impact resistant resin having excellent weather resistance.

EPDM which is a constituent component of the above graft copolymer resin (B)
Known materials can be used without any special restriction. EPDM
Is a rubber obtained by coordinately anionically polymerizing each component such as ethylene, propylene, and non-conjugated diene in an appropriate combination. Of these components, what is important in the case of graft polymerization is the type and amount of the non-conjugated diene which is the starting point of the branch component of the graft polymerization, and usually ethylidene norbornene and the like are contained in EPDM in a proportion of 0.1 to 20% by weight. Used in.

The aromatic vinyl monomer and the vinyl cyanide monomer which are the components of the monomer mixture (V) are exemplified as the components used in the third step of producing the graft copolymer resin (A) first. Each of the vinyl monomers described above. The monomer mixture (V) comprises 10 to 90% by weight of an aromatic vinyl monomer, 10 to 40% by weight of a vinyl cyanide monomer, and 0 to 80% by weight of methyl methacrylate. If it is out of this range, not only the graft polymerizability changes, it is necessary to change the polymerization conditions, but also the characteristics of the graft polymerized resin change and the types of other resins to be mixed are limited, which is not preferable.

20 to 2 parts of this monomer mixture (V) is added to 100 parts by weight of the EPDM.
Graft polymerization is carried out by adding in an amount of 000 parts by weight, preferably in an amount of 200 to 1000 parts by weight. If the amount of the monomer mixture (V) added at this time is less than 20 parts by weight, EPDM rubber particles cannot be formed and the surface of the rubber particles cannot be coated with the resin of the graft branch component. Therefore,
It is not preferable because it reduces the impact resistance of the graft copolymer resin (B) and the dispersibility of EPDM rubber particles. The amount added
If it exceeds 2000 parts by weight, only the resin not graft-polymerized increases, and the concentration of the EPDM component in the graft copolymer resin decreases, which is not preferable. When the graft polymerization is carried out by a bulk polymerization method described later (including solution bulk polymerization method, solution bulk-suspension polymerization method, bulk-suspension polymerization method, etc.), EP
Since DM is dissolved in the monomer mixture (V), the addition amount is
It is particularly preferable to select from the range of 200 to 1000 parts by weight.

This graft polymerization is a known bulk polymerization method, solution polymerization method,
A suspension polymerization method and / or an emulsion polymerization method or the like can be employed in a batch or continuous manner, and these methods and schemes can be appropriately combined and employed. As an example of the solution bulk-suspension polymerization method, first, a solution system in which EPDM is completely dissolved in an aromatic vinyl monomer and a solvent for EPDM is once formed, and then the vinyl cyanide monomer is added to this system. And / or methylmethacrylate are added batchwise or continuously and polymerization is carried out under shear stress. Then EPDM
After the rubber particles are stably formed, transition to suspension polymerization,
The polymerization is completed and the EPDM solvent is recovered. EPDM
As the solvent for use, various known solvents can be used alone or as a mixture, and for example, n-heptane, cyclohexane and the like are most often used.

In this graft polymerization, a known polymerization initiator of acrylonitrile-rubber component-styrene copolymer, and
If necessary, auxiliary agents such as a molecular weight modifier, a stabilizer, an antioxidant, a surfactant and a suspension stabilizer can be used in appropriate combination.

The rubber particle diameter of the EPDM component of the graft copolymer resin (B) in the present invention is adjusted within the range of 0.5 to 5 μm. EPD
If the rubber particle size of the M component is smaller than 0.5 μm, the impact resistance of the resin composition cannot be improved, which is not preferable.
If it is larger than 5 μm, the number of rubber particles in the resin is reduced when compared with the same rubber concentration, so that the impact resistance of the resin composition is also lowered, which is not preferable.

In the present invention, the rubber particle size of the EPDM component means the use of a Coulter Electronics Ltd. Coulter Counter to dissolve a small amount of the graft copolymer in dimethylformamide and add a trace amount of potassium thiocyanate. The weight average rubber particle diameter of the solution measured at 23 ° C.

The copolymer resin (C) constituting the composition of the present invention comprises 10 to 90% by weight of an aromatic vinyl monomer and 10 to 90% of a vinyl cyanide monomer.
It is produced by polymerizing a monomer mixture (VI) consisting of 40% by weight and 0 to 80% by weight of methyl methacrylate. This copolymer resin (C) is a known acrylonitrile-styrene copolymer (AS resin) having an appropriate molecular weight and composition in accordance with the resin composition according to the present invention.

The polymerization method and polymerization conditions of the above monomer mixture (VI) are
A method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method can be appropriately selected from batch or continuous methods according to known AS resin production techniques. The aromatic vinyl monomer and vinyl cyanide monomer, which are the components of the monomer mixture (VI), are the respective vinyl monomers exemplified above. The monomer mixture (VI) is an aromatic vinyl monomer 10
.About.90% by weight, vinyl cyanide monomer 10 to 40% by weight, and methyl methacrylate 0 to 80% by weight. Outside of this range, not only the polymerization conditions need to be changed, but also the type and composition of other graft copolymer resin to be blended are limited, which is not preferable.

The resin composition according to the present invention comprises a graft copolymer resin (A), a graft copolymer resin (B),
And a copolymer resin (C) are mixed, and mixed and kneaded to produce.

At this time, it is derived from the acrylic rubber component derived from the graft copolymer resin (A) and the graft copolymer resin (B).
The weight ratio of EPDM component is acrylic rubber component / E
It is recommended to selectively combine PDM components within the range of 97/3 to 30/70. Particularly preferred within this range is acrylic rubber component / EPDM component = 97/3 to 50/50. Separate the ratio of this acrylic rubber component and EPDM component to
If the content of the components is too small or too large, the impact resistance tends to decrease, so it is preferable to select and combine the components within the above range.

Further, it is preferable that the total of the acrylic rubber component and the EPDM component contained in the resin composition according to the present invention is in the range of 5 to 40% by weight with respect to the resin composition adult. . If the total of the acrylic rubber component and the EPDM component is too small outside the above range, the impact resistance tends to decrease, and if it is excessive, the rigidity of the resin composition, the melt fluidity, etc. will decrease, and the appearance of the molded product will decrease. Since it has an unfavorable effect on the above, it is preferable to set it in the above range.

In addition, the graft copolymer resin (A) has a rubber particle diameter of 0.
Acrylic rubber of 15 to 0.5 μm is used, and the rubber particle diameter of EPDM component of the graft copolymer resin (B) is 0.5 to 5 μm, and it is used for the graft copolymer resin (A). For the rubber particle size of the acrylic rubber and the rubber particle size of the EPDM component in the graft copolymer resin (B),
It is preferable to combine and blend so that a difference in particle diameter of at least 0.2 μm occurs. When the difference in rubber particles is less than 0.2 μm, the effect of improving impact resistance cannot be obtained by satisfying rubber.

To mix and knead the graft copolymer resin (A), the graft copolymer resin (B) and / or the copolymer resin (C), the known mixing and kneading method may be used.

For example, one or a mixture of two or more of these copolymer resins in the form of powder, beads, or pellets is added to an extruder such as a single-screw extruder or a twin-screw extruder, or a Banbury mixer, a pressure kneader, a twin extruder. With a kneader such as this roll,
It can be a resin composition. Depending on the case, one or two of these copolymer resins which have been polymerized are also used.
It is also possible to employ a method in which at least one seed is mixed in an undried state, precipitated, washed, dried and kneaded.

As the order of this mixing and kneading, three kinds of component resins may be mixed and kneaded at the same time.
One kind or two kinds may be mixed and kneaded, and one kind or two or more kinds may be separately kneaded and then kneaded to obtain a desired resin composition.

The resin composition according to the present invention can be directly used for molding and the like. In addition, by mixing and kneading with another thermoplastic resin such as polystyrene, polymethylmethacrylate, polyvinyl chloride, polycarbonate, polyamide, polybutylene terephthalate, polyphenylene oxide, acrylonitrile / N-phenylmaleimide / styrene copolymer, etc. It can be used as a high impact resistance resin.

The resin composition according to the present invention includes various types of resins such as lubricants, mold release agents, colorants, ultraviolet absorbers, light resistance stabilizers, heat resistance stabilizers, fillers, etc., in types and amounts that do not impair the properties of the resin. The additives can be added in an appropriate combination.

The resin composition according to the present invention includes an injection molding method, an extrusion molding method,
It is made into a desired molded product by various processing methods such as compression molding, and can be used in applications where excellent weather resistance and impact resistance are required.

"Effects of the Invention" As described above, the present invention has particularly remarkable effects as described below, and its industrial utility value is extremely large.

(1) Since the resin composition according to the present invention optimizes the refractive index of the acrylic rubber particles of the graft copolymer resin (A) from the inner layer to the outer layer in a stepwise manner, it has excellent colorability and surface gloss. With and.

(2) In the resin composition according to the present invention, the ratio of each rubber component and each rubber component of the acrylic rubber component in the graft copolymer resin (A) and the EPDM component in the graft copolymer resin (B) are changed. Since the total amount and the respective rubber particle diameters are optimized and compounded, it can be used as a thermoplastic resin having excellent impact resistance.

(3) Since the resin composition according to the present invention uses the acrylic rubber and EPDM having a saturated carbon bond main chain as the base rubber, the weather resistance is extremely excellent.

(4) Since the resin composition according to the present invention has excellent compatibility with other hard thermoplastic resins, a different type of resin composition having excellent weather resistance and impact resistance can be produced by kneading and mixing. be able to.

[Examples] Next, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 (1) Production of Graft Copolymer Resin (A): (i) First Step 937.5 g of butyl acrylate (hereinafter abbreviated as BA), 62.5 g of acrylonitrile (hereinafter abbreviated as AN), and acrylic. 5 g of methacrylate (hereinafter abbreviated as AMA) was weighed and mixed to prepare a monomer mixture (I).

In a 3I glass flask equipped with a stirrer, a reflux condenser, a thermometer, and an auxiliary additive addition device, 1520 g of deionized water, 20 g of higher fatty acid soap (mainly containing sodium salt of fatty acid having 18 carbon atoms), and 10 g of sodium hydrogen carbonate was charged and the internal temperature was raised to 75 ° C. under a nitrogen stream. Then, 20 m of an aqueous solution of potassium persulfate (hereinafter abbreviated as KPS) was added to this flask.
1 (containing 0.75 g of KPS) was added, followed by addition of 40 g of the monomer mixture (I), and the polymerization reaction was started at the same temperature. After 15 minutes from the initiation of the polymerization reaction, the remaining 965 g of the monomer mixture (I) was continuously added to the polymerization system at an addition rate of about 65 g / 10 minutes.

15 minutes after starting the polymerization reaction, 20 ml of KPS aqueous solution (0.7
Includes 5g KPS. ) 1 hour and 30 minutes later, the higher fatty acid soap 6
g was added. The addition of the monomer mixture (I) was completed 2 hours and 45 minutes after the initiation of the polymerization reaction. Further, the polymerization reaction was continued at the same temperature for 1 hour to complete the reaction, and acrylic seed rubber particles were obtained. The conversion rate of the used monomer is 98.5%
Met. The rubber particle diameter of the obtained latex was measured and found to be 0.08 μm.

(Ii) Second step In a 2 liter glass flask equipped with a stirrer, a reflux condenser, a thermometer, and an auxiliary addition device, the acrylic seed rubber particles obtained by the method described in (i) above. The latex 3
4.1g, deionized water 750g, and sodium bicarbonate 3.9g
Was charged, and the temperature inside the flask was raised to 75 ° C. KPS aqueous solution 8
ml (containing 0.3 g of KPS) was added to prepare for polymerization.

On the other hand, the following composition 3 added to the polymerization system in the second step
Type of monomer mixture (II) -A, (II) -B, (II)-
C was prepared.

The above three monomer mixtures (II) -A, (II) -B,
(II) -C was continuously added to a sequential flask divided into three stages by the following procedure to start and continue the polymerization reaction.

45 minutes, 1 hour 30 minutes, 3 hours, and 4 hours after the initiation of the polymerization reaction, 10 ml of an aqueous soap solution (containing 0.92 g of higher fatty acid soap) was added, respectively, and 1 hour 3
After 0 minute and 3 hours, 4 ml of KPS aqueous solution (KPS0.15
Including g. ) Each was added. After 4 hours and 30 minutes from the start of the polymerization reaction, the addition of the monomer mixture was completed, and then the reaction was continued at the same temperature for an additional 1 hour to complete the polymerization reaction. The rubber particle size of the obtained acrylic rubber was measured.

The results are shown in Table 1.

(Iii) Third step In the same 3 liter glass flask used in the first step, the total amount of the acrylic rubber latex obtained by the method described in (ii) above, 750 g of deionized water, and sodium hydrogen carbonate.
6 g was charged, and the temperature inside the flask was raised to 75 ° C. 8 ml of a KPS aqueous solution (containing 0.3 g of KPS) was added to prepare for polymerization.

On the other hand, a monomer mixture (III) having the following composition to be added to the polymerization system in the third step was prepared.

Monomer mixture (III) MMA * 4 58.5 g St 95.6 g AN 40.9 g AMA 1 g [Note] * 4: Mean methyl methacrylate. Hereinafter, they have the same meaning.

The above monomer mixture (III) was continuously added to the flask at an addition rate of about 16.3 g / 10 min to initiate the polymerization reaction.
1 hour and 30 minutes after starting the polymerization reaction, the soap solution 20
ml (containing 1.95 g of higher fatty acid soap) was added. After 2 hours, the addition of the monomer mixture (III) was completed, and the crosslinking graft reaction was completed.

(Iv) Fourth step The polymerization system that has been subjected to the third step described in (iii) above is left as it is, the flask internal temperature is maintained at 75 ° C., and KP is added under stirring.
8 ml of S aqueous solution (containing 0.3 g of KPS) was added. Then, a monomer mixture consisting of St286.6g and AN122.9g (I
V) was continuously added at an addition rate of about 22.8 g / 10 minutes to initiate the graft polymerization reaction.

1 hour and 3 hours after starting the polymerization reaction,
20 ml of each aqueous soap solution (containing 2 g of higher fatty acid soap) was added, and 1 hour later, 8 ml of an aqueous KPS solution (containing 0.3 g of KPS) was additionally added. 3 after starting the polymerization reaction
After a lapse of time, the addition of the monomer mixture (IV) was completed, and then the reaction was continued at the same temperature for 1 hour to complete the graft polymerization reaction.

The monomer conversion used was 99%. Graft-polymerized latex was salted out by a conventional method, washed well with water, and dried to obtain about 1 kg of a graft copolymer.

(2) Production of graft copolymer resin (B) St552 was placed in a 2 liter autoclave equipped with an Ikari type stirrer.
g, EPDM [Moonie viscosity ML _{1 + 4} (100 ℃) 45, iodine value 2
5. Ethylidene norbornene as the third component] 140 g and n-heptane 100 g were charged, and the atmosphere was replaced with nitrogen.
It was completely dissolved by stirring for 100 hours at 100 rpm. Then, under the same stirring, AN258g was charged at a rate of 40g / 10 minutes, and then
0.5 g of rt-butyl peroxide, 0.13 g of tert-butyl peracetate and 0.5 g of terpyrenone were charged and bulk polymerization was carried out at 97 ° C. for 7 hours and 20 minutes. About 30 minutes before the end of bulk polymerization,
tert-butyl peroxide 1.5g and terpinolene 1.5g
Was dissolved in St50g and charged. At the end of the polymerization, the EPDM rubber particle size was 1.6 μm.

The syrup obtained in the bulk polymerization process was added to 2.5 g of a suspension agent (acrylic acid / alkyl acrylate copolymer) in 1100 g of water.
Was charged in a 3 l autoclave (equipped with a three-blade agitator) containing the above aqueous solution and replaced with nitrogen, and then this aqueous suspension system was subjected to suspension polymerization at 130 ° C and 500 rpm for 2 hours and then to 150 ° C. The temperature was raised and stripping was carried out for 1 hour. The obtained resin composition was washed with water and dried at 100 ° C to obtain 920 g.
A graft copolymer resin of was obtained.

(3) Production and evaluation of resin composition Graft copolymer resin obtained by the method described in (1) above
Fat (A) 552.5 g, obtained by the method described in (2) above.
Raft copolymer resin (B) 278.6g, and acrylonite
Ryl / styrene copolymer (SAN -C, Mitsubishi Monsanto
Kasei Co., Ltd.) 468.9 g, butylated hydroxytoluene 3
g and magnesium stearate 5 g
Weighed and controlled Banbury mixer at 180 ℃
Kneaded with, and the acrylic rubber content was 17% by weight.
And a resin composition containing 3% by weight of EPDM rubber component
Created a set.

The pellets of this resin composition were molded into a test piece for impact resistance measurement and a test piece for gloss evaluation by an injection molding machine.
According to JIS K7110, the Izod impact strength (with notch) was measured according to JIS K7105, and the gloss based on the reflectance at an incident angle of 60 ° was measured. The results are shown in Table 1.

In order to evaluate the colorability, when kneading the raw materials for the composition by the above-mentioned Banbury mixer for test, 5.2 g of carbon black for color is mixed and added, and by the same operation as above, the colored resin composition Made with pellets.

A test piece was molded from the pellet of the resin composition by an injection molding machine. With respect to the molded test piece, the colorability and the appearance were visually judged based on the following criteria. The results are shown in Table 1.

Criteria for judging colorability and appearance ⊚: Colorability is good. It becomes deep black (black). Weld line (resin fusion line) with no pearly luster
Is hardly recognized.

◯: Colorability is normal. The depth of black is lacking, and it is necessary to increase the amount of colorant for color matching. There is no pearly luster. Weld lines are slightly recognized.

X: Poor colorability. It becomes a dull gray-like black color. Color matching is difficult even if the amount of colorant is increased. It has a pearly luster and some delamination is observed. Weld lines are clearly visible.

Example 2 (1) Production of graft copolymer resin (A): (i) First step Same as described in Example 1 (1) (i).

(Ii) Second step The same as described in Example 1 (1) (ii).

(Iii) Third step In the example described in Example 1 (1) (iii), except that the composition of the monomer mixture (III) was changed as shown below,
The same procedure as in Example (1) (iii) was performed.

Monomer mixture (III) St 136.5g AN 58.5g AMA 1 g (iv) Fourth step Same as described in Example 1 (1) (iv).

(2) Production of Graft Copolymer Resin (B) Same as described in Example 1 (2).

(3) Production and Evaluation of Resin Composition Same as described in Example 1 (3).

Example 3 (1) Production of Graft Copolymer Resin (A): (i) First Step Same as described in Example 1 (1) (i).

(Ii) Second Step In the example described in Example 1 (1) (ii), the composition of the monomer mixture (II) was changed to the following two types, and the addition was changed to the following two-stage addition. Otherwise, the same procedure as in Example (1) (ii) was performed.

(Iii) Third step The same as described in Example 2 (1) (iii).

(Iv) Fourth step The same as described in Example 1 (1) (iv).

(2) Production of Graft Copolymer Resin (B) Same as described in Example 1 (2).

(3) Production and Evaluation of Resin Composition Same as described in Example 1 (3).

Comparative Example 1 (1) Production of Graft Copolymer Resin (A): (i) First Step Same as described in Example 1 (1) (i).

(Ii) Second Step In the example described in Example 1 (1) (ii), the composition of the monomer mixture (II) was BA390g and AMA1.95g, and the addition method was 4 hours immediately after the initiation of the polymerization reaction. Until the minutes elapse,
The procedure was the same as in Example (1) (ii), except that the monomer mixture (II) was continuously added at an addition rate of about 14.5 g / 10 minutes.

(Iii) Third step The same as described in Example 2 (1) (iii).

(Iv) Fourth step The same as described in Example 1 (1) (iv).

(2) Production of Graft Copolymer Resin (B) Same as described in Example 1 (2).

(3) Production and Evaluation of Resin Composition Same as described in Example 1 (3).

Comparative Example 2 (1) Production of Graft Copolymer Resin (A): (i) First Step The same as described in Example 1 (1) (i).

(Ii) Second step In the example described in the present invention 1 (1) (ii), the composition of the monomer mixture (II) is BA195g, MMA195g, and AMA1.95g.
Except that the addition method was changed so that the monomer mixture (II) was continuously added at an addition rate of about 14.5 g / 10 minutes from immediately after the initiation of the polymerization reaction to 4 hours and 30 minutes later. ) The procedure was the same as in (ii).

(Iii) Third step The same as described in Example 2 (1) (iii).

(Iv) Fourth step The same as described in Example 1 (1) (iv).

(2) Production of Graft Copolymer Resin (B) Same as described in Example 1 (2).

(3) Production and Evaluation of Resin Composition Same as described in Example 1 (3).

Comparative Example 3 (1) Production of graft copolymer resin (A): (i) First step Same as described in Example 1 (1) (i).

(Ii) Second step The same as used in the second step of Example 1 (1) (ii).

A 2 l glass flask was charged with 34.1 g of a latex of acrylic seed rubber particles obtained by the method described in (i), 750 g of deionized water, and 3.9 g of sodium hydrogen carbonate,
The temperature inside the flask was raised to 75 ° C. KPS aqueous solution 3 ml (0.1 g
Including KPS. ) Was added.

A monomer mixture (II) consisting of 57 g of BA and 0.3 g of AMA was continuously added at an addition rate of about 14.3 g / 10 minutes to initiate a polymerization reaction. 45 minutes after starting the polymerization reaction, 5m of soap aqueous solution
l (including 0.35 g of higher fatty acid soap) was added. After 40 minutes from the start of the polymerization reaction, the addition of the monomer mixture (II) was completed, and then the reaction was continued at the same temperature for 1 hour to complete the polymerization reaction. The rubber particle size of the obtained acrylic rubber was measured. The results are shown in Table 1.

(Iii) Third step The same 3 l glass flask used in Example 1 (1) (iii) third step was charged with the total amount of the latex of the acrylic rubber obtained by the method described in (ii) above. The temperature inside the flask was raised to 75 ° C. 4 ml of KPS aqueous solution (containing 0.15 g of KPS) was added. The monomer mixture (III) consisting of St21g, AN9g, and AMA0.15g was continuously added at an addition rate of about 12.0 / 10 minutes to start the polymerization reaction. 25 minutes after starting the polymerization reaction, the addition of the monomer mixture (II) was completed,
The cross-linking graft reaction was completed.

(Iv) Fourth Step The polymerization system obtained by the method described in (iii) above and subjected to the cross-linking graft reaction was continuously maintained at a flask internal temperature of 75 ° C. and stirred.

Monomer mixture (IV) consisting of St52.5g and AN22.5g,
Graft polymerization reaction was initiated by continuous addition at an addition rate of about 30 g / 10 minutes. 40 minutes after starting the polymerization reaction, 10 ml of an aqueous soap solution (containing 1.05 g of higher fatty acid soap) was added. After 25 minutes from the start of the polymerization reaction, the addition of the monomer mixture (IV) was completed, and then the reaction was continued at the same temperature for 1 hour to complete the polymerization reaction.

The polymerization addition rate was 98%. The graft-polymerized latex was salted out by a conventional method, washed and dried to obtain a graft copolymer.

(2) Production of Graft Copolymer Resin (B) Same as described in Example 1 (2).

(3) Production and Evaluation of Resin Composition In order to match the content of the acrylic rubber component of the resin composition obtained in the example described in Example 1 (3) with 17% by weight, the above graft copolymer resin (A The procedure was the same as in Example (3), except that the amount of a) was decreased and the amount of the acrylonitrile-styrene copolymer was increased so that the total amount of the kneaded sample was the same as that of Example (3).

The following is clear from Table 1.

(1) The resin composition according to the present invention is excellent because the refractive index of the inner layer and the outer layer of the acrylic rubber particles of the graft copolymer resin (A) and the refractive index of the diluted resin are gradually increased. Has excellent coloring and surface gloss. Moreover, the coexisting EPDM particles of the graft copolymer resin (B) do not adversely affect these coloring properties and surface gloss (see Examples 1 to 3).

On the other hand, in the case of the comparative example in which the refractive index of the acrylic rubber particles is small, the refractive index of the diluted resin is large, and the refractive indexes are not close to each other and changes largely discontinuously, the coloring property or the surface gloss becomes poor. (See Comparative Examples 1 and 2).

(2) In the resin composition according to the present invention, the ratio of each rubber component and each rubber component of the acrylic rubber component in the graft copolymer resin (A) and the EPDM component in the graft copolymer resin (B) are different from each other. Since the total compounding amount and the respective rubber particle diameters are optimized and compounded, it has excellent impact resistance (see Examples 1 to 3).

Further, the resin composition obtained outside the scope of the present invention is inferior in impact resistance (see Comparative Examples 1 and 3).

Claims (3)

[Claims] 1. An alkyl acrylate monomer having 1 to 8 carbon atoms in an alkyl group, 70 to 100% by weight, 0 to 30% by weight of a vinyl monomer copolymerizable with the alkyl acrylate, and a polyfunctional vinyl monomer. Monomer mixture consisting of 0 to 5% by weight (however, the total monomer mixture is 100% by weight)
Emulsion polymerized to give a rubber particle size of 0.03 μm to 0.15 μm.
a first step for producing acrylic seed rubber particles having a size of less than m; 1 part by weight of the acrylic seed rubber particles obtained in the first step as a seed, and an alkyl acrylate monomer having an alkyl group having 1 to 8 carbon atoms 20-94.9% by weight, the refractive index of a single polymer is
A monomer mixture consisting of 5 to 79.9% by weight of a vinyl monomer copolymerizable with the above-mentioned alkyl acrylate of 1.50 or more and 0.1 to 5% by weight of a polyfunctional vinyl monomer (however, the monomer mixture is 100% by weight in total). The second step of producing an acrylic rubber having a rubber particle diameter of 0.15 to 0.5 μm by the seed emulsion polymerization method by adding 2.5 to 125 parts by weight, and the acrylic resin obtained in the second step. 100 parts by weight of rubber,
Aromatic vinyl monomer 0 to 80% by weight, vinyl cyanide monomer 0 to 40% by weight, vinyl monomer copolymerizable with the above aromatic vinyl monomer whose refractive index of a single polymer is less than 1.50 Body 0
A monomer mixture consisting of 99.9% by weight and 0.1 to 5% by weight of a polyfunctional vinyl monomer (however, the total amount of the monomer mixture is 10%).
It is 0% by weight. ) Addition of 10 to 100 parts by weight and a cross-linking graft reaction by a seeded emulsion polymerization method, a third step, a polymerization system after the third step is further added, 10 to 90% by weight of an aromatic vinyl monomer, and cyan. Grafting is performed by adding 55 to 185 parts by weight of a monomer mixture consisting of 10 to 40% by weight of vinyl chloride monomer and 0 to 80% by weight of methyl methacrylate (however, the total amount of the monomer mixture is 100% by weight). Fourth step of polymerizing, graft copolymer resin (A) obtained by, ethylene / propylene / non-conjugated diene copolymer rubber (EP
DM) 100 parts by weight, aromatic vinyl monomer 10 to 90% by weight,
20 to 2000 parts by weight of a monomer mixture consisting of 10 to 40% by weight of vinyl cyanide monomer and 0 to 80% by weight of methyl methacrylate (however, the total amount of the monomer mixture is 100% by weight) is added, The rubber particle size obtained by graft polymerization is 0.5 to
Graft copolymer resin (B) having a thickness of 5 μm, aromatic vinyl monomer 10 to 90% by weight, vinyl cyanide monomer
Monomer mixture consisting of 10 to 40% by weight and methyl methacrylate 0 to 80% by weight (however, the total monomer mixture is
100% by weight. And a copolymer resin (C) obtained by polymerizing the above), and a shock-resistant resin composition. 2. A weight ratio of the acrylic rubber component derived from the graft copolymer resin (A) and the EPDM component derived from the graft copolymer resin (B) is acrylic rubber component / EPDM component. = 97/3 to 30/70. The impact resistant resin composition according to claim (1), characterized in that it is blended in the range of 97/3 to 30/70. 3. The total of the acrylic rubber component and the EPDM component contained in the impact resistant resin composition is in the range of 5 to 40% by weight with respect to the entire resin composition, The impact resistant resin composition according to any one of claims (1) and (2).