JPS63132956A - Impact-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition outstanding in dyeability and surface gloss, by incorporating AES resin and AS resin in a thermoplastic resin prepared by graft polymerization of an aromatic vinyl monomer to an acrylic rubber made by seeding emulsion polymerization with the refractive index regulated. CONSTITUTION:(A) First, using, as the seed, 1pt.wt. of acrylic rubber particles with a size 0.03-0.15mum prepared by emulsion polymerization between an alkyl acrylate, vinyl monomer copolymerizable therewith, and polyfunctional vinyl monomer, a seeding polymerization is carried out between (1) 20-94.9pts.wt. of an alkyl acrylate and (2) 2.5-125pts.wt. of a mixture of a) a vinyl monomer copolymerizable therewith, capable of giving a homopolymer of a refractive index >=1.50 and (b) a polyfunctional vinyl monomer to form an acrylic rubber with a particle size 0.15-0.5mum followed by two-step graft polymerization of aromatic vinyl or vinyl cyanide compound thereto, thus obtaining a resin. This resin is blended with (B) an acrylonitrile-EPDM-styrene copolymer and (C) an acrylonitrile-styrene copolymer, thus obtaining the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to impact-resistant resin compositions. More specifically, a thermoplastic resin (AAS resin) is made by graft polymerizing an aromatic vinyl monomer, etc. to an acrylic rubber produced by adjusting the refractive index to WI4 by a seeded emulsion polymerization method, and acrylonitrile, ethylene, propylene, non- The present invention relates to an impact-resistant resin composition containing a conjugated tsene-styrene copolymer (AES resin) and having excellent coloring properties and surface gloss.

``Prior Art'' Conventionally, many methods are known for blending rubber with hard resins and obtaining impact-resistant resins reinforced by the rubber. ABStH fat is a typical example of this type, but
Diene rubber is mainly used as the base rubber component. Due to the poor weather resistance of this base rubber, ABS resins based on diene rubber are restricted from being used outdoors, which is the biggest drawback of this resin.

Based on this theory, α, it has become possible to use materials other than tsene-based rubber as the base rubber, and various examples have been proposed in which saturated rubbers with good weather resistance are used. Acrylate rubber-like polymers (hereinafter referred to as acrylic rubber) and ethylene-propylylene-nonconjugated diene copolymer rubber (hereinafter referred to as EPDM) are often used as examples of these.

However, even if acrylic rubber is simply substituted for the diene rubber of ABS resin as the base rubber and graft polymerized, a resin with satisfactory properties cannot be obtained.It is true that diene rubber is used as the base rubber. Although the weather resistance is greatly improved compared to the ABS resin, there are problems with the colorability of the resin, the surface gloss and impact strength of the molded product, and it is difficult to say that it is practically satisfactory.

Rubber reinforced with acrylic rubber, etc. (Bi-branch resins are usually made by graft polymerizing a latex-like rubber component with a monomer mixture that forms the branch components of the graft copolymer. Acrylic rubber, which is used as a rubber component with good weather resistance, has a lower optical refractive index and is softer than diene rubber, so it has a low elastic modulus, slows elastic recovery, and is prone to plastic deformation. When a rubber-resin two-component resin is produced using such soft acrylic rubber with a low refractive index and molded by injection molding etc. as a molding material, the base material There is a large difference in refractive index between the rubber, the branch components of the graft copolymer, and the diluent resin blended into the graft copolymer (and the deformed orientation of the rubber particles becomes difficult, so the surface of the molded product It exhibits a pearl-like luster and has a whitish appearance due to diffuse reflection of light by the rubber particles, making it difficult to express the depth and saturation of the color especially when it is colored, which tends to reduce its commercial value.

In such molded products, the color of the molded surface and mechanical strength such as impact strength vary greatly depending on the flow direction during molding and the location of the molded product. It has the disadvantage of causing defects.

Furthermore, since EPDM cannot normally be produced by emulsion radical polymerization and is produced by solution type coordination anion polymerization, it is possible to obtain it as a latex-like water-dispersed rubber with a rubber particle size of about 0.5 μm or less. Technically and economically extremely difficult. For this reason, it is difficult to perform a graft polymerization reaction using the emulsion polymerization method, and it is difficult to create a material with a rubber particle size distribution and rubber component content suitable for impact resistance as a rubber-resin two-component resin. However, this was a drawback of AES resin.

"Problems to be Solved by the Invention" The present inventors have solved the above-mentioned shortcomings that existed in conventional rubber-resin two-component resins that used acrylic rubber or EPDM as the base rubber. With the purpose of
As a result of extensive research, we have arrived at the present invention.

That is, first, a two-step polymerization reaction was carried out using a seeded emulsion polymerization method to adjust the refractive index to produce an acrylic rubber, and then a two-step graft polymerization reaction was performed to adjust the refractive index and rubber particle size to a specific range. Acrylonitrile/acrylic rubber/styrene copolymer (AAS resin) is added to this resin, and then acrylonitrile/EPDM/styrene copolymer (AES resin) with a rubber particle size adjusted to a specific range is added to this resin. By blending 7crylonitrile-styrene copolymer (AS tree 111t) in a specific ratio, moldability and weather resistance are good, and
The object of the present invention is to provide an impact-resistant resin composition with excellent coloring properties and surface gloss.

[Means for Solving the Problems] The gist of the present invention is that the number of carbon atoms in the alkyl group is 1.
~8 alkyl acrylate monomer 70-100% by weight
, 0 to 30% by weight of a vinyl monomer copolymerizable with the above alkyl acrylate, and θ to 5 of a polyfunctional vinyl monomer.
Acrylic seed rubber having a rubber particle size of 0.03 μm to less than 0.15 μm is obtained by emulsion polymerizing a monomer mixture consisting of 100% by weight (however, the total monomer mixture is 100% by weight). A first step of producing particles, using 1 part by weight of the acrylic seed rubber particles obtained in the above step P141 as a seed, and adding 20 to 94. ．． 9% by weight, 5 to 79.9% by weight of a vinyl monomer copolymerizable with the alkyl acrylate having a refractive index of 1.50 or more as a single polymer, and 0.1 to 5% of a polyfunctional vinyl monomer. 2.5 to 125 parts by weight of a monomer mixture consisting of 100% by weight (the total monomer mixture is 100% by weight) is added, and a rubber particle size of 0.15 to 0.5% is added by a seeded emulsion polymerization method. The second step of producing acrylic rubber with a thickness of 5 μm. The acrylic rubber obtained in the second step above! 00 weight jft
In part, aromatic vinyl monomer 0, 80 [i%, vinyl cyanide monomer 0-, 40% by weight, the above aromatic vinyl monomer having a refractive index of less than 1.50 as a single polymer. A monomer mixture consisting of 0 to 99.9% by weight of a vinyl monomer that can be copolymerized with )10～
Add 100 parts by weight L% of 10 to 90 parts by weight of aromatic vinyl mono-11, vinyl cyanide mono Quantity 10~
A monomer mixture consisting of 40% by weight and 0 to 80% by weight of methyl methacrylate (however, the monomer mixture consists of a total of 1% by weight)
00% by weight. 4th step of adding 55 to 185 parts by weight of the graft copolymer resin (A) and performing graft polymerization.
Propylene/non-conjugated tsene copolymer rubber (EPDM) 1
00 parts by weight, 10 to 90 ifi% aromatic vinyl monomer
, a monomer mixture consisting of 10 to 40% by weight of vinyl cyanide 41, and 0 to 80% by weight of methyl methacrylate (however, the total amount of the monomer mixture is 100 il%71.)
Graft copolymer resin (B) having a rubber particle size of 0.5 to 5 μm obtained by graft polymerization by adding 11 parts of 20 to 2000), and aromatic vinyl monomer 10 to 9
0% by weight, 10 to 40i% by weight of vinyl cyanide monomer, and 0 to 80% by weight of methyl methacrylate (however, the total monomer mixture is 100% by weight). The present invention provides an impact-resistant resin composition having a vt characteristic of containing the resulting copolymer resin (C).

The present invention will be explained in detail below.

The graft copolymer resin (A) constituting the resin composition according to the present invention is produced through the first step, #12 step, third step, and fourth step described later. This graft copolymer resin (A) is made of 7-crylonitrile, acrylic rubber,
It is a type of styrene copolymer (AAS resin), and is a weather-resistant and impact-resistant resin with excellent coloring properties and surface gloss.

The first step for producing the graft copolymer (A) in the present invention refers to the step of producing acrylic seed rubber particles during seeded emulsion polymerization, and the acrylic seed produced in this first step. Rubber particles are first added to the emulsion polymerization system during the production of acrylic rubber, and serve as seeds for producing acrylic rubber with large rubber particle diameters.

The acrylic seed rubber particles in the present invention refer to 70 to 1 alkyl acrylate monomers having an alkyl group of 1 to 8 carbon atoms.
00% by weight, 0 to 30% by weight of a vinyl monomer copolymerizable with the above alkyl acrylate, and 0 to 5% by weight of a polyfunctional vinyl monomer (however, the monomer mixture has a total of 100% by weight). (wt%) (same below) (1)
Rubber particles are produced by emulsion polymerization and have a rubber particle diameter of 0.03 μm to less than 0.15 μm.

The alkyl acrylate monomer, which is the constituent R&component of the above acrylic seed rubber particles, refers to alkyl acrylate having a furkyl group having 1 to 8 carbon atoms.The A-form side includes ethyl acrylate, n-butyl acrylate, and 2-ethyl. Examples include full-kyl 7-acrylates such as xyl acrylate. These may be Ill or a mixture of two or more.

The monomer mixture (1) used for producing the acrylic seed rubber particles contains the furkyl 7 acrylate monomer in a proportion of 70 to 1
If the content is less than 70% by weight, the rubber elasticity of the seed rubber particles decreases and the compatibility with the acrylic rubber layer formed on the outer layer of the seed rubber particles decreases. This is not preferable because it reduces performance.

Examples of vinyl monomers copolymerizable with the alkyl acrylate include aromatic vinyl monomers described later, vinyl cyanide monomers described later, acrylamide, methacryl 7mide, vinylidene chloride, furkyl vinyl ether, alkyl vinyl ester, Examples include alkyl methacrylates and halogen-substituted compounds thereof. These may be used alone or in a mixture of two or more.

The amount of this copolymerizable vinyl monomer to be included in the monomer mixture (1) must be selected in the range of 0 to 30% by weight. Exceeding this is not preferable because 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 vinyl monomers include divinylbenzene,
Aromatic polyfunctional vinyl monomers such as divinyltoluene, ethylene glycol dimethacrylate, methacrylates and acrylates of polyhydric alcohols such as )rimethylolpropane triacrylate, diallyl maleate, triallyl isocyanate, diallyl phthalate, 7lyl methacrylate etc. can be mentioned. These are one or two types.
The amount of this polyfunctional vinyl monomer to be included in the monomer mixture (1) must be selected within the range of 0 to 5% by weight. If the vinyl monomer content exceeds 5% by weight, the compatibility with the acrylic rubber layer formed as the outer layer will be poor, and the properties of the seed rubber particles will deteriorate, which is not preferable.

The acrylic seed rubber particles in the present invention are prepared by appropriately modifying various known conditions such as the types and amounts of emulsifiers and polymerization catalysts, the method of adding them, and the method of adding monomers in emulsion polymerization using known water as a medium. They can be manufactured together.

The acrylic seed rubber particles have a rubber particle diameter of 0.03 μm.
If the rubber particle size is smaller than 0.03 μm, it cannot be produced by a normal emulsion polymerization method, and a special product containing a high concentration of emulsifier becomes uneconomical. 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, resulting in an impact-resistant resin with excellent coloring properties and surface gloss. cannot be manufactured.

In the present invention, the particle size of rubber particles such as acrylic rubber dispersed in water is defined by Coulter Electronics Co., Ltd. (USA).
electronics Ltd,) 1 Nanosizer (C
Measured using a system in which latex was dispersed in water at 23°C using
Weight average rubber particle diameter.

In the second step for producing graft copolymer 0 (fat (A)) in the present invention, acrylic rubber is produced by a seeded emulsion polymerization method.In this second step, a monomer with a high refractive index is By copolymerizing, an acrylic rubber with a higher refractive index than conventional acrylic rubber can be obtained.

The acrylic rubber in the present invention refers to 1 part by weight of the acrylic seed rubber particles obtained in the first step as a seed, and 20% of a fulkylacrylage monomer having an alkyl group of 1 to 8 carbon atoms.
~94.9% by weight, -79.9% by weight of vinyl monomer 5 copolymerizable with the above alkyl acrylate having a refractive index of 1.50 or more as a single polymer, and 0 polyfunctional vinyl monomer. Monomer mixture (II) consisting of .1 to 5% by weight2.
5 to 125 parts by weight is added, and the rubber particle size is 0.15 to 0.5 μm and manufactured by a seeded emulsion polymerization method.

Examples of the alkyl acrylate monomer that is a constituent component of the acrylic rubber include the alkyl acrylate monomers exemplified above as constituent components of the acrylic seed rubber particles. These may be one type or a mixture of two or more types, and the monomer mixture (
II) contains 20 to 9 of the above alkyl acrylate monomers.
It is contained in a range of 4.9% by weight. Content is 20% by weight
If the amount is less, the rubber elasticity of the acrylic rubber becomes lower, which is not preferable.Also, since the monomer mixture (■) contains other components, the content of the alkyl acrylate monomer is 94. It does not exceed 9% by weight.

The vinyl monomer copolymerizable with the above-mentioned alkyl acrylate, which is a constituent component of this acrylic rubber and whose single polymer has a refractive index of 1.50 or more, is obtained by homopolymerizing this vinyl monomer. A polymer having a refractive index of 1.50 or more. Examples of vinyl monomers copolymerizable with the furkyl 7-acrylate whose single polymer has a refractive index of 1.50 or higher include butadiene, vinyl chloride, vinylidene chloride, 7-crylonitrile, vinylnaphthalene, vinylcarbazole, styrene, α-methylstyrene, a-chlorostyrene, vinyltoluene, dichlorostyrene, cyclohexyl methacrylate 1. Examples include benzyl methacrylate. These may be used alone or in a mixture of two or more.

The vinyl monomer component copolymerizable with the alkyl acrylate whose single polymer has a refractive index of 1.50 or more is contained in the monomer mixture (If) in an amount of 5 to 79.9% by weight. Must be selected within a range. If this copolymerizable vinyl monomer component is less than 5% by weight, the refractive index of the acrylic rubber obtained will be small, and the branch components of the graft copolymer and the r, rl #i diluting resin will Since the monomer mixture (II) contains other components, this copolymerizable vinyl monomer component, which is undesirable because it increases the difference in refractive index of Never.

In the present invention, the refractive index refers to JIS K 7105
-1981, using an Atsube refractometer at 23℃N.
This refers to what was measured by DAB in a.

The acrylic rubber in the present invention contains the polyfunctional vinyl monomer component exemplified above as a constituent component of the acrylic seed rubber particles. It must be contained in the range of 0.1 to 5% by weight of the monomer mixture (II) used for.If the content is less than 0.1% by weight, the acrylic rubber
The content of polyfunctional vinyl monomer, which is undesirable because it becomes soft and fluid, is 51! ′! If it exceeds Ik%, the rubber loses its elasticity and becomes hard, which is not preferable.

In the acrylic rubber of the present invention, 2.5 to 1 parts of the monomer mixture (II) is added to the acrylic seed rubber particles IIi.
It is added in an amount of 25 parts by weight and produced by a seeded emulsion polymerization method. If the amount of monomer mixture (II) is less than 2.5 parts by weight, the rubber particle size of the acrylic rubber will not deviate from the desired rubber particle size, which is not preferable. If the amount is more than 125 parts by weight, it takes a long time to polymerize by seeded emulsion polymerization, making it uneconomical.

In this seeded emulsion polymerization of acrylic rubber, polymerization is initiated by adding monomer mixture (II), a polymerization initiator, etc. to a seeded polymerization system containing latex-like acrylic seed rubber particles. At this time, according to the polymerization rate of seeded polymerization,
It is preferable to divide the monomer mixture (TI), emulsifier gJ, intermediate initiator, etc. as appropriate and add them over time.Also, the addition composition of the monomer mixture (II) is as follows:
For example, by changing the refractive index as appropriate from the early stage to the late stage of the polymerization reaction, the refractive index can be gradually increased from the inner layer to the outer layer of the acrylic rubber. By making the refractive index similar to that of the combined technique component, it is possible to improve the appearance of the molded product.

The rubber particle diameter of the acrylic rubber in the present invention is 0.1
5, adjust to within 0.5 μ ring. When the rubber particle diameter of the acrylic rubber is smaller than 0.1 Sμm,
If it is thicker than 0.5 μm, it is not economical because the polymerization takes too much time.

In the third step for producing the graph) copolymer resin (A) in the present invention, a crosslinking graft reaction is performed on the acrylic rubber by a seeded emulsion polymerization method.

The hard crosslinked graft copolymer formed in this third step coats the acrylic rubber produced in the second step, and is located between the acrylic rubber and the diluent resin, and is located between the acrylic rubber having a low refractive index and the diluting resin. The refractive index is approximated to that of a diluent resin with a high refractive index. This can reduce defects such as pearl-like luster and poor coloring properties that appear in the appearance of molded articles of the graft copolymer.

In the crosslinking graft reaction in the third step of the present invention, 100 parts by weight of the acrylic rubber obtained in the second step is
Aromatic vinyl monomer θ ~ 80% by weight, vinyl cyanide monomer 0 ~ 40% by weight, refractive index of single polymer is 1.50
A monomer mixture consisting of 0 to 99.9% by weight of a vinyl monomer copolymerizable with the above-mentioned aromatic vinyl monomer and 0.1 to 5% by weight of a polyfunctional vinyl monomer ( It) 10～
Add 100 parts by weight and carry out seeding emulsion polymerization.

Specific examples of the aromatic vinyl monomer used in the crosslinking graft reaction include styrene, α-methylstyrene, etc.
Examples include nuclear-substituted alkylstyrenes such as furkylstyrene and p-methylstyrene, and vinylnaphthalene. These may be used alone or in a mixture of two or more.

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 will increase and the miscibility of the produced resin will be poor when mixed with other hard resins.

Specific examples of vinyl cyanide monomers include acrylonitrile, notacrylonitrile, and the like. these are,
The proportion of vinyl cyanide monomer, which may be one type or a mixture of two or more types, in the monomer mixture (III) must be 0 to 40% by weight, and if it exceeds 40% by weight, This is not preferable because the dispersibility of the crosslinked graft polymerized resin with other resins deteriorates, resulting in poor moldability.

A vinyl monomer that can be copolymerized with the aromatic vinyl monomer having a refractive index of less than 1.50 as a single polymer is a vinyl monomer that can be copolymerized with the aromatic vinyl monomer having a refractive index of less than 1.50. 1.5
It means something that is less than 0.

Specific examples of vinyl monomers copolymerizable with this aromatic vinyl monomer include methyl acrylate, t-butyl methacrylate, inbutyl methacrylate, n-hexyl methacrylate, n-butyl methacrylate, and methyl methacrylate. It will be done. These are one or two types.
It may be a mixture of more than one species.

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) of this single polymer is 0 to 99.9% by weight. %. Monomer mixture (I) contains other components, so 99
．． It does not exceed 9% by weight.

The monomer mixture (III) is a monomer mixture of polyfunctional vinyl monomers (II[
) The proportion in the range is 0.1 to 5 times the weight. 0.1
If it is less than % by weight, it becomes difficult to wrap the rubber particles of the acrylic rubber through a crosslinking graft reaction and form a layered Mt structure. If the polyfunctional vinyl monomer exceeds 5% by weight, the crosslinking density will increase, making graft polymerization in the next fourth step difficult, which is not preferable.

In the crosslinking graft reaction in the present invention, a monomer mixture (I) is added to 100 parts by weight of the acrylic rubber obtained in the second step.
T) is added in an amount of 10 to 100 parts by weight, and polymerization is carried out by a seeded emulsion polymerization method. If the amount of monomer mixture (1) added is less than 10 parts by weight, the crosslinked graft copolymer will only cover a part of the surface of the rubber particles of the acrylic rubber, which is undesirable. If (1) exceeds 100 parts by weight, the amount of acrylic rubber in the crosslinked graft particles decreases, which is not preferable.

This crosslinking graft reaction can be carried out by the usual emulsion polymerization method using water as a medium, similar to that used in the second step. At this time, it is preferable to appropriately divide the monomer mixture (III), emulsifier, polymerization initiator, etc. according to the polymerization rate of the seeded emulsion polymerization, and add them over time.

In the fourth step for producing the graft copolymer resin (A) in the present invention, 10 to 90% by weight of aromatic vinyl monomer and vinyl cyanide monomer are added to the polymerization system that has completed the third step. A monomer mixture (mV) consisting of 10 to 40% by weight of methyl methacrylate and 0 to 80% by weight of methyl methacrylate
The aromatic vinyl monomer and the vinyl cyanide monomer, which are the components of the above IIl@temperature polymer (IV), to which 5 to 185 parts by weight are added and graft polymerized are previously added in the third step. These are the vinyl monomers exemplified as components used in the crosslinking graft reaction. The above monomer mixture (W) includes 10 to 90% by weight of aromatic vinyl monomer, 10 to 40% by weight of vinyl cyanide monomer, and 0% of V/methyl methacrylate.
Constructed of ~80 wt.

If it is outside this range, the graft polymerizability will not only change, making it necessary to change the polymerization conditions, but also change the characteristics of the graft-polymerized resin and limit the types of other resins to be mixed, which is undesirable6. In the fourth step, this monomer mixture (■) in a range of 55 to 185 parts by weight is further added to the polymerization system in which 100 parts of acrylic rubber in the fjtJ3 step was crosslinked and grafted to carry out graft polymerization. The amount of monomer mixture (IV) added at this time is 5
If it is less than 5 parts by weight, a sufficient resin type cannot be generated by graft polymerization to coat the surface of the rubber particles of the acrylic rubber latex, and the grafting rate becomes small, resulting in a decrease in the impact resistance and impact resistance of the graft copolymer. If the amount added exceeds 185 parts by weight, which is undesirable because it reduces the dispersibility, the grafting rate becomes saturated and becomes constant, only the I4 fat that has not undergone graft polymerization increases, and the concentration of acrylic rubber in the resin decreases. Undesirable.

The graft polymerization in the fourth step can be carried out by emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or the like. In the case of emulsion polymerization, it can be carried out by the usual emulsion polymerization method using water as a medium as explained in the above-mentioned seeded emulsion polymerization method.

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

After completing the fourth step, the polymerization system is subjected to 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.

Graft copolymer resin (vII7&) of the composition of the present invention (
B) means 00 parts by weight of EPDMl, 10 to 90% by weight of aromatic vinyl monomer, and 10 to 4% by weight of vinyl cyanide monomer.
Adding 20 to 2000 parts by weight of a monomer mixture (V) consisting of 0% by weight and 0 to 80% by weight of methyl methacrylate,
The rubber particle size obtained by GL/7 polymerization is 0.5 to 5μ.
This graft copolymer resin (B) is
is an acrylonitrile/EPDM/styrene copolymer (
It is a type of AES resin) and is an impact-resistant resin with excellent weather resistance.

EP, which is a constituent component of the graft copolymer resin (B)
Any known DM can be used without any special restrictions.

EPDM is a rubber obtained by appropriately combining components such as ethylene, propylene, and non-conjugated diene, and polymerizing them with coordination 7 ions. Among these components, what is important when performing graft polymerization is the type and amount of non-conjugated diene that serves as the starting point for the branch components of graft polymerization. Usually, ethylidene norbornene etc. are contained in EPDM in an amount of 0.1 to 20% by weight. used at a rate of

The aromatic vinyl monomer and vinyl cyanide monomer, which are the components of the monomer mixture (V), are the same as those previously exemplified as components used in step Ij43 for producing the graft copolymer resin (A). Each vinyl monomer. The monomer mixture (V) contains 10 to 90% by weight of aromatic vinyl monomers.
, 10 to 40% by weight of vinyl cyanide monomer, and 0 to 80% by weight of methyl methacrylate. If it is outside this range, the graft polymerizability will not only change, making it necessary to change the polymerization conditions, but also change the characteristics of the graft-polymerized resin and limit the types of other resins to be mixed, which is not preferable.

This monomer mixture (V) is added to 100 parts by weight of the above EPDM.
in the range of 20 to 2000 parts by weight, preferably 200 to 2000 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 are formed and the rubber particles are cannot be coated with the resin of the graph F branch component, therefore, the surface of the graph) copolymer resin (B)
If the amount added exceeds 2000 parts by weight, only the non-grafted resin will increase and the EPDM component in the graft copolymer resin will decrease. EPDM is undesirable because it lowers the concentration of EPDM. is dissolved in the monomer mixture (V), so the amount added is 200 to 1
It is particularly preferred to select from the range of 0.000 parts by weight.

This graft polymerization can be carried out using known bulk polymerization methods, solution polymerization methods,
Methods such as a suspension polymerization method, a pour-over/emulsion polymerization method, etc. can be employed in a batch or continuous manner, or in appropriate combinations of these methods and methods. To give an example of the solution bulk-suspension polymerization method, first, a solution system is formed in which EPDM is completely dissolved in an aromatic vinyl monomer and an EPDM solvent, and then vinyl cyanide monomer is added to this system. and/or methyl methacrylate is added batchwise or continuously to perform polymerization while applying shear stress. Then, after EPDM rubber particles are stably formed, suspension polymerization is started and polymerization is completed. At the same time, the EPDM solvent is recovered. As a solvent for EPDM, various known solvents can be used alone or as a mixture. For example, n-
Hebutane, cyclohexane, etc. are most commonly used.

In this graft polymerization, a known polymerization initiator for a 7-crylonitrile rubber component-styrenic copolymer and
If necessary, add molecular weight, regulators, stabilizers, antioxidants,
Auxiliary agents such as surfactants and suspension stabilizers may be used in appropriate combinations.

E of the graft copolymer tree 111t (B) in the present invention
The rubber particle size of the PDM component is adjusted within the range of 0.5 to 5 μm. If the particle size of the component that may cause EPDM is smaller than 0.5 μm, it is not preferable because the impact resistance of the resin composition cannot be improved. If it is larger than 5 μm, the resin Since the number of rubber particles in the resin composition decreases, the impact resistance of the resin composition also decreases, which is not preferable.

In the present invention, the rubber particle size of the EPDM component is defined by Coulter Electron Co., Ltd. (USA).
Using a Coulter counter made by icsLid, ),
A small amount of the graft copolymer was dissolved in dimethylformamide, and a small amount of potassium thousocyanate was added to the solution, and the solution was heated at 23°C.
The weight average rubber particle diameter measured by

The copolymer resin (C) constituting the composition of the present invention contains 10 to 90% by weight of aromatic vinyl monomer, 10 to 40% by weight of vinyl cyanide monomer, and 0 to 40% by weight of methyl methacrylate.
It is produced by polymerizing a monomer mixture (Vl) consisting of 80% by weight. This copolymer resin (C) is a known 7-acrylonitrile-styrene copolymer (AS resin) having a molecular weight and composition suitable for the resin composition according to the present invention.

The polymerization method and polymerization conditions for the above monomer mixture (Vl) are based on known AS resin manufacturing techniques, such as emulsion polymerization method, breath polymerization method, solution polymerization method, bulk polymerization method, etc., in batch or continuous manner. The method can be selected as appropriate. The aromatic vinyl monomer and vinyl cyanide monomer which are the components of the monomer mixture (Vl) are each of the vinyl monomers exemplified above.

The monomer mixture (VI) contains 10 to 9 aromatic vinyl monomers.
0% by weight, 10 to 40% by weight of vinyl cyanide monomer, and 0 to 80% by weight of methyl methacrylate. If it is outside this range, it is not preferable because it not only requires changing the polymerization conditions, but also limits the type and composition of the other graft copolymer U (fat) to be blended.

The resin composition according to the present invention includes a graft copolymer tree 111t (A) as described above, a graft copolymer resin (
B) and the copolymer resin (C) are mixed and kneaded to make 91.

At this time, the ratio of the acrylic rubber component to be polished in the graft copolymer resin (A) and the EPDM component to be polished in the graft copolymer resin (B) is determined by weight ratio: acrylic rubber component/EPDM component= It is preferable to select a combination within the range of 97/3 to 30/70, and particularly preferred within this range is acrylic rubber component/EPDM bokmin = 97/3.
The range is from 50,150 to 50,150. Apart from this ratio of the acrylic rubber component and EPDM component, if the content of the EPDM component is too little or too much, the impact resistance tends to decrease, so it is better to select and combine them within the above ratio range. .

Further, the total of the acrylic rubber component and E PDM 111 minutes contained in the resin composition according to the present invention is
It is preferable to blend the acrylic rubber component and the EPDM component in a range of 5 to 40% by weight based on the entire resin composition. If the total amount of the acrylic rubber component and the EPDM component is too small outside the above range, the impact resistance will deteriorate. If it is too excessive, the rigidity, melt flowability, etc. of the material will decrease, and this will have an unfavorable effect on the appearance of the molded product, so it is better to keep it within the above range.

In addition, the graft copolymer resin (A) has a rubber particle size of 0.
．． Acrylic rubber having a diameter of 15 to 0.5 μm is used, and the rubber particle size of the EPDM component of graft copolymer O (fat (B) is 0.5 to 5 μm), and The rubber particle size of the acrylic rubber used for the resin (A) and the rubber particle size of the EPDM component in the graft copolymer resin (B) are combined and blended so that there is a particle size difference of at least 0.2 μm. is preferable; if the rubber particle difference is less than 0.2 μm, a satisfactory effect of improving impact resistance due to rubber cannot be obtained.

Graft copolymer resin (A), graft copolymer resin (
B) and/or the copolymer of fat (C) may be blended and mixed and kneaded by any known mixing and kneading method.

For example, a mixture of one or more of these copolymer resins in the form of powder, beads, or pellets is processed using an extruder such as a -screw extruder or a twin-screw extruder, or a Banbury mixer-1 pressurized knee gun. , using a kneading machine such as two rolls, etc.
It can be made into a resin composition. In some cases, one of these copolymer resins after polymerization or 2N
It is also possible to adopt a method in which the above materials are mixed in an undried state, precipitated, washed, dried, and kneaded.

As for the order of this mixing and kneading, three types of component resins may be mixed and kneaded at the same time, or one of the component resins may be mixed and kneaded first.
A desired resin composition may be obtained by mixing and kneading one or more types, and separately kneading one or more types and then combining and kneading the mixture.

The resin composition according to the present invention can be used as it is for molding and the like. It can also be mixed and kneaded with other thermoplastic resins, such as polystyrene, polymethyl methacrylate, polyvinyl chloride, polycarbonate, polyamide, polybutylene terephthalate, polyphenylene oxide, acrylonitrile/N-7 enylmaleimide/styrene copolymer, etc. , can be used as a weather-resistant and impact-resistant resin.

The resin composition according to the present invention contains lubricants, mold release agents, colorants, ultraviolet absorbers, light resistance stabilizers, heat resistance stabilizers, photoplants, etc., in types and amounts that do not inhibit the properties of the resin. (a) Resin additives can be added in appropriate combinations.

The resin composition according to the present invention can be produced by injection molding method, extrusion molding method,
It can be made into desired molded products by various processing methods such as compression molding, and used in applications that require excellent weather resistance and impact resistance.

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

(1) The resin composition according to the present invention has excellent colorability and surface gloss because the refractive index of the acrylic rubber particles of the graft copolymer resin (A) is optimized in stages from the inner layer to the outer layer. has.

(2) The resin composition according to the present invention has the ratio of each rubber component and the ratio of each rubber component to the acrylic rubber component in the graft copolymer resin (A) and the EPDM component in the graft copolymer resin (B). Total compounding amount,
Since each rubber particle size is optimized and blended, it can be used as a thermoplastic resin with excellent impact resistance.

(3) The resin composition according to the present invention has extremely excellent weather resistance because the base rubber is an acrylic rubber having a main chain of saturated carbon bonds and EPDM.

(4) The resin composition according to the present invention has excellent compatibility with other hard thermoplastic resins, so by cross-mixing, a different type of resin composition with excellent weather resistance and impact resistance can be manufactured. be able to.

[Examples] Next, the present invention will be specifically explained based on Examples and Comparative Examples, but the present invention is not limited to the following examples as long as the essential points 19 are not exceeded.

Example 1 (1) Production of graft copolymer tree 11W (A): (i)
First step Butyl 7 acrylate (hereinafter abbreviated as BA) 937.
5. , acrylonitrile (hereinafter abbreviated as AN) 62
．． 5 g and allyl methacrylate (hereinafter abbreviated as AMA) were weighed and mixed to form a monomer mixture (1).
was prepared.

1520 g of deionized water in a 3-1 glass flask equipped with a stirrer, reflux condenser, thermometer, and auxiliary additive addition device;
20 gb of higher fatty acid soap (mainly composed of sodium salt of fatty acid with 18 carbon atoms) and 1 portion of sodium bicarbonate
Charge 0g and raise the internal temperature to 75℃ under a nitrogen stream.
Next, 20 ml of potassium persulfate (hereinafter abbreviated as KPS) aqueous solution (containing 0.75 g of KPS) was added to the flask, followed by 40 g of monomer mixture (1), and the mixture was heated at the same temperature. 0 When the polymerization reaction started 15 minutes after starting the polymerization reaction, the remaining monomer mixture (1) 96
5 g was added continuously to the polymerization system at an addition rate of approximately 65 g/10 minutes.

15 minutes after starting the polymerization reaction, add 20% of KPS aqueous solution.
After 1 hour and 30 minutes, 6 g of higher fatty acid soap was added to start the hexapolymerization reaction, and the addition of the monomer mixture (Ii) was completed in 2 hours and 45 minutes. Furthermore, the polymerization reaction was continued for 1 hour at the same temperature to complete the reaction and obtain acrylic seed rubber particles.The conversion rate of the monomer used was 98.5%.The obtained latex The rubber particle diameter was measured.The results are shown in Table 1.

(ii) Second step: The acrylic seed rubber obtained by the method described in (i) above is placed in a glass flask with a capacity of 21 equipped with a stirrer, a reflux condenser, a thermometer, and an auxiliary agent addition device. 34.1 g of latex particles, 750 g of ionized water, and 3.9 g of sodium bicarbonate were charged, and the internal temperature of the flask was raised to 75°C. 8 ml of KPS aqueous solution (containing 0.3 g of KPS,
) was added to prepare for polymerization.

On the other hand, 3 consisting of the following composition added to the polymerization system in the second step
Monomer mixtures of types (n)-A, (17)-B, (If
)-C was prepared.

[Note 1*1 means nibutyl acrylate.

The following shall have the same meaning.

The above three types of monomer mixtures (1)-A, (H)-B, (
11) -C was sequentially added to the flask in three stages according to the following procedure to start and continue the polymerization reaction.

45 minutes after starting the polymerization reaction, 30 minutes after opening at 1 o'clock,
After 3 hours and 4 hours, soap aqueous solution 101 (
Contains 0.92g of higher fatty acid soap.

After starting the polymerization reaction, 4 ml of KPS aqueous solution (containing 0.15 g of KPS) was added after 130 minutes and 3 hours after starting the polymerization reaction.
After 4 hours and 30 minutes, the addition of the monomer mixture was completed, and the reaction was continued for an additional hour at the same temperature, and after the polymerization reaction was completed, the rubber particle diameter of the obtained acrylic rubber was measured.

The results are shown in Table 1.

(iii) In the same 31 glass flasks as used in the first step of the third culm, the entire amount of the acrylic rubber latex obtained by the method described in (ii) above and 750 g of deionized water were added.

and 6 g of F hydrogen carbonate were charged, and the internal temperature was raised to 75° C. for 7 rasps. KPS Water Soluble 8!8 Port 1 (KPSO
, 3 g) was added to prepare for polymerization.Meanwhile, a monomer mixture <l1l) having the following composition to be added to the polymerization system in the third step was prepared.

Monomer mixture (Iff) MMA book 4 58.5g 5t 95.6g AN 40.91+ AMA 1 g [Note 1 4: Means methyl methacrylate.

The following shall have the same meaning.

The above monomer mixture (III) was added at an addition rate of 16.3
g/ 105tllllt'7u
After 1 hour and 30 minutes, 20 ml of an aqueous soap solution (containing 1.95 g of higher fatty acid soap) was added. After 2 hours, the addition of monomer mixture (III) was completed and the crosslinking graft reaction was completed.

(i) 4th step Leave the polymerization system that has completed the 3rd step described in (iii) above as it is, maintain the flask internal temperature at 75°C, and add 8 ml of KPS aqueous solution (0.3 g of KPS) with stirring. including,
) was added. and 5L286.61 and ANl
22.9 g of monomer mixture (IV) was continuously added at an addition rate of 22.8 g/10 minutes to start the graft polymerization reaction.

1 hour and 3 hours after starting the polymerization reaction,
20ml of each soap aqueous solution (containing 2g of higher fatty acid soap,
), and after 1 hour, KPS aqueous solution 8 theory!
(KPSo, 3 [including 1, included)] was added to the monomer mixture (It/) 3 hours after starting the polymerization reaction.
After completing the addition, the reaction was continued for an additional hour at the same temperature to complete the graft polymerization reaction.

The conversion rate of the monomers used was 99%. The graft-polymerized latex was salted out by a conventional method, thoroughly washed with water, and dried to obtain Graph F copolymer lk.

(2) Production of graft copolymer resin (B) St552g% in a 2-1 autoclave equipped with an Ikari-type stirrer
EPDM [Mooney viscosity ML, (100°C) 45
, iodine value 25, 1140. containing ethylidene norbornene as the main component. After charging 100 g of n-heptane and purging with nitrogen, the solution was completely dissolved by stirring at 100 rpm for 2 hours at 50°C.
After charging at a rate of 40g/10 minutes,
Butyl Peroxide"5L 0.13 g of tcrt-butyl peracetate and 0.5 g of Terpircin were charged and bulk polymerization was carried out at 97 DEG C. for 7 hours and 20 minutes.

Approximately 30 minutes before the end of bulk polymerization, 1.5 g of di-tert-butyl peroxide and 1.5 g of terpircin were added to St50.
The EPDM rubber particle size at the end of zero polymerization was 1.6 μm.

The syrup obtained in the bulk polymerization step was added to 1100 g of water.
Suspending agent (acrylic acid, alkyl acrylate copolymer)
2.5. 31 autoclave (equipped with a 3-blade stirrer) containing an aqueous solution of
This aqueous suspension system was heated at 130°C and 500 rpm for 2 hours.
Suspension polymerization was carried out for a period of time, and then the temperature was raised to 150°C and stripping was carried out for 1 hour. After washing the obtained resin composition with water, it was dried at 100°C to a temperature of 920°C. A graft copolymer resin was obtained.

(3) Production and evaluation of resin compositions 552.5 g of graft copolymer resin (A) obtained by the method described in (1) above, graft copolymer obtained by the method described in (2) above 278.6g of resin (B).

and acrylonitrile/styrene copolymer (SAN/
-〇, manufactured by Mitsubishi Monsanto Chemicals Co., Ltd.) 468.9 g, butylated hydroxytoluene 3 g.

Weighed 5 g of magnesium stearate and kneaded it in a test Banbury mixer whose temperature was adjusted to 180°C. % of the resin composition was made.

A pellet of this resin composition was molded into test pieces for impact resistance measurement and gloss evaluation using an injection molding machine.

In accordance with JIS K7110, the gloss by reflectance at an incident angle of 60' was measured in accordance with JIS K7105. The results are shown in Table 1.

In order to evaluate the coloring property, when the raw materials for the composition were kneaded in the Banbury mixer for testing, 5.2 g of carbon black for coloring was mixed and added, and coloring was carried out in the same manner as above. A pellet of the resin composition was prepared.

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

Judgment criteria for colorability and appearance ◎: Good colorability. It becomes a deep black (jet black).

There is no pearl-like luster, and weld lines (t, 41 fat fusion bond #l) are hardly observed.

○: Colorability is normal. The black lacks depth and requires an increased amount of colorant to match. There is no pearl-like luster, but some weld lines are observed.

X: 5? y-chromaticity is poor. Even by increasing the amount of one colorant, which results in a dull gray-like black, color matching is difficult.

It exhibits pearl-like luster and some delamination is observed. Weld lines are clearly visible.

Example 2 (1) &! of graft copolymer resin (A) Construction: (1)
First step example H1) (same as described in i>).

(ii) Second step Same as described in Example 1(1)(ii).

(iii) Third Step Example 1 In the example described in (1)(iii), the composition of the monomer mixture (Ill) was changed as shown below. The procedure was the same as in .

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

(2) Production Example 1 (2) of graft copolymer resin (B)
).

(3) Production and evaluation of resin compositions 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 (IHi).

(ii) @2 steps In the example described in Example 1 (1) (ii), the composition of the monomer mixture (II) is the following two types, and the addition is performed in two stages as shown below. Except for changes, ipsilateral (1) < i
The procedure was the same as in i).

have the same meaning.

(iii) Third step Same as described in Example 2 (1) (iii).

V) 4th step Same as described in Example 1 (1) (iv).

(2) Production Example 1 of graft copolymer tree *(B) (
Same as described in 2).

(3) Production and evaluation of resin compositions Same as described in Example 1 (3).

Comparative Example 1 (1) G1 construction of graft copolymer resin (A): (i)
First step Same as described in Example 1(1)(i).

(11) Second step In the example described in Example 1 (1) (ii), the composition of the monomer mixture ([1) was changed to 390 g of BA and AMAl,
95g, and the addition method was 4 hours 3 immediately after the start of the polymerization reaction.
The procedure was the same as in (1) (ii) on the same side, except that the monomer mixture (n) was added continuously at a rate of 14.5+r/10 minutes until 0 minutes elapsed. did.

(iii) Third step Same as described in Example 2 (1) (iii).

Nima) 4th process Same as described in Example 1(1)<iv).

(2) Production Example 1 (2) of graft copolymer resin (B)
).

(3) Production and evaluation of resin compositions Same as described in Example 1 (3).

Comparative Example 2 (1) g of graft copolymer resin (A)! Construction: (1) First step Example 1 Same as described in (1)(i).

(ii) Second step In the example described in Example 1 (1) (ii), the composition of the monomer mixture (ff> is BA 195., MMΔ195
g, and AMAl, 9S, the addition method was changed from immediately after the start of the polymerization reaction to Q4 hours and 30 minutes after the start of the polymerization reaction, and the monomer mixture <1
The procedure was the same as in (1) (ii) on the same side, except that 1) was added continuously at a rate of 14.5 g/10 minutes.6 (iii) Third step Example 2 (1) ) Same as described in (iii).

(iv> 4th step Same as described in Example 1(1)(iv).

(2) Production Example 1 of graft copolymer resin (B) (
Same as described in 2).

(3) Production and evaluation of resin compositions Same as described in Example 1 (3).

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

(ii) Second step Same as used in the second step of Example 1 (1) (ii), 2
In the glass flask of No. 1, latex 34 of acrylic seed rubber particles obtained by the method described in (i) above, Ig,
750 g of deionized water, and 3.9 g of sodium bicarbonate
KPS.
3 ml of aqueous solution (containing 0.1 g of KPS) was added.

BA57g and AMAo, 3. Monomer mixture (II) consisting of 14.3 g of monomer mixture (II) was added continuously over 710 minutes to start the polymerization reaction. 45 minutes after starting the polymerization reaction, 5 coats of soap aqueous solution (higher fatty acid soap) 0.3
After starting the polymerization reaction, 4
After 0 minutes, the addition of monomer mixture (II) was completed, and the reaction was then continued at the same temperature for an additional hour to complete the polymerization reaction. The rubber particle diameter of the obtained acrylic rubber was measured. The results are shown in Table 1.

(iii) tJS3 step example 1 (1) (iii) Into the same 31 glass flask as used in the third step, charge the entire amount of the acrylic rubber latex obtained by the method described in (ii) above, The internal temperature of the flask was raised to 75°C. 4 parts of KPS aqueous solution (containing 0.15 g of KPS) was added. St
Monomer mixture (III) consisting of 2 ig, AN9[, t(yo(/AMA) 0.15 g was added at an addition rate of 12.0 g.
The polymerization reaction was started by continuous addition for 10 minutes. 25 minutes after starting the polymerization reaction, the monomer mixture (tit
) was completed, and the crosslinking graft reaction was completed.

(1v) Fourth step: The polymerization system obtained by the method described in (iii) above and subjected to the crosslinking graft reaction was continuously heated to a temperature of 75
℃ and stirred.

A monomer mixture (IV) consisting of 52.5 g of St and 22.5 g of AN was continuously added at an addition rate of about 30 g/10 minutes to start the graft polymerization reaction.

40 minutes after starting the polymerization reaction, soap aqueous solution 101
(containing higher fatty acid soap 1.05.
) was completed, and the reaction was continued for an additional hour at the same temperature to complete the polymerization reaction.

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

(2) Production Example 1 of graft copolymer resin (B) (
Same as described in 2).

(3) Production and Evaluation of Resin Composition The graft copolymer resin (A ), reduce the amount of
So that the total amount of kneaded sample is the same weight as the same side (3),
7 The procedure was the same as on the same side (3) except that the amount of the acrylonitrile-styrene copolymer was increased.

From Table 1, the following becomes clear.

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

On the other hand, in the case of a comparative example in which the refractive index of the acrylic rubber particles is small and the refractive index of the diluted resin is large, and the refractive indices do not approximate each other and vary discontinuously, the colorability or surface gloss will be poor. (See Comparative Example 1.2).

(2) The resin composition according to the present invention has a ratio of each rubber component, a ratio of each rubber component, and an EPDM component in the graft copolymer resin (B). The total blending amount of the components and the rubber particle diameter of each component are optimized and blended, so it has excellent impact resistance (Examples 1 to 3).
3) 6 Furthermore, resin compositions obtained outside the scope of the present invention have poor impact resistance (see Comparative Example 1.3).

Claims (3)

[Claims] (1) 70 to 100% by weight of an alkyl acrylate monomer whose alkyl group has 1 to 8 carbon atoms, 0 to 30% by weight of a vinyl monomer copolymerizable with the above alkyl acrylate, and 0% by weight of a polyfunctional vinyl monomer. Monomer mixture consisting of ~5% by weight (however, the total monomer mixture is 100% by weight)
is subjected to emulsion polymerization to obtain a rubber particle size of 0.03 μm to 0.
．． A first step of producing acrylic seed rubber particles having a diameter of less than 15 μm, 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. 20 to 94.9% by weight, 5 to 79.9% by weight of a vinyl monomer copolymerizable with the above alkyl acrylate whose single polymer has a refractive index of 1.50 or more, and 0 polyfunctional vinyl monomer. A monomer mixture consisting of .1 to 5% by weight (however, the total monomer mixture is 100% by weight).
A second step of adding 2.5 to 125 parts by weight and producing an acrylic rubber having a rubber particle size of 0.15 to 0.5 μm by a seeded emulsion polymerization method, the acrylic rubber obtained in the second step above. 100 parts by weight of rubber, 0 to 80% by weight of aromatic vinyl monomer, 0 to 40% by weight of vinyl cyanide monomer, and the refractive index of the single polymer is 1.5.
A monomer mixture consisting of 0 to 99.9% by weight of a vinyl monomer copolymerizable with less than 0 of the above aromatic vinyl monomers and 0.1 to 5% by weight of a polyfunctional vinyl monomer (but (The total monomer mixture is 100% by weight.) 10 to 100 parts by weight is added to the third step of cross-linking and grafting reaction by seeded emulsion polymerization method. Group vinyl monomer 10-90% by weight, vinyl cyanide monomer 10-4
0% by weight, and methyl methacrylate 0-80% by weight
(However, the monomer mixture consists of a total of 10
0% by weight. ) Graft copolymer resin (A) obtained by adding 55 to 185 parts by weight and carrying out graft polymerization, ethylene propylene non-conjugated diene copolymer rubber (EPDM)
100 parts by weight, 10 to 90% by weight of aromatic vinyl monomer
, 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 monomer mixture is 100% by weight) 20 to
A graft copolymer resin (B) in which 2000 parts by weight is added and the rubber particle diameter obtained by graft polymerization is 0.5 to 5 μm, and 10 to 90 weight % of aromatic vinyl monomer.
, 10 to 40% by weight of vinyl cyanide monomer, and 0 to 80% by weight of methyl methacrylate (however, the total monomer mixture is 100% by weight).
An impact-resistant resin composition characterized by containing a copolymer resin (C) obtained by polymerizing the following. (2) The ratio of the acrylic rubber component derived from the graft copolymer resin (A) to the EPDM component derived from the graft copolymer resin (B) is such that the weight ratio is acrylic rubber component/EPDM component = 97. The impact-resistant resin composition according to claim 1, characterized in that the composition is blended within the range of /3 to 30/70. (3) A patent claim characterized in that 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 based on the entire resin composition. The impact-resistant resin composition according to any one of item (1) and item (2).