JPH06228409A - Graft copolymer resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition excellent in impact resistance, chemical resistance and moldability and useful for inner box materials for electric refrigerators, by including two kinds of graft copolymers and rigid copolymer. CONSTITUTION:The composition contains (A) a graft copolymer whose rubber- based polymer has a form of globular particles 1, obtained by subjecting 20-90 pts.wt. mixture consisting of an aromatic vinyl, vinyl cyanide and other vinyl monomer to emulsion polymerization in the presence of 10-80 pts.wt. rubber- based polymer latex having 0.1-0.65mum (weight-average) particle diameter, (B) a graft copolymer whose rubber-based polymer has grape-like secondary particles 2 having 0.4-3mum particle diameter, obtained by subjecting a mixture consisting of an aromatic vinyl, vinyl cyanide and other vinyl monomer to emulsion polymerization in the presence of 10-80 pts.wt. rubber-based polymer latex having 0.05-0.2mum particle diameter and obtained by a conjugated diene monomer to emulsion polymerization with a vinyl monomer and (C) a rigid polymer obtained by polymerizing an aromatic vinyl with vinyl cyanide and other vinyl monomer in ratios of formula I, formula II and formula III.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a graft copolymer resin composition. More specifically, the present invention has two types of specific graft copolymers or two types of specific graft copolymers and a hard copolymer, and has impact resistance, chemical resistance and good moldability. The present invention relates to a graft copolymer resin composition which is useful not only as an impact resistant material itself but also as a compounded with another resin to form an impact resistant resin composition.

[0002]

2. Description of the Related Art A graft copolymerization method is well known as one of methods for obtaining an impact resistant resin, and it is known that a resinous resin is prepared in the presence of a rubbery polymer (for example, a latex of a conjugated diene polymer). A graft copolymer resin composition produced by polymerizing a monomer (for example, styrene + acrylonitrile) to give a polymer is widely used as an impact resistant resin. Of these, the graft copolymer composed of polybutadiene / styrene / acrylonitrile is well known as an ABS resin.

However, for example, ABS resin is inferior in properties such as chemical resistance, for example, when it is brought into contact with a specific chemical agent under a stress load, a crack is generated, and in a remarkable case, a phenomenon of breaking is observed. there were. In order to obtain a resin excellent in these properties, a method of increasing the content ratio of the acrylonitrile component in the ABS resin (for example, JP-A-47-5594), ABS resin and acrylic rubber / styrene / acrylonitrile (ASA resin) (JP-B-54-40258), a method of mixing an acrylic acid ester polymer with an ABS resin (JP-B-63-22222), and a method of mixing two types of characteristic graft copolymers. (Japanese Patent Publication No. 57-22064 and Japanese Patent Application Laid-Open No. 2-175745) have been proposed.

However, although these techniques can be said to be meaningful as a solution to the existing problems, they are not completely satisfactory as far as the present inventors know. That is, among the proposed methods, JP-A-47-5594 and JP-B-54-40
In No. 258, etc., a defective phenomenon such as a surface appearance defect called a flow mark or a surface peeling phenomenon may be observed in the surface condition of the injection molded product, and the surface condition of the extruded molded product is referred to as die band. Such a poor surface appearance was sometimes observed, which was a big problem in use.

In addition, in the fields proposed in Japanese Patent Publication No. 57-22064 and Japanese Patent Application Laid-Open No. 2-175745, the chemical resistance is insufficient, and in the field where more chemical resistance is required, After all, it was a problem in use.

[0006]

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned problems, and two kinds of rubbery polymers having a specific average particle diameter are individually and individually treated with a specific grafting ratio and a specific grafting ratio. As described above, a monomer mixture comprising an aromatic vinyl monomer, a vinyl cyanide monomer and another vinyl monomer copolymerizable therewith, is subjected to a graft polymerization reaction by an emulsion polymerization method. It is intended to achieve this object by uniformly mixing the graft copolymers (A) and (B) having a certain particle morphology and the hard copolymer (C) having an affinity with them.

[0007]

SUMMARY OF THE INVENTION However, the gist of the present invention lies in that the following graft copolymer A, graft copolymer B and hard polymer C are prepared from the following (1) to (3): The graft copolymer resin composition is characterized in that it is contained in a composition ratio.

Graft Copolymer A : The graft copolymer A is defined as follows. (1) In the presence of 10 to 80 parts by weight (based on the solid content) of a rubbery polymer latex having a weight average particle size of 0.10 to 0.65 μm, 30 to 80% by weight of an aromatic vinyl monomer and cyan A graft copolymer obtained by emulsion-polymerizing 20 to 90 parts by weight of a monomer mixture consisting of 20 to 70% by weight of a vinyl chloride monomer and 0 to 20% by weight of another vinyl monomer copolymerizable therewith. (2) Rubbery polymer 1
20 to 120 parts by weight of aromatic vinyl monomer, vinyl cyanide monomer and other vinyl monomer copolymerizable with these are chemically bonded to 00 parts by weight,
(3) The rubbery polymer has a form of dispersed spherical particles.

Graft Copolymer B : The graft copolymer B is defined as follows. (1) A monomer mixture of 60% by weight or more of a conjugated diene-based monomer and 40% by weight or less of a vinyl monomer copolymerizable with the conjugated diene-based monomer has a weight average particle diameter of 0 obtained by emulsion polymerization. Rubber polymer latex 1 having a particle size of 0.05 to 0.2 μm
In the presence of 0 to 80 parts by weight (based on solid content), aromatic vinyl monomer 12 to 80% by weight, vinyl cyanide monomer 8 to
20 to 90 parts by weight of a monomer mixture consisting of 70% by weight, 2 to 60% by weight of a conjugated diene monomer and 0 to 20% by weight of another vinyl monomer copolymerizable therewith, and obtained by emulsion polymerization. (2) 10 to 70 parts by weight of an aromatic vinyl monomer, a vinyl cyanide monomer, and the other copolymerizable with 100 parts by weight of the rubbery polymer. That the vinyl monomers of are chemically bonded,
(3) The rubbery polymer contains grape-like secondary particles having an average particle diameter of 0.4 to 3.0 μm in which primary particles are aggregated.

Hard Copolymer C : The hard copolymer C is defined as follows. (1) A monomer mixture comprising 30 to 80% by weight of an aromatic vinyl monomer, 20 to 70% by weight of a vinyl cyanide monomer, and 0 to 20% by weight of another vinyl monomer copolymerizable therewith. A hard copolymer obtained by polymerizing.

[0011]

[Equation 4]

[0012]

[Equation 5]

[0013]

[Equation 6]

[Detailed Description of the Invention] In the graft copolymer resin composition of the present invention, two kinds of rubbery polymers having a specific average particle diameter are individually made to have a specific graft ratio. A characteristic particle morphology is obtained by a graft polymerization reaction of a monomer mixture consisting of an aromatic vinyl monomer, a vinyl cyanide monomer and another vinyl monomer copolymerizable therewith by an emulsion polymerization method. The graft copolymers (A) and (B) are blended with the hard copolymer (C) having a uniform composition and having an affinity for them.

[I] Graft Copolymer 1) General Description As a graft copolymer, as usual, all the monomers to be "branches" are combined with a rubbery polymer having a "stem" to form "branches". However, the "graft copolymer" in the present invention is also a polymer derived from a "branch" monomer which is not such "branch" according to the commonly used place. It allows the coexistence of.

(1) Rubbery Polymer Latex The rubbery polymer used in the present invention generally has a glass transition temperature lower than room temperature. Examples of such rubbery polymers include (a) rubber elasticity mainly derived from a conjugated diene monomer, that is, a conjugated diene polymer, (b) acrylic acid ester polymer, and (c) ethylene. -Propylene binary copolymer or ethylene-propylene-non-conjugated diene terpolymer (so-called E
It is an olefin rubber such as PDM).

As the conjugated diene polymer rubber (a), a homopolymer of a diene having 4 to 5 carbon atoms, for example, 1,3 butadiene, isoprene or chloroprene, and its copolymerization weight containing 50% by weight or more of such a conjugated diene. Coalescence is typical. In that case, as a monomer that can be used for copolymerization with a conjugated diene, particularly butadiene, styrene, α
-Aromatic vinyl monomers such as methylstyrene and vinyltoluene, acrylic acid, methacrylic acid and its methyl,
Acrylic monomers such as ethyl, propyl, n-butyl,
Examples thereof include vinyl cyanide-based monomers such as acrylonitrile and methacrylonitrile.

As the acrylic ester polymer rubber (b), acrylic acid and 2 to 12 carbon atoms, preferably 4 to
Esters with eight monohydric alcohols are suitable. When the carbon number is out of the above range, sufficient rubber elasticity cannot be obtained, which is not preferable. These esters may be used alone or in combination of two or more. Examples of the olefin rubber (c) include a binary copolymer (EPR) composed of ethylene and propylene or butene, and a terpolymer (E) composed of ethylene, propylene or butene and a non-conjugated diene.
PDM) and the like, and one kind or two or more kinds are used.
Examples of the non-conjugated diene in the terpolymer (EPDM) include dicyclopentadiene, ethylidene norbornene,
1,4-hexadiene, 1,4-cyclopentadiene,
1,5-cyclooctadiene and the like can be mentioned. The molar ratio of ethylene to α-olefin in the binary copolymer (EPR) and the ternary copolymer (EPDM) is from 5: 1 to 1:
It is preferably within the range of 3. In the terpolymer (EPDM), the proportion of the non-conjugated diene is preferably in the range of 2 to 50 in terms of iodine value.

Among these rubbery polymers, the conjugated diene polymer rubber (a), which is easy to obtain in the form of latex, is most preferable. That is, the conjugated diene polymer latex can be produced by emulsion polymerization of a predetermined monomer or a mixture thereof in an aqueous medium at once or stepwise. The rubbery polymers used for the graft copolymers A and B in the present invention may be the same or different.

(2) Graft Polymerization The graft copolymers A and B in the present invention are aromatic vinyl monomers, vinyl cyanide monomers and graft copolymers in the presence of the rubbery polymer latex as described above. The polymer B is obtained by a graft polymerization reaction of a monomer mixture containing a conjugated diene monomer and another vinyl monomer copolymerizable therewith by an emulsion polymerization method.

The conditions for the graft polymerization reaction are essentially the same as those conventionally used in the production of ABS resins, as long as they satisfy the requirements prescribed in the present invention. The conditions for the graft polymerization reaction of the graft copolymers A and B do not have to be the same, and the optimum conditions can be selected for each particle size. <Monomer> The aromatic vinyl monomer used in the present invention includes styrene, and side-chain or / and nucleus-substituted styrene (substituents are a lower alkyl group, a lower alkoxy group, a trifluoromethyl group, a halogen). Atom, etc.), for example α
-Methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, nuclear halogenated styrene,
There are α- or β-vinylnaphthalene and others.
These may be used in combination within a group or between groups. The types of monomers used in the graft copolymers A and B (as well as the hard copolymer C) may be the same or different.

The vinyl cyanide monomer used in the present invention includes acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like. These may be one kind or a mixture of two or more kinds. In the graft copolymer B, a conjugated diene-based monomer is made to coexist with a monomer to be graft-polymerized with a rubbery polymer. Examples of the conjugated diene-based monomer include 1,3 butadiene, isoprene, chloroprene and the like. These may be one kind or a mixture of two or more kinds.

As the monomer, a small amount of another monomer copolymerizable with the above-mentioned monomer may be used in combination, as long as the object of the present invention is not impaired. Examples of such a monomer include acrylic acid, an ester of methacrylic acid and an alkanol having a carbon number of 1 to 10, particularly methyl methacrylate, divinylbenzene, (poly) alkylene glycol di (meth) acrylate, and the like. There is.

<Graft Polymerization Reaction> The graft copolymerization reaction is carried out in the presence of a polymerization initiator. As the initiator (or catalyst) that can be used, persulfuric acid, peracetic acid, perphthalic acid and other peracid catalysts, potassium persulfate and other peracid catalysts, hydrogen peroxide, benzoyl peroxide, chlorobenzoyl peroxide, etc. There are peroxide catalysts such as naphthyl peroxide, acetyl peroxide, benzoylacetyl peroxide, lauroyl peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, and azo catalysts such as azobisisobutyronitrile. These may be used alone or in admixture of two or more. They can also be used as redox catalysts in combination with reducing agents.

The graft copolymerization reaction can be carried out in the presence of a chain transfer agent. The chain transfer agent used in the present invention is not particularly limited, but for example, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, etc., or terpinolene, α-methylstyrene linear dimer, etc. are used. The polymerization reaction temperature when carrying out the graft copolymerization reaction is 50 to 85 ° C., preferably 5
A range of 5 to 75 ° C is suitable. When the temperature is lower than 50 ° C, the polymerization reaction rate is too slow to be practical, and when the temperature exceeds 85 ° C, the reaction occurs at once, and the solidified product is generated in the reaction product or the deposit on the reaction vessel (can). (Scale) is increased, and the polymerization rate and the quality of the final product are deteriorated, which is not preferable.

Other graft polymerization reaction conditions are ABS.
It is essentially the same as is commonly used in the manufacture of resins. The total amount of the graft copolymerization monomer may be introduced into the polymerization system at once, or may be introduced stepwise. Moreover, the polymerization initiator and the chain transfer agent may be introduced into the polymerization system all at once, or may be introduced stepwise. Further, the temperature of the polymerization system can be changed with time during the polymerization.

In producing a graft copolymer resin composition, first, a graft copolymer latex specified in the above range is produced, and then an aromatic vinyl monomer, a vinyl cyanide monomer, and a copolymer with them are produced. A hard polymer latex obtained by copolymerizing a monomer mixture of other possible vinyl monomers may be mixed, or the graft copolymer resin composition may be directly grafted without mixing the hard polymer latex. You may manufacture a thing. In the former case, the weight ratio of the monomers of the "branching" monomer of the graft copolymer latex to be mixed and the weight ratio of the monomers of the hard polymer latex may be the same or different.

2) Graft Copolymer A The graft copolymer A used in the present invention is a limited graft copolymer resin satisfying the above-mentioned specific conditions. That is, the rubbery polymer content is 10
-80 parts by weight, preferably 20-70 parts by weight.
When the rubbery polymer content is less than this range, the resin composition of the present invention does not have sufficient impact resistance, and when it is higher than this range, sufficient rigidity cannot be obtained.

Graft Copolymer A is a relatively large amount of "branching" monomer chemically bonded to the "branching" polymer. That is, based on 100 parts by weight of the rubbery polymer, the total amount of the monomer mixture consisting of the aromatic vinyl monomer, the vinyl cyanide monomer, and the other vinyl monomer copolymerizable therewith is used. 20 to 120 parts by weight, preferably 30 to 10
0 parts by weight are chemically bonded. If the amount of the chemical bond of the “branch” monomer to the “stem” polymer, that is, the graft ratio is less than this range, impact resistance is not expressed, and if it is more than this range, the processability is deteriorated. There is a tendency. The amount or content of chemically linked “branches”. That is, the graft ratio is measured by the following method.

(Measurement of Graft Ratio) A certain amount (X) of the graft copolymer is put into acetonitrile and left overnight. After sonicating for 15 minutes to completely dissolve the free copolymer, use a centrifuge to obtain 2000 rp.
Centrifuge at m for 1 hour to obtain insoluble matter. This is dried at 60 ° C. overnight using a vacuum dryer to obtain an insoluble matter (Y). The graft ratio was calculated by the following formula.

[0031]

[Equation 7] The rubber fraction (R) of the graft copolymer resin composition is calculated from the rubbery polymer and the graft copolymer used.

The weight ratio of the "branching" monomer in the graft copolymer A is such that the aromatic vinyl monomer is 30 to 80% by weight, the vinyl cyanide monomer is 20 to 70% by weight, and the amount thereof is Other polymerizable vinyl monomer 0 to 20% by weight, preferably 40 to 80% by weight, 20 to 60% by weight, 0
Is about 20% by weight. If the amount of the vinyl cyanide monomer is more than the range of these weight ratios, the processability and the color tone are deteriorated, and if it is less, the chemical resistance is decreased, which is not preferable.

(Particle Diameter of Rubbery Polymer) The weight average particle diameter of the rubbery polymer is in the range of 0.10 to 0.65 μm, preferably 0.15 to 0.45 μm. 0.
When it is less than 10, the impact resistance of the finally obtained resin is remarkably inferior and the moldability is also insufficient. 0.65
If it exceeds μm, the appearance of the molded product deteriorates, and only a resin having low impact resistance can be obtained. Moreover, the latex becomes unstable during emulsion graft polymerization, and the resin adheres to the polymerization container (can) during the polymerization. Since problems such as an increase in the amount of kimono (scale) will occur,
Not preferable. The rubbery polymer particles in the graft copolymer A have a spherical morphology dispersed in the graft copolymer composition.

The weight average particle diameter of the rubbery polymer latex is measured by "Nanosizer" manufactured by Coulter Co., USA. The weight average particle size of the rubbery polymer in the graft copolymer can be measured by an electron microscope for an ultrathin section cut from a test piece molded by an injection molding machine. The rubbery polymer latex having a relatively large particle size may be obtained by performing a particle size enlargement operation on a rubbery polymer latex having a small particle size in order to obtain a target particle size. , A known method, for example, a method in which the latex is once frozen and then thawed again, a method in which a mineral acid or the like is added to the latex to temporarily lower the pH of the latex, a method in which a shearing force is applied to the latex, etc. It can be carried out according to JP-A-54-133588 and JP-A-59-202121). In particular, the method of adding phosphoric acid or acetic anhydride to the latex is preferable because the particle size can be easily adjusted.

2) Graft Copolymer B The graft copolymer B used in the present invention is a limited graft copolymer resin as in the case of the graft copolymer A. That is, the rubbery polymer content is
It is 10 to 80 parts by weight, preferably 20 to 70 parts by weight. When the rubbery polymer content is less than this range, the resin composition of the present invention does not have sufficient impact resistance, and when it is higher than this range, sufficient rigidity cannot be obtained.

The degree of grafting is from 10 to 70 parts by weight of "branched" polymer, preferably 2 per 100 parts by weight of "stem" polymer.
0 to 60 parts by weight. If the graft ratio is lower than this range, the impact resistance is not expressed, and if it is higher than this range, the processability tends to decrease, and the graft copolymer B has a morphological characteristic (in both clusters and clusters). Say)
The flocculation structure (details below) is not taken, and the chemical resistance is reduced.

The weight ratio of the "branching" monomer in the graft copolymer B is 12 to 80% by weight of the aromatic vinyl monomer, 8 to 70% by weight of the vinyl cyanide monomer, and the conjugated diene-based monomer. 2 to 60% by weight, and 0 to 20% by weight of other vinyl monomers copolymerizable with them, preferably 25 to 25%, respectively.
75% by weight, 12-65% by weight, 10-45% by weight, and 0-20% by weight. From these weight ranges,
If the amount of vinyl cyanide monomer is large, the processability and color tone are deteriorated, and if it is small, the chemical resistance is deteriorated, which is not preferable. When the conjugated diene-based monomer is present in the above range, a grape-like aggregate structure is likely to be formed, which has the effect of improving chemical resistance.

The graft copolymer B is characterized by the particle shape of the rubbery polymer. That is, the particles of the rubbery polymer of the latex for the graft copolymer B have a content of 0.05 to 0.
It has a weight average particle diameter of 20 μm, preferably 0.07 to 0.18 μm, and when they are aggregated, 0.4 to
Grape-shaped particles having an average particle diameter of 3.0 μm are contained to give good chemical resistance to the composition of the present invention. The average particle size of the grape-shaped particles is 0.4 μm
If it is smaller than this, this effect is small, and if it is larger than 3.0 μm, the rigidity is largely reduced due to aggregates.

As in the case of the graft copolymer A, such a rubbery polymer latex having a relatively large particle diameter is used to increase the particle diameter of the latex having a small particle diameter so that the latex has a desired particle diameter. May be obtained by performing. The grape-like aggregates were rubbery polymer particles in the rubbery polymer latex (particle diameter of the graft copolymer B was 0.05
~ 0.20 μm) (hereinafter referred to as primary particles)
Graft polymerization, while substantially maintaining the particle morphology,
The secondary particles are in the form of grapes or clusters, which have undergone agglomeration and association by several or more through post-treatments such as salting-out, acidification, and drying, and processing operations such as extrusion and molding. The secondary particles composed of the grape-like aggregates are considered to be those in which the primary rubber particles in the matrix of the resin composition are physically or chemically associated with each other and are aggregated and frozen.
The primary particles are not dissociated by the usual blending and kneading operation of the graft copolymer. Such secondary particles are
It can be measured by an electron microscope. The average particle size of the graft-polymerized rubber-like polymer of the rubbery polymer, that is, the secondary particles, means the average of the maximum dimensions.

FIG. 1 is a schematic diagram showing a dispersed state of rubbery polymer particles obtained from an electron micrograph of a section of an ultrathin layer cut from an injection-molded test piece of the resin composition of the present invention. It shows that the rubbery polymer is mainly composed of grape-like (cluster-like) particles 1 derived from the graft copolymer B and single particles 2 mainly derived from the graft copolymer A. Is.

4) Rubbery Polymer Fraction of Graft Copolymer Graft copolymers A and B according to the present invention are aromatic vinyl monomer and vinyl cyanide monomer in the presence of rubbery polymer latex. And the graft copolymer B are obtained by a graft polymerization reaction of a monomer mixture of a conjugated diene-based monomer and another vinyl monomer copolymerizable therewith by an emulsion polymerization method. That is, as described above. The rubbery polymer fraction (weight fraction) of the obtained graft copolymer is 5 to 50%, preferably 10 to 3
Must be 5%. When it is less than 5%, it becomes difficult to develop the impact resistance of the produced resin composition, and the effect as an impact resistance improver is reduced. On the other hand, if it exceeds 50%,
When molding the graft copolymer resin composition, the processability is lowered, and not only the gloss of the molded article is impaired but also the impact resistance is lowered.

[II] Hard Copolymer C The hard copolymer that constitutes the resin composition according to the present invention comprises 30 to 80% by weight of an aromatic vinyl monomer and 20 to 70% by weight of a vinyl cyanide monomer. , And 0 to 20% by weight of other vinyl monomers copolymerizable therewith, preferably 4 each
It is a polymerization product of a monomer mixture consisting of 0 to 80% by weight, 20 to 60% by weight, and 0 to 20% by weight. If the amount of the vinyl cyanide monomer is larger than these weight ranges, the processability and color tone are deteriorated, and if it is smaller, the chemical resistance is deteriorated, which is not preferable.

Specific examples of the aromatic vinyl monomer, the vinyl cyanide monomer, and other vinyl monomers copolymerizable with these, which are the constituents of the above copolymer, are mentioned above in the graft copolymer. It can be found among those exemplified as the constituents of A and B. The polymerization method and polymerization conditions of the above copolymer can be appropriately selected from batch or continuous methods such as a solution polymerization method, a bulk polymerization method, and a suspension polymerization method (details of the production method are described in (See Japanese Patent Laid-Open No. 62-1720).

The composition of the monomer components constituting the graft copolymers A and B and the hard copolymer C in the present invention may be within the ranges defined above, and both compositions are completely the same. Does not necessarily mean that. However, even if both are selected within the above range and combined, if the compositions of both are significantly different, the compatibility of both graft copolymers will be poor and the physical properties will be deteriorated, which is not preferable.

[III] Graft Copolymer Resin Composition The graft copolymer resin composition according to the present invention is composed of the graft copolymers A and B and the hard copolymer C as described above. The composition ratio is within the range represented by the formulas (1) to (3). If the blending amount of each copolymer is out of the range defined by the formulas (1) to (3), the desired physical properties cannot be obtained, and a thermoplastic resin composition having good moldability cannot be obtained. .

[0046]

[Equation 8]

[0047]

[Equation 9]

[0048]

[Equation 10] As shown in the above formula (1), in the rubbery polymer contained in the graft copolymer resin composition according to the present invention, the rubbery polymer contained in the graft copolymer A is the graft copolymer A or It must be 5 to 50% by weight, based on the total of the rubbery polymer of B.

Further, as shown in the above formula (2), the hard copolymer C must be 0 to 90% by weight based on the total of the graft copolymers A, B and the hard copolymer C. Furthermore, as shown in the above formula (3), the total amount of the rubber-like polymers obtained from the graft copolymers A and B is 5 to 5 per the total amount of the graft copolymers A and B and the hard copolymer C.
Must be 0% by weight.

As is clear from the above formula (2), the hard copolymer C may not be present. Therefore, it can be said that the essential features of the present invention are the graft copolymer B, the rubbery polymer being grape-like, and the blending composition ratio of the graft copolymers A and B. A known mixing and kneading method may be used for mixing and kneading the graft copolymer and the hard copolymer and mixing and kneading them. At this time, the kneading temperature is preferably selected in the range where the resin composition does not cause resin burning.

Mixtures of two or three of these copolymers in the form of powders, beads, flakes or pellets can be used in single screw extruders, twin screw extruders, or Banbury mixers, pressure kneaders, twin rolls, etc. A resin composition can be prepared by using a kneader or the like. Further, in some cases, a method of mixing two or three kinds of these copolymers which have completed the polymerization reaction in an undried state, precipitating, washing, drying and kneading can be adopted.

The resin composition according to the present invention comprises a lubricant, a plasticizer, a colorant, an antistatic agent, a flame retardant, an ultraviolet absorber, a light stabilizer and a heat resistant agent of a type and an amount which do not impair the properties of the resin. Various resin additives such as a sex stabilizer and a filler can be appropriately combined and added. The resin composition according to the present invention is formed into a molded article by various molding methods such as an injection molding method, an extrusion molding method, a thermoforming method and a compression molding method, and is required to have excellent chemical resistance, processability and impact resistance. For example, it can be used as electric parts and industrial parts such as materials for inner boxes of electric refrigerators.

[0053]

EXAMPLES The following examples and comparative examples are for more specifically explaining the present invention, and the present invention is not limited to the following examples unless it exceeds the gist.
In the following examples, "part" means part by weight. In each of the following examples and comparative examples, the physical properties of the impact-resistant styrene resin were measured by the following methods.

(1) Izod impact strength Measured according to JIS K7110. Unit: Kg-cm /
cm (2) Melt flow rate According to JIS K7210, temperature 220 ° C, load 10
The measurement was carried out under the condition of kg, and the value was expressed as the number of g flowing out for 10 minutes.
Unit: g / 10 minutes (3) Tensile strength Measured according to JIS K7113. Unit: Kg / cm2 (4) Gloss Based on ASTM D523, it was measured by a 60 ° -60 ° specular gloss method.

(5) Color tone In accordance with JIS K7103, the yellowness YI is measured by SM color computer SM-4-CH manufactured by Suga Test Instruments Co., Ltd. (6) Weight average particle size of latex "Nanosizer manufactured by Coulter Co., USA" It was measured by. (7) Average Aggregated Particle Diameter An electron micrograph was taken of a test piece molded by the injection molding method, and the average particle diameter of 200 particles observed from the photograph was measured, and this was taken as the average aggregate particle diameter. (8) Chemical resistance Compression molded test pieces (thickness 2 mm, width 35 mm, length 230
(mm) was measured by a bending foam method at 23 ° C. to determine the critical strain value for crack initiation with respect to Freon 123. Chemical resistance of 0.8% or more of critical strain is extremely good (◎),
0.8 to 0.6% was judged to be good (◯), and 0.6% or less was judged to be bad (x).

[Production Example] 1: Production of graft copolymer (A) A-1 (1) Production of conjugated diene rubbery polymer Stirrer, heating / cooling device, thermometer, raw materials, additives added In the stainless steel autoclave equipped with the device,

[0057]

[Table 1] Deionized water 150 parts (parts by weight) Butadiene monomer (BD) (# 1) 90 〃 Styrene monomer (ST) (# 1) 10 〃 t-dodecyl mercaptan (TDM) (# 1) 0.3 〃 Higher fatty acid thorium 4 〃 Thorium pyrophosphate 0.8 〃 Sodium hydroxide 0.075 〃 Potassium persulfate 0.15 〃 is charged with nitrogen gas and the internal temperature is raised to 68 ° C to carry out the reaction. Started. While continuing the polymerization at this temperature, from 1 hour to 5 hours,

[0058]

Table 2 Butadiene monomer (# 2) 72〃 Styrene monomer (# 2) 8〃 t-dodecyl mercaptan (# 2) 0.3〃 was continuously added to the same autoclave and the polymerization reaction was continued for 6 hours. did. Next, the internal temperature was raised from 68 ° C. to 80 ° C. over 1 hour, and the reaction was further continued for 2 hours and 30 minutes. Immediately thereafter, the internal temperature was cooled to room temperature to obtain a butadiene-styrene rubber copolymer. The obtained rubbery polymer latex has a solid content of 40.2% by weight and an average particle size of 0.0.
It was 8 μm. (Particle size enlargement) The rubbery polymer latex obtained above was subjected to a particle size enlargement operation in the following procedure using the same autoclave. First, in the autoclave

[0059]

[Table 3] Rubber polymer latex 100 parts (parts by weight) 200 deionized water (including water in the latex) was charged at a temperature of 25 ° C.

[0060]

Table 4 Acetic anhydride 1.2 〃 deionized water 50 〃 was added and mixed. After leaving for 30 minutes after the addition, in the same otoclave,

[0061]

[Table 5] Sodium β-naphthalenesulfonate formaldehyde condensate 1.5 〃 sodium hydroxide 0.8 〃 deionized water 25 〃 were added, mixed and stirred, and butadiene-styrene rubber containing expanded rubber particles A copolymer latex was obtained.
The obtained latex had a solid content of 27.5% by weight and an average particle diameter of 0.16 μm.

A1-2 Using the same autoclave as used in A1-1, a rubber polymer was produced in the same manner as in the same example, and the obtained rubber polymer latex was the same as that in the same example. The particle size was enlarged in the same manner as in (1).
At this time, only the amount of acetic anhydride used was changed. The obtained latex had a solid content of 27.3% by weight and an average particle size of 0.20 μm.

A1-3 Using the same autoclave as used in A1-1, production of a rubbery polymer and enlargement of the rubbery polymer latex particle size were carried out in the same manner as in the same example. . During the enlargement operation, only the amount of acetic anhydride used in A1-1 was changed. The obtained latex had a solid content of 27.3% by weight and an average particle diameter of 0.32 μm.

A1-4 A rubbery polymer was produced in the same manner as in the same example, using the same autoclave as used in A1-1. At this time, the polymerization initiator, the emulsifier, and the auxiliary are A1-1.
In the same manner as in the above, except that the styrene monomer is 0 parts by weight, the butadiene monomer # 1 is 20 parts by weight, # 2 is 80 parts by weight, and t-dodecyl mercaptan # 1 is 0.1 part by weight.
Part # 2 was changed to 0.4. The obtained latex has a solid content of 40.5% by weight and an average particle size of 0.15μ.
It was m.

A1-5 Using the same autoclave as used in A1-1, a rubbery polymer was produced in the same manner as in the same example. At this time, the polymerization initiator, the emulsifier, and the auxiliary are A1-1.
In the same manner as in, the acrylonitrile monomer was used instead of the styrene monomer, and t-dodecyl mercaptan # 1 was changed to 0.1 part and # 2 was changed to 0.4 part. The obtained latex has a solid content of 40.5% by weight,
The average particle size was 0.15 μm.

A1-6 A rubbery polymer was produced in the same manner as in the same example, using the same autoclave as used in A1-1. At this time, the monomer composition, the polymerization initiator, and the auxiliary agent are A1.
Same as -1, except that the amount of emulsifier used was changed. The obtained latex had a solid content of 40.2% by weight and an average particle diameter of 0.07 μm. 1-2: Production of graft copolymer (A)

A-1, 2 stirrer, heating and cooling device, thermometer, each raw material, in a polymerization can equipped with an auxiliary addition device, 50 parts (solid content) of the rubbery polymer shown in Table-1, And, 180 parts of water in which 0.5 parts of dextrose, 0.5 parts of sodium pyrophosphate and 0.005 parts of ferrous sulfate are dissolved (including water in latex),
I prepared it. After replacing the gas phase in the polymerization vessel with nitrogen gas, while controlling the internal temperature to 70 ° C and performing the graft reaction,
The monomer mixture shown in 1 above, and a mixed aqueous solution of 0.25 parts of cumene hydroperoxide, 1.0 part of rosin acid soap, and 14 parts of deionized water were added to the polymerization vessel over 3 hours.

After the addition was completed, the reaction was continued for another 30 minutes.
The temperature inside the polymerization vessel was cooled to complete the reaction. After the addition of 1 part of the anti-aging agent, the obtained graft polymer latex was mixed with 9
The mixture was added to an aqueous magnesium sulfate solution heated to 5 ° C with stirring to coagulate. The coagulated product was washed with water and dried to obtain powders of the graft copolymers A-1 and A-2. A-3 In the same polymerization container as used in A-1, 35 parts (solid content) of the rubbery polymer shown in Table 1 and 180 parts of water in which 0.1 part of potassium persulfate was dissolved (latex (Including water inside) was charged. After replacing the gas phase in the polymerization vessel with nitrogen gas, while controlling the internal temperature to 75 ° C and performing the graft reaction, the monomer mixture shown in Table 1 and 0.2 parts of potassium persulfate and stearic acid were used. A mixed aqueous solution consisting of 1.5 parts of sodium and 14 parts of deionized water was added to the polymerization vessel in 4 hours and 30 minutes.

After the completion of the addition, the reaction was continued for another hour, the temperature inside the polymerization vessel was cooled, and the reaction was completed. After adding 0.7 parts of the anti-aging agent to the obtained graft polymer latex,
It was added to the magnesium sulfate aqueous solution heated to 95 ° C. with stirring to coagulate. The coagulated product was washed with water and dried to obtain a powder of graft copolymer A-3.

A-4, 6 In the same polymerization vessel as used in A-1, 50 parts (solid content) of the rubbery polymer shown in Table-1, 0.8 parts of dextrose, and sodium pyrophosphate were used. 0.5 part and 180 parts of water in which 0.005 parts of ferrous sulfate were dissolved (including water in latex) were charged. After substituting the gas phase in the polymerization vessel with nitrogen gas, while controlling the internal temperature to 70 ° C. and performing the graft reaction, the monomer mixture shown in Table 1 and 0.25 part of cumene hydroperoxide, rosin Acid soap 1.
A mixed aqueous solution consisting of 0 part and 14 parts of deionized water was added to the polymerization vessel over 4 hours.

After the addition was completed, the reaction was continued for another 30 minutes.
The temperature inside the polymerization vessel was cooled to complete the reaction. After the addition of 1 part of the anti-aging agent, the obtained graft polymer latex was mixed with 9
The mixture was added to an aqueous magnesium sulfate solution heated to 5 ° C with stirring to coagulate. The coagulated product was washed with water and dried to obtain powders of the graft copolymers A-4 and 6.

A-5 In the same polymerization vessel as used in A-1, 35 parts (solid content) of the rubbery polymer shown in Table-1, 1.1 parts of dextrose, sodium pyrophosphate (0.1 part) were added. 7 parts and 180 parts of water in which 0.01 part of ferrous sulfate was dissolved (including water in latex) were charged. After replacing the gas phase in the polymerization vessel with nitrogen gas, while controlling the internal temperature to 70 ° C and performing the graft reaction, the monomer mixture shown in Table 1 and 0.3 parts of cumene hydroperoxide and rosin were added. Acid soap 1.5
Part, and a mixed aqueous solution of 14 parts of deionized water were added to the polymerization vessel over a period of 6 hours.

After the completion of the addition, the reaction was continued for another hour, the temperature inside the polymerization vessel was cooled, and the reaction was completed. The resulting graft polymer latex was added with 95 parts of anti-aging agent,
The mixture was added to an aqueous magnesium sulfate solution heated to 0 ° C. with stirring to solidify. The coagulated product was washed with water and dried to obtain a powder of the graft copolymer A-5.

A-7, 8, 9 In the same polymerization vessel as used in A-1, 50 parts (solid content) of the rubbery polymer shown in Table 1 and 1.0 part of sodium alkyldiphenyl ether disulfonate are used. Parts, dextrose 0.8 parts, sodium pyrophosphate 0.5
Parts, and 180 parts of water in which 0.005 parts of ferrous sulfate was dissolved (including water in the latex) were charged. After substituting the gas phase in the polymerization vessel with nitrogen gas, while controlling the internal temperature to 65 ° C and performing the graft reaction, the monomer mixture shown in Table 1 and 0.25 part of cumene hydroperoxide, alkyl Sodium diphenyl ether disulfonate 1.0
Part, and a mixed aqueous solution of 14 parts of deionized water were added to the polymerization vessel over 4 hours.

After the addition was completed, the reaction was continued for another 1 hour, the temperature inside the polymerization vessel was cooled, and the reaction was completed. After adding 0.7 parts of the anti-aging agent to the obtained graft polymer latex,
It was added to the magnesium sulfate aqueous solution heated to 95 ° C. with stirring to coagulate. The coagulated product was washed with water and dried to obtain powders of graft copolymers A-7, 8, and 9.

A-10 In the examples described in A-7, 8, and 9, the graft reaction was performed in the same manner as in the same example except that the addition time of the mixed aqueous solution was changed to 5 hours. A powder of -10 was obtained. A-11, 13 In the examples described in A-7, the graft reaction was performed in the same manner as in the same example except that the rubbery polymer and the monomer mixture were as shown in Table 1. Polymer A
Powders of -11 and 13 were obtained.

A-12 In the same polymerization vessel as used in A-1, 20 parts (solid content) of the rubber-like polymer shown in Table-1, 1.5 parts of dextrose, and sodium pyrophosphate 1. 180 parts of water in which 0 part and 0.015 part of ferrous sulfate were dissolved (including water in the latex) was charged. After substituting the gas phase in the polymerization vessel with nitrogen gas, while controlling the internal temperature to 70 ° C. and performing the graft reaction, the monomer mixture shown in Table 1 and 0.25 part of cumene hydroperoxide, rosin Acid soap 1.
A mixed aqueous solution of 5 parts and 14 parts of deionized water was added to the polymerization vessel over 8 hours.

After the completion of the addition, the reaction was further continued for 1 hour and the temperature inside the polymerization vessel was cooled to complete the reaction. After adding 0.5 parts of the anti-aging agent to the obtained graft polymer latex,
It was added to the magnesium sulfate aqueous solution heated to 95 ° C. with stirring to coagulate. The coagulated product was washed with water and dried to obtain a powder of the graft copolymer A-12. 2: Manufacture of graft copolymer (B) 2-1: Manufacture of rubbery polymer (B1) B1-1 (rubbery polymer) Stirrer, heating and cooling device, thermometer, and addition of raw materials and auxiliaries In the stainless steel autoclave equipped with the device,

[0079]

[Table 6] Deionized water 165 parts (parts by weight) Butadiene monomer (BD) 90 〃 Styrene monomer (ST) 10 〃 t-dodecyl mercaptan (TDM) 0.4 〃 Higher fatty acid sodium 6 〃 Potassium chloride 0 0.6 〃 0.15 〃 potassium persulfate was charged and the reaction was started at a temperature of 53 ° C. During the course of continuing the polymerization reaction at this temperature, 0.8 hours of ethylene glycol dimethacrylate was added to the same autoclave after 5 hours, and the polymerization reaction was further continued for 5 hours. At this point, the polymerization conversion was 85.0%, and the average particle diameter of the obtained butadiene-styrene copolymer rubber was 0.09 μm.
It was m.

B1-2 In the example described in B1-1, 100 parts of butadiene monomer was used.
Except that the parts and the styrene monomer were replaced by 0 parts, the polymerization reaction was performed in the same manner as in the same example to obtain a butadiene rubber. At this point, the polymerization conversion was 75.1% and the obtained butadiene rubber had an average particle diameter of 0.09 μm.

B1-3 In the example described in B1-1, 3 higher fatty acid sodium was used.
Parts and potassium chloride 0.1 parts, except that the polymerization reaction was carried out at a temperature of 53 ° C. in the same manner as in the same example. After 10 hours, 0.8 part of ethylene glycol dimethacrylate was added to the same autoclave, and the polymerization reaction was continued for another 20 hours. At this point, the polymerization conversion rate was 79.8%, and the obtained butadiene-styrene copolymer rubber had an average particle diameter of 0.35 μm.

B1-4 In the example described in B1-1, the polymerization reaction was conducted at a temperature of 53 ° C.
The reaction after adding 0.8 parts of ethylene glycol dimethacrylate to the same autoclave at the time of 0 hours,
The polymerization reaction was performed in the same manner as in the same example except that the time was changed to 15 hours. At this point, the polymerization conversion rate was 99.8%, and the average particle diameter of the obtained butadiene-styrene copolymer rubber was 0.09 μm. 2-2: Production of hard polymer latex (C1) C1-1 Stirrer , heating and cooling device, thermometer, and autoclave equipped with each raw material and auxiliary agent adding device,

[0083]

[Table 7] Deionized water 165 parts (parts by weight) Higher fatty acid sodium 2 〃 Potassium chloride 0.2 〃 Sodium carbonate 0.3 〃 Potassium persulfate 0.15 〃 were charged and the temperature was raised. When the internal temperature of the autoclave reached 80 ° C., the zero batch time (ZBT) was set, and from this point, the monomer mixture shown in Table 2 and 16 parts of deionized water and 0.4 part of potassium persulfate were used. Then, the addition of a mixed aqueous solution containing 2 parts of higher fatty acid sodium was started and continuously added until 4 hours after ZBT. After completion of addition
The reaction was further continued for 30 minutes, the internal temperature of the autoclave was cooled, the reaction was terminated, and a hard polymer latex C1-1 was obtained.

In the examples described in C1-2, 3, 4 C1-1, the ratio of the monomer mixture is shown in the table.
The reaction was carried out by the same procedure as in the example except that the hard polymer latexes C1-2 and C1 were used.
-3 and C1-4 were obtained. 2-3: Production of graft copolymer (B)

Following the production of B-1 to 10 rubbery polymers B1-1, 0.15 parts of potassium persulfate and 10 parts of deionized water were charged into the same autoclave, and then the single autoclave shown in Table 3 was used. The monomer mixture was added over 4 hours. After the completion of charging, the reaction was continued for another hour and then the internal temperature was cooled to obtain a graft copolymer latex. In addition, the hard polymer latex (C
1) was added and the content of the rubbery polymer was adjusted to be the weight% shown in Table-3.

After adding 1 part of the anti-aging agent to the latex mixture, it was added to an aqueous magnesium sulfate solution heated to 95 ° C. with stirring to coagulate. Wash the coagulum with water, dry it,
Powders of graft copolymers B-1 to 10 containing agglomerated particles having the particle sizes listed in Table 3 were obtained.

B-11, 12 In the examples described in B1-1 to B- 10, the rubber polymer is B
Except for replacing with 1-2, the reaction was conducted in the same manner as in the same example, mixing with the hard polymer latex (C1) shown in Table-2, addition of an antioxidant, coagulation, and washing with water were carried out, and graft copolymerization was carried out. Powders of the combined latex B-11 and 12 were obtained.

B-13 In the same autoclave as used in B-1, 30 parts (parts by weight) of the rubbery polymer B1-1, 10 parts of deionized water,
After charging 0.25 part of potassium persulfate, the monomer mixture shown in Table 3 was added over 5 hours. After the completion of charging, the reaction was continued for another hour and then the internal temperature was cooled to obtain a graft copolymer latex. This is mixed with the hard polymer latex (C1) shown in Table-2, added with an antioxidant, coagulated and washed with water to obtain a graft copolymer latex B.
A powder of -13 was obtained.

B-14 In the examples described in B1-1 to B-10 , the rubbery polymer is added to B
Other than substituting for 1-3, the reaction was carried out in the same procedure as in the same example, mixing with the hard polymer latex (C1) shown in Table-2, addition of an antioxidant, coagulation, and washing with water were carried out, and graft copolymerization was performed. A powder of combined latex B-14 was obtained.

B-15, 16 The rubbery polymer B1-4 was charged into the same autoclave as used in B-1, and the internal temperature was raised while bubbling with nitrogen gas. When the internal temperature reached 53 ° C, 0.15 parts of potassium persulfate and 10 parts of deionized water were charged, and then the monomer mixture shown in Table 3 was added over 4 hours. After the completion of charging, the reaction was continued for another hour and then the internal temperature was cooled to obtain a graft copolymer latex. to this,
The hard polymer latex (C1) shown in Table 2 was added, and the content of the rubber-like polymer was adjusted to be the weight% shown in Table 3. After adding 1 part of the antioxidant to the latex mixture, it was added to an aqueous magnesium sulfate solution heated to 95 ° C. with stirring to coagulate. Wash the coagulum with water, dry it,
The powder of graft copolymer B-15, 16 was obtained. 3: Production of rigid copolymer (C2)

The following raw materials and auxiliary agents were charged into a stainless steel autoclave equipped with a C2-1 curved turbine stirrer, a heating / cooling apparatus, a thermometer, each raw material, and auxiliary agent addition apparatus, and the gas phase inside the autoclave was charged. Was replaced with nitrogen gas.

[0092]

[Table 8] Deionized water 70 parts (parts by weight) Acrylonitrile monomer (AN) 58 〃 Styrene monomer (ST) (# 1) 6 〃 Di-t-butyl-p-cresol 0.02 〃 Acrylic acid・ 2-Ethylhexyl acrylate copolymer (suspension stabilizer) 0.03 〃 Sodium bromide 0.4 〃

The internal temperature of the autoclave was adjusted to 106 with stirring.
1-t- dissolved in a small amount of styrene monomer
0.15 parts of azo-cyanocyclohexane was added, and the polymerization reaction was started at the same temperature. Immediately after the polymerization was started, 36 parts of styrene monomer (# 2) was continuously added to the polymerization system at a constant rate for 4 hours 30 minutes, and at the same time, 4 hours 30 minutes were required. The temperature was raised to 128 ° C.

After the continuous addition of the polymerization system of the styrene monomer was completed, it took 45 minutes to raise the internal temperature to 145 ° C. 5 hours and 15 minutes after starting the polymerization, the temperature inside the autoclave was set to 1
Stripping for 1 hour while maintaining at 45 ° C
Unreacted monomer was recovered. After this stripping,
The internal temperature of the autoclave was cooled down, filtered, washed with water, and dried to obtain a bead-shaped hard copolymer C-1. The acrylonitrile content (AN%) of the hard copolymer C-1 is
It was 49.8%.

[0095]C2-2 In the example described in C-1, the acrylonitrile monomer is
45 parts, 10 parts of styrene monomer (# 1) and styrene
In the same example except that the monomer (# 2) was replaced with 45 parts
The reaction is carried out by the same procedure, and the bead-shaped hard copolymer C-
Got 2. Hard copolymer C-2 containing acrylonitrile
The rate (AN%) was 39.9%. C2-3 SAN-T (AN% = 32) manufactured by Monsanto Kasei Co., Ltd.
%) Was used as is. II. Manufacture of composition

Example 1 Graft copolymer A obtained by the method described in the above Production Example
-1, B-8 and the hard copolymer C2-2 were kneaded using a Bus Co kneader according to the blending ratio (parts) shown in Table 4 to give pellets of the copolymer resin composition. Created.

From the pellets of this copolymer resin composition,
Test pieces for measuring physical properties and for chemical resistance were molded by injection molding and press molding. The melt flow rate of the pellet, the Izod impact strength of the injection molded test piece, and the chemical resistance of the press molded test piece were measured.

The results are shown in Table 4. Figure 1
Is a schematic diagram showing a dispersed state of rubbery polymer particles,
1 means grape-like secondary particles, and 2 means primary particles. Examples 2-18, Comparative Examples 1-12 Each of the graft copolymers A, B and the hard copolymer C obtained by the method described in the above-mentioned Production Example was mixed in proportions (parts) shown in Table-4. According to the same manner as in Example 1,
Kneading was performed using a Bus Co Kneader to prepare pellets of the copolymer resin composition.

The melt flow rate of the pellets is
The Izod impact strength of the injection-molded test piece and the chemical resistance of the press-molded test piece were measured. The results are shown in Table-4. In Tables 1 to 3 below, the abbreviations have the following meanings.

[0100]

[Table 9] ST = styrene monomer AN = acrylonitrile monomer MMA = methyl methacrylate monomer BT = butadiene monomer TDM = t-dodecyl mercaptan

[0101]

[Table 10]

[0102]

[Table 11]

[0103]

[Table 12]

[0104]

[Table 13]

[0105]

[Table 14]

[0106]

[Table 15]

The following is clear from Table-4. (1) The graft copolymer resin composition according to the present invention is
It is excellent in impact resistance and workability and well balanced (see Examples 1 to 18). (2) The graft copolymer resin composition according to the present invention is
It has excellent chemical resistance (see Examples 1 to 18).

[0108]

The graft copolymer resin composition according to the present invention has a specific ratio of the specific graft copolymers A and B and the hard polymer C, and thus cannot be obtained by the conventional resin composition. It exhibits such excellent processability, impact resistance and chemical resistance, and its industrial utility value is extremely large.

[Brief description of drawings]

FIG. 1 is a schematic view showing a dispersed state of rubbery polymer particles in a graft copolymer resin composition according to the present invention.

[Explanation of symbols]

 1 Grape-like secondary particles 2 Primary particles

Claims (1)

[Claims] 1. A graft copolymer comprising the following graft copolymer A, graft copolymer B and hard polymer C in the following composition ratios (1) to (3). Resin composition. Graft Copolymer A : The graft copolymer A is defined as follows. (1) In the presence of 10 to 80 parts by weight (based on the solid content) of a rubbery polymer latex having a weight average particle size of 0.10 to 0.65 μm, 30 to 80% by weight of an aromatic vinyl monomer and cyan A graft copolymer obtained by emulsion-polymerizing 20 to 90 parts by weight of a monomer mixture consisting of 20 to 70% by weight of a vinyl chloride monomer and 0 to 20% by weight of another vinyl monomer copolymerizable therewith. (2) Rubbery polymer 1
20 to 120 parts by weight of aromatic vinyl monomer, vinyl cyanide monomer and other vinyl monomer copolymerizable with these are chemically bonded to 00 parts by weight,
(3) The rubbery polymer has a form of dispersed spherical particles. Graft Copolymer B : The graft copolymer B is defined as follows. (1) A monomer mixture of 60% by weight or more of a conjugated diene-based monomer and 40% by weight or less of a vinyl monomer copolymerizable with the conjugated diene-based monomer has a weight average particle diameter of 0 obtained by emulsion polymerization. Rubber polymer latex 1 having a particle size of 0.05 to 0.2 μm
In the presence of 0 to 80 parts by weight (based on solid content), aromatic vinyl monomer 12 to 80% by weight, vinyl cyanide monomer 8 to
20 to 90 parts by weight of a monomer mixture consisting of 70% by weight, 2 to 60% by weight of a conjugated diene monomer and 0 to 20% by weight of another vinyl monomer copolymerizable therewith, and obtained by emulsion polymerization. (2) 10 to 70 parts by weight of an aromatic vinyl monomer, a vinyl cyanide monomer, and the other copolymerizable with 100 parts by weight of the rubbery polymer. That the vinyl monomers of are chemically bonded,
(3) The rubbery polymer contains grape-like secondary particles having an average particle diameter of 0.4 to 3.0 μm in which primary particles are aggregated. Hard Copolymer C : The hard copolymer C is defined as follows. (1) A monomer mixture comprising 30 to 80% by weight of an aromatic vinyl monomer, 20 to 70% by weight of a vinyl cyanide monomer, and 0 to 20% by weight of another vinyl monomer copolymerizable therewith. A hard copolymer obtained by polymerizing. [Equation 1] [Equation 2] [Equation 3]