JPH05320273A - Graft copolymer resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having good chemical resistance, impact resistance and flowability by the emulsion polymerization of a higher percentage of vinyl cyanide and a lower percentage of an aromatic vinyl monomer in a conjugated diene/ acrylate copolymer rubber latex. CONSTITUTION:The composition compriser 20-100 pts.wt. graft copolymer (A) obtained by the emulsion polymerization of 90-30 pts.wt. mixture comprising 50-85wt.% vinyl cyanide monomer, 15-50wt.% aromatic vinyl monomer and 0-30wt.% vinyl monomer copolymerizable therewith in a latex of 10-70 pts.wt. elastic rubber made by the emulsion polymerization of a monomer mixture comprising 20-95wt.% conjugated diene monomer, 5-80wt.% ester of a 2-12C monohydric alcohol with acrylic acid, 0-30wt.% vinyl monomer copolymerizable therewith and 0-3wt.% polyfunctional vinyl monomer, and 0-80 pts.wt. copolymer (B) of a mixture comprising 50-85wt.% vinyl cyanide, 15-50wt.% aromatic vinyl monomer and 0-30wt.% vinyl monomer copolymerizable therewith.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

[Industrial applications]

The present invention relates to a graft copolymer resin composition. More specifically, the present invention provides a conjugated diene-acrylic acid ester-based copolymer rubber with a monomer mixture comprising a high proportion of a vinyl cyanide monomer and a small proportion of an aromatic vinyl monomer by emulsion polymerization. The present invention relates to a graft copolymer resin composition obtained by a graft reaction and having an excellent balance of physical properties and excellent chemical resistance.

[0003]

2. Description of the Related Art Conventionally, a rubber-reinforced styrene copolymer represented by ABS resin has been known as a thermoplastic resin having good moldability and excellent physical properties, and is used for electric appliances, automobiles and other parts, It is widely used as a material for housings. However, for example, the ABS resin usually has a lower content of the acrylonitrile component than the content of the styrene component, and thus has poor properties such as chemical resistance and gas barrier properties. In order to obtain a resin having these excellent properties, there is known a method for producing a graft copolymer in which the blending ratio of an acrylonitrile component in an ABS resin is increased (see, for example, JP-A-47-5594).

[0004]

[Outline of Invention]

[0005]

SUMMARY OF THE INVENTION The present invention aims to provide a solution to the above-mentioned problems, and a high proportion of vinyl cyanide monomer and a low proportion in a conjugated diene-acrylic ester copolymer rubber latex. It is an object of the present invention to achieve this object by a graft copolymer resin composition obtained by emulsion-polymerizing a monomer mixture containing the aromatic vinyl monomer.

<Summary> That is, the graft copolymer resin composition according to the present invention is characterized by comprising the following components I and II. Component I: 20 to 95% by weight of a conjugated diene monomer, 5 to 80% by weight of an ester compound of a monohydric alcohol having 2 to 12 carbon atoms and acrylic acid, and a vinyl monomer 0 copolymerizable therewith Rubber elastomer obtained by emulsion polymerization of a monomer mixture of 30 to 30% by weight and a polyfunctional vinyl monomer of 0 to 3% by weight in a latex of 10 to 70 parts by weight of vinyl cyanide monomer 50 to 85. % By weight, aromatic vinyl monomer 15 to
50% by weight and vinyl monomer copolymerizable therewith 0
90 to 30 parts by weight of a monomer mixture consisting of 30 to 30% by weight (however, the total amount of the rubber elastic body and the monomer mixture is 100 parts by weight) 20 to 100 parts by weight of a graft copolymer obtained by emulsion polymerization Component II: a monomer mixture consisting of 50 to 85% by weight of a vinyl cyanide monomer, 15 to 50% by weight of an aromatic vinyl monomer, and 0 to 30% by weight of a vinyl monomer copolymerizable therewith. Copolymer 0
-80 parts by weight (however, the total of the component I and the component II is 100 parts by weight, and the content of the rubber elastic body in this composition is 5 to 40% by weight)

<Effect> The graft copolymer resin composition according to the present invention has good chemical resistance. Further, it has good impact resistance and fluidity, and has an excellent balance of physical properties.

[Detailed Description of the Invention] << Component I >><Rubber Elastic Body> The component I of the resin composition of the present invention is a graft copolymer, and the rubber elastic body as a "stem" polymer thereof is a conjugated diene. -It is an acrylic ester-based copolymer rubber. Specifically, this copolymer rubber is an ester compound 5 of a conjugated diene monomer 20 to 95% by weight and a monohydric alcohol having 2 to 12 carbon atoms and acrylic acid.
Emulsion polymerization of a monomer mixture of ˜80% by weight, 0 to 30% by weight of a vinyl monomer copolymerizable with the conjugated diene and the acrylic ester, and 0 to 3% by weight of a polyfunctional vinyl monomer. The obtained product is used as a latex for producing the composition of the present invention.

If the amount of the conjugated diene monomer is less than 20% by weight, it is not preferable because sufficient impact strength cannot be imparted to the graft copolymer. If the conjugated diene monomer content exceeds 95% by weight, the desired chemical resistance cannot be imparted, which is not preferable.

This conjugated diene-acrylic ester copolymer rubber is a synthetic rubber latex obtained by an emulsion polymerization method, and imparts impact resistance and chemical resistance to the graft copolymer obtained by the present invention.

The conjugated diene monomer used in the production of the conjugated diene-acrylic acid ester copolymer rubber preferably has about 4 to 6 carbon atoms, specifically, for example, 1, 3-butadiene, isoprene, 1,3
-Pentadiene, chloroprene and the like. From the viewpoint of easy availability and polymerizability, 1,3-butadiene and isoprene are preferable. These may be used alone or in combination.

As the acrylic ester, an ester of acrylic acid and a monohydric alcohol having 2 to 12, preferably 4 to 8 carbon atoms is suitable. Specifically, butyl acrylate, 2-ethylhexyl acrylate and the like are preferable. If the carbon number of the alcohol is outside 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.

The rubber elastic body of the component I contains these two monomers as essential components, but it may be one obtained by copolymerizing a third monomer copolymerizable therewith, if necessary. Good. In this case, the third monomer is a vinyl monomer having a function of improving and improving the properties of the conjugated diene-acrylic acid ester-based copolymer rubber obtained by copolymerization as a reinforcing rubber and the graft polymerization reactivity. A monomer is preferred. Such vinyl monomers are specifically vinyl cyanide monomers,
For example, acrylonitrile, methacrylonitrile, styrene, or nucleus and / or side chain-substituted styrene (substituents are halogen, lower alkyl, halo lower alkyl, etc.), for example, α-methylstyrene, p-vinyltoluene and other vinyltoluenes. Alkyl methacrylate, for example, ester with alcohol as described above, 2-chloroethyl vinyl ether, vinyl monochloroacetate, methoxyethyl acrylate and the like can be mentioned.

The rubber elastic body of the component I is obtained by further copolymerizing a polyfunctional vinyl monomer, that is, a monomer having a plurality (preferably two) of ethylenically unsaturated bonds. Good. In general, the use of a polyfunctional vinyl monomer facilitates intermolecular crosslinking of a conjugated diene-acrylic acid ester-based copolymer, graft bonding with a matrix, etc. The impact resistance of is improved.

As the polyfunctional vinyl monomer, divinylbenzene, mono- or oligoethylene glycol di (meth) acrylate, diallylmaleate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, trimethylolpropane tri (meth) are used. ) Acrylate and allyl (meth) acrylate.

The above-mentioned conjugated diene used in the present invention
The rubber particle size of the acrylate copolymer rubber is
0.05 to 0.50 μm, preferably 0.10 to 0.3
5 μm. Rubber particle size is, for example, 0.05
When the particle size is smaller than μm, the moldability (fluidity) of the molded product as the final product decreases, and more important impact resistance decreases. Bring worse. On the other hand, if the rubber particle size is, for example, a large particle size exceeding 0.50 μm, destabilization of the latex is caused during emulsion graft polymerization and problems such as an increase in the amount of scale during the polymerization occur, which is not preferable. ..

When the rubber elastic latex obtained or produced does not have a predetermined rubber particle diameter, the particle diameter can be increased by a particle diameter increasing method known per se. The above-mentioned rubber particle size is the particle size of the rubber particles in the rubber latex used for graft copolymerization. The present invention relates to a resin composition, and specifies the particle size of rubber particles in the composition, but the rubber particle size in the latex and the rubber particle size in the resin composition are largely different. Therefore, the rubber particle size of 0.05 to 0.50 μm is applied to both the rubber particle size in the latex and the rubber particle size in the resin composition.

Here The rubber particle size in the latex is the average particle size measured by "Nanosizer" manufactured by U.S. Coulter, Inc., and the rubber particle size in the resin composition is the average particle size measured from an electron micrograph of an ultrathin section of the composition molded product. Is.

<Monomer for “branch” polymer> The monomer constituting the “branch” polymer with respect to the above “stem” polymer is a vinyl cyanide monomer or an aromatic vinyl monomer. The monomer is an essential component.

Specific examples of the vinyl cyanide monomer include:
Examples thereof include acrylonitrile, methacrylonitrile and α-chloroacrylonitrile. These may be one kind or a mixture of two or more kinds.

The proportion of vinyl cyanide monomer in the monomer mixture should be 50 to 85% by weight.
If it is less than 50% by weight, the desired physical properties such as chemical resistance cannot be imparted to the graft copolymer, which is not preferable. Particularly preferably, it is 55% by weight or more. On the other hand, if it exceeds 85% by weight, properties of the graft copolymer such as molding and processing and coloring property upon heating are deteriorated, which is not preferable.

As the aromatic vinyl monomer, styrene,
Alternatively, nucleus and / or side chain-substituted styrene (substituent is lower alkyl, halogen, halo lower alkyl, etc.) is preferable. Specific examples thereof include styrene, α-alkylstyrene such as α-methylstyrene, nuclear-substituted alkylstyrene such as p-methylstyrene, halogenated styrene, vinylnaphthalene and the like. These may be one kind or a mixture of two or more kinds.

The proportion of the aromatic vinyl monomer in the monomer mixture should be 15 to 50% by weight. When the ratio is out of the above range, the properties of the resulting graft copolymer are unfavorable since the properties such as desired chemical resistance, gas barrier property, moldability and colorability upon heating are deteriorated.

The "branched" polymer may be, in addition to the above-mentioned two essential monomers, a copolymer of a third monomer copolymerizable with both monomers. Specific examples of the vinyl monomer suitable as the third monomer can be found in those exemplified as the third monomer for the rubber elastic body. The content of the third monomer in the "branch" polymer monomer is 0 to 30% by weight.

<Graft Copolymer (Part 1)> Component I of the resin composition according to the present invention is a graft copolymer comprising the above-mentioned "stem" polymer and "branch" polymer.

Such a graft copolymer is produced by polymerizing a "branch" polymer monomer in the presence of a "stem" polymer, and specifically, in the former latex, the latter polymerization. , Ie, emulsion polymerization, but by following such a method, the resulting graft copolymer is an ideal graft copolymer in which a “branch” polymer is bonded to a “stem” polymer. Outside, "branch" that does not become a branch
It also contains a polymer of a monomer for polymer. Considering that such a graft copolymer is considered to be an impact resistant resin, there is a considerable amount of polymer in the "graft copolymer" that does not bond as a "branch" to the "stem" polymer. Can be said to exist. Therefore, it is virtually impossible to distinguish between Component II (details below) optionally incorporated in the present invention and the non- "branched" polymer present in the graft copolymer.

<Graft Copolymer (Part 2)> Component I in the graft copolymer resin composition according to the present invention comprises the above-mentioned "stem" polymer and "branch" polymer, and the total amount of both is 100% by weight. The content of the "stem" polymer in the part, that is, the conjugated diene-acrylic acid ester-based copolymer rubber, is
It should be 10 to 70 parts by weight.

When the ratio of the conjugated diene-acrylic acid ester copolymer rubber is less than 10 parts by weight, the impact resistance of the resulting graft copolymer is lowered and a molded article having the desired physical properties is obtained. However, it is not preferable because it is less effective in use as an impact resistance imparting agent. 70
When the amount is more than parts by weight, the graft ratio of the obtained graft copolymer becomes small, and the dispersibility of rubber particles and the rubber efficiency, that is, impact resistance are deteriorated, which is not preferable.

This component I is prepared by a conventional emulsion graft copolymerization process, that is, by emulsion polymerizing a "branch" polymer monomer in a rubber elastomer latex as a "stem" polymer. can do.

The preferred method in the present invention is to remove the oxygen at a temperature of about 0 to 100 ° C. and mix the monomers separately or, if necessary, to add a component other than the monomer such as an emulsifier, Dispersing agents, polymerization initiators, molecular weight regulators or chain transfer agents, pH regulators, etc., are supplied to the polymerization system as they are or in an emulsified state, temporarily, batchwise or continuously, for polymerization. That is. Polymerization initiators (or catalysts) that can be used include persulfuric acid, peracetic acid, perphthalic acid and other peracid catalysts, potassium persulfate and other peracid catalysts, hydrogen peroxide, benzoyl peroxide, chlorobenzoyl peroxide. , Naphthyl peroxide, acetyl peroxide, benzoylacetyl peroxide, lauryl peroxide, di-t-peroxide
There are peroxide catalysts such as butyl, dicumyl peroxide, t-butyl peroxide, and sodium peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, and azo catalysts such as azobisbutyronitrile. Or a mixture of two or more kinds can be used. These can also be used as a redox catalyst in combination with a reducing agent.

Examples of emulsifiers that can be used in the present invention include fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates and the like. ..

The chain transfer agent which can be 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 product is obtained in the form of a latex, and the polymer is coagulated by a conventionally known method, for example, an agglomeration method using an electrolyte or a solvent, a freezing method, etc., and further washed with water and dried to obtain the polymer. After mixing, kneading, devolatilization,
It can be used as a molding material by appropriately combining steps such as pelletization.

<Component II> Component II is used to adjust the content of the rubber elastic body of the graft copolymer resin composition according to the present invention to a predetermined value, that is, 5 to 40% by weight, or a predetermined molecular weight for the resin component. It is a component that is blended as necessary in order to have.

The specific contents of component II are the same as those described above for the "branch" polymer. The composition having the same or different composition as that of the "branch" polymer is selected, and components I20 to 100
1 in total by blending in a proportion of 0 to 80 parts by weight with respect to parts by weight.
It may be 00 parts by weight.

<< Graft Copolymer Resin Composition >> The graft copolymer resin composition of the present invention comprises Component I and, if necessary, Component II. The content of the rubber elastic body in this composition is 5 to 40% by weight, preferably 10%.
˜30% by weight.

When one or both of the components II and II are in the latex state, they can be mixed in the latex state and coagulated and washed in a conventional manner. The composition of the present invention can also be blended with a plasticizer, a stabilizer, a lubricant, a dye and a pigment, a filler and the like according to the conventional practice in this type of graft copolymer resin composition. In addition, these auxiliary components,
It can also be compounded in the polymerization step.

[0038]

EXAMPLES The following examples and comparative examples serve to more specifically explain the present invention. The present invention is not limited to the following examples as long as the gist thereof is not exceeded. 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 The Izod impact strength was measured according to JIS K7110. (2) Melt flow rate: Measured in accordance with JIS K7210 under the conditions of 220 ° C. and 10 kg, and expressed as the number of g flowing out for 10 minutes.

(3) Average Particle Size of Latex The average particle size of the latex was measured by "Nanosizer" manufactured by Coulter Co., USA. (4) Chemical resistance The final product was compression-molded into a dumbbell shape, and a rigid polyurethane foam was adhered by an in-situ foaming method using Freon 123 to obtain a test piece. The test piece was pulled at 23 ° C., fixed to a jig while being strained, immediately cooled with the jig to −20 ° C. and left for 17 hours. The lower limit strain value (critical strain) corresponding to was measured. The dumbbell had a thickness of 1 mm for a tensile test defined in JIS-K6734, and the rigid polyurethane foam was adhered to its parallel portion with a width of 10 mm, a length of 40 mm and a thickness of 10 m. .. When the critical strain is 0.6% or more, it is judged that the chemical resistance is good.

Example 1 (1) Production of Conjugated Diene-Acrylate Ester Copolymer Rubber In an autoclave made of 5LSUS, 2400 g of deionized water (hereinafter simply referred to as water), higher fatty acid soap (having 18 carbon atoms as a main component) 64.0 g of the fatty acid sodium salt) and 16.0 g of sodium hydrogen carbonate were charged, and after substitution with nitrogen, 68
The temperature was raised to ° C. After charging 320 g of a monomer mixture consisting of 800 g of 1,3-butadiene (BD) and 800 g of acrylic acid butyl ester (BA), 2.16 g of potassium persulfate was added, and heat was generated in about several minutes. The initiation of polymerization was confirmed. One hour after the addition of potassium persulfate, continuous charging of 1280 g of the monomer mixture was started.
Finished at the time. After the addition of the monomer mixture was completed, the temperature was raised to 80 ° C. and the polymerization was further proceeded for 1 hour. Solid content concentration 39.5%, conversion rate 98%, average particle size 0.08 μm
Met.

(2) Production of Graft Copolymer The latex of (1) above is treated with acetic anhydride to give an average particle size of 0.15.
Latex with particle size enlarged to μm 1646 g (solid content 65
0 g), sodium alkyl diphenyl ether disulfonate 13.0 g, water (as total water content) 741 g
Was charged into a 5 L glass flask equipped with a stirrer, a reflux condenser, a thermometer, and an auxiliary agent addition device, and the inner temperature was raised to 65 ° C. while stirring under a nitrogen stream.

Subsequently, an aqueous solution of potassium persulfate (I) (containing 0.98 g of potassium persulfate) was added to the flask.
100 g of acrylonitrile was added at the same temperature.
The grafting reaction was initiated by the continuous addition of a monomer mixture of 5 g, styrene 292.5 g, and n-dodecyl mercaptan 3.3 g. From immediately after the reaction to 4 hours later, the monomer mixture was added to the polymerization system at a constant addition rate. In addition, 30 minutes after starting the reaction, 4 hours 3
Until 0 minutes, potassium (II) persulfate aqueous solution (2.2
Contains 8 g of potassium persulfate. ) Was continuously added to the polymerization system at a constant addition rate of 230 g.

After 4 hours from the start of the reaction, after the addition of the monomer mixture was completed, the reaction was further continued at the same temperature for 1 hour to complete the graft reaction. The solid content concentration of the obtained latex was 34% by weight. Then, 15 g of an antioxidant was added to the obtained graft polymer latex and then added to an aqueous magnesium sulfate solution heated to 95 ° C. with stirring to coagulate. The solidified product was washed with water and dried to obtain a white powdery resin composition having a high rubber content.

A styrene-acrylonitrile copolymer (AN / St weight ratio 60/40, melt flow rate 10 g / 10 min (220 ° C., 10 kg) of the same composition excluding rubber was obtained from the resin composition thus obtained. )) And the content of the rubbery polymer in the whole composition to be 20% by weight by using an extruder, and after pelletizing, each test piece is prepared by injection molding to obtain each physical property. Was evaluated by the above method. The results are as shown in Table 1.

Example 2 (1) Production of Conjugated Diene-Acrylate Ester Copolymer Rubber Same as described in Example 1 (1). (2) Preparation of Graft Copolymer In the example described in Example 1 (2), the procedure was the same as in Example (2) except that the composition of the monomer mixture was changed as follows. Monomer mixture Acrylonitrile 520 g Styrene 130 g n-dodecyl mercaptan 19.5 g The solid content of the obtained latex was 34% by weight. The results of measuring the physical properties of the graft copolymer are shown in Table 1.

Example 3 (1) Production of Conjugated Diene-Acrylate Ester Copolymer Rubber In the example described in Example 1 (1), the composition of the monomer mixture was changed as follows. The procedure was the same as in Example (2). Monomer mixture 1,3-butadiene 1200 g Butyl acrylate 400 g Conversion 96%, average particle size 0.08 μm. (2) Production of graft copolymer Same as that described in Example 1 (2). The results of measuring the physical properties of the graft copolymer are shown in Table 1.

Example 4 (1) Production of Conjugated Diene-Acrylate Ester Copolymer Rubber In the example described in Example 1 (1), the composition of the monomer mixture was changed as follows. The procedure was the same as in Example (2). Monomer mixture 1,3-butadiene 400 g Butyl acrylate 1200 g Conversion 99%, average particle size 0.07 μm. (2) Production of graft copolymer Same as that described in Example 1 (2). The results of measuring the physical properties of the graft copolymer are shown in Table 1.

Example 5 (1) Production of Conjugated Diene-Acrylate Ester Copolymer Rubber In the example described in Example 1 (1), the composition of the monomer mixture was changed as follows. The procedure was the same as in Example (2). Monomer mixture 1,3-butadiene 800 g Butyl acrylate 792 g Allyl methacrylate 8 g Conversion 97%, average particle size 0.08 μm. (2) Production of graft copolymer Same as that described in Example 1 (2). The results of measuring the physical properties of the graft copolymer are shown in Table 1.

Example 6 (1) Production of Conjugated Diene-Acrylate Ester Copolymer Rubber In the example described in Example 1 (1), the composition of the monomer mixture was changed as follows. The procedure was the same as in Example (2). Monomer mixture 1,3-butadiene 640 g Butyl acrylate 720 g Acrylonitrile 80 g Styrene 160 g Conversion was 97% and average particle size was 0.08 μm. (2) Production of graft copolymer Same as that described in Example 1 (2). The results of measuring the physical properties of the graft copolymer are shown in Table 1.

Example 7 (1) Production of Conjugated Diene-Acrylate Ester Copolymer Rubber Same as described in Example 1 (1). (2) Production of Graft Copolymer The latex of (1) above is treated with acetic anhydride to give an average particle size of 0.15.
Latex with particle size enlarged to μm 1646 g (solid content 65
0g), sodium alkyldiphenyl ether disulfonate 13.0g, water (as total water content) 541g
Was charged into a 5 L glass flask equipped with a stirrer, a reflux condenser, a thermometer, and an auxiliary agent addition device, and the internal temperature was raised to 65 ° C. while stirring under a nitrogen stream. Water 2 while heating
Sodium pyrophosphate 6.5 g, dextrose 13.0 g and ferrous sulfate 0.065 g dissolved in 00 g
Was added. When the temperature reached 65 ° C., 0.49 g of cumene hydroperoxide, 3.9 g of sodium alkyldiphenyl ether disulfonate and 9 g of water were added to this flask.
5g was added. Acrylonitrile 390 after 15 minutes
g, styrene 260 g, n-dodecyl mercaptan 9.
The graft reaction was started by starting continuous addition of the monomer mixture in which 8 g was mixed. From immediately after the reaction to 4 hours later, the monomer mixture was added to the polymerization system at a constant addition rate.

From the start of the reaction, 30 minutes to 4 hours and 30 minutes later, 2.28 g of cumene hydroperoxide, 9.1 g of sodium alkyldiphenyl ether disulfonate and 222 g of water were added over 4 hours. To do. After the addition is complete, the reaction is continued for another hour, cooled,
The reaction is complete.

After adding 15 g of an antioxidant to the obtained graft polymer latex, it was added to an aqueous magnesium sulfate solution heated at 95 ° C. with stirring to coagulate. The solidified product was washed with water and dried to obtain a white powdery resin composition having a high rubber content.

The resin composition thus obtained was treated with a styrene-acrylonitrile copolymer (AN / St weight ratio 60/40, melt flow rate 10 g / 10 minutes (22
0 ° C., 10 kg)) and a rubbery polymer content in the entire composition of 20% by weight using an extruder.
After pelletizing, each test piece was prepared by injection molding, and each physical property was evaluated by the following methods. The results are as shown in Table 1.

Example 8 (1) Production of Conjugated Diene-Acrylate Ester Copolymer Rubber Same as described in Example 1 (1). (2) Production of Graft Copolymer In the example described in Example 1 (2), the rubber particle size was adjusted to 0.
The procedure was the same as in Example (2) except that the thickness was changed to 35 μm.

Example 9 (1) Production of Conjugated Diene-Acrylate Ester Copolymer Rubber Same as described in Example 1 (1). (2) Production of Graft Copolymer The latex of (1) above is treated with acetic anhydride to give an average particle size of 0.15.
Latex with particle size enlarged to μm 1646 g (solid content 65
0g), sodium alkyldiphenyl ether disulfonate 13.0g, water (as total water content) 541g
Was charged into a 5 L glass flask equipped with a stirrer, a reflux condenser, a thermometer, and an auxiliary agent addition device, and the inner temperature was raised to 65 ° C. while stirring under a nitrogen stream. Water 2 while heating
6.5 g of sodium pyrophosphate dissolved in 00 g, 6.5 g of dextrose and 0.065 g of ferrous sulfate were added. When the temperature reached 65 ° C., 0.49 g of cumene hydroperoxide, 3.9 g of sodium alkyldiphenyl ether disulfonate and 95% of water were added to the flask.
g was added. Acrylonitrile 455 after 15 minutes
g, 151.7 g of styrene, and 29.3 g of n-dodecyl mercaptan were started to be added continuously,
The graft reaction was started. From immediately after the reaction to 4 hours later,
The monomer mixture was added to the polymerization system at a constant addition rate.

Then, immediately after the continuous addition of the above-mentioned monomer mixture was completed, 43.3 g of styrene was continuously added to the polymerization system over 1 hour. Also, after starting the reaction, 30
From the minute to 4 hours and 30 minutes later, 2.28 g of cumene hydroperoxide, 9.1 g of sodium alkyldiphenyl ether disulfonate and 222 g of water were added over 4 hours.

After the addition of styrene was completed, the reaction was continued for another hour and cooled to complete the reaction. After adding 15 g of an anti-aging agent to the obtained graft polymer latex, it was added to an aqueous magnesium sulfate solution heated to 95 ° C. with stirring to coagulate. The solidified product was washed with water and dried to obtain a white powdery resin composition having a high rubber content.

The resin composition thus obtained was treated with a styrene-acrylonitrile copolymer (AN / St weight ratio 60/40, melt flow rate 10 g / 10 minutes (22
0 ° C., 10 kg)) and a rubbery polymer content in the entire composition of 20% by weight using an extruder.
After pelletizing, each test piece was prepared by injection molding, and each physical property was evaluated. The results are as shown in Table 1.

Comparative Example 1 (1) Production of Conjugated Diene-Acrylate Ester Copolymer Rubber In the example described in Example 1 (1), the composition of the monomer mixture was changed as follows. The procedure was the same as in Example (2). Monomer mixture 1,3-Butadiene 1400 g Styrene 160 g Conversion 97%, average particle size 0.08 μm. (2) Production of graft copolymer Same as that described in Example 1 (2). The results of measuring the physical properties of the graft copolymer are shown in Table 1.

Comparative Example 2 (1) Production of Conjugated Diene-Acrylate Ester Copolymer Rubber In the example described in Example 1 (1), the composition of the monomer mixture was changed as follows. The procedure was the same as in Example (2). Monomer mixture 1,3-butadiene 80 g Butyl acrylate 1520 g Conversion 99%, average particle size 0.07 μm. (2) Production of graft copolymer Same as that described in Example 1 (2). The results of measuring the physical properties of the graft copolymer are shown in Table 1.

Comparative Example 3 (1) Production of Conjugated Diene-Acrylate Ester Copolymer Rubber Same as described in Example 1 (1). (2) Preparation of Graft Copolymer In the example described in Example 1 (2), the procedure was the same as in Example (2) except that the composition of the monomer mixture was changed as follows. Monomer mixture acrylonitrile 585 g styrene 65 g n-dodecyl mercaptan 19.5 g The solid content of the obtained latex was 34% by weight. The results of measuring the physical properties of the graft copolymer are shown in Table 1.

Comparative Example 4 (1) Production of Conjugated Diene-Acrylate Ester Copolymer Rubber Same as described in Example 1 (1). (2) Preparation of Graft Copolymer In the example described in Example 1 (2), the procedure was the same as in Example (2) except that the composition of the monomer mixture was changed as follows. Monomer mixture acrylonitrile 195 g styrene 455 g n-dodecyl mercaptan 3.3 g The solid content concentration of the obtained latex was 34% by weight. The results of measuring the physical properties of the graft copolymer are shown in Table 1.

Comparative Example 5 (1) Production of Conjugated Diene-Acrylate Ester Copolymer Rubber Same as described in Example 1 (1). (2) Production of graft copolymer In the example described in Example 1 (2), the rubber particle size is 0.6.
The procedure was the same as in Example (2) except that the thickness was changed to 5 μm. The solid content concentration of the obtained latex was 31% by weight. The results of measuring the physical properties of the graft copolymer are shown in Table 1.
Shown in.

As shown in Table 1, the graft copolymer resin composition which does not satisfy the conditions specified in the present invention has any physical properties, particularly chemical resistance and / or impact resistance and / or impact resistance of molded articles. The resin fluidity is unsatisfactory, in other words, the graft copolymer resin composition according to the present invention is particularly excellent in the chemical resistance and / or impact resistance of the molded article and / or the resin fluidity. It is clear that they are excellent in physical property balance.

[0065]

[Table 1]

[0066]

EFFECT OF THE INVENTION The graft copolymer resin composition according to the present invention has excellent chemical resistance, good impact resistance and fluidity, and excellent physical property balance, as described above in [Summary of Invention]. By the way.

Claims (2)

[Claims] 1. A graft copolymer resin composition comprising the following component I and component II. Component I: 20 to 95% by weight of a conjugated diene monomer, 5 to 80% by weight of an ester compound of a monohydric alcohol having 2 to 12 carbon atoms and acrylic acid, and a vinyl monomer 0 copolymerizable therewith Rubber elastomer obtained by emulsion polymerization of a monomer mixture of 30 to 30% by weight and a polyfunctional vinyl monomer of 0 to 3% by weight in a latex of 10 to 70 parts by weight of vinyl cyanide monomer 50 to 85. % By weight, aromatic vinyl monomer 15 to
50% by weight and vinyl monomer copolymerizable therewith 0
90 to 30 parts by weight of a monomer mixture consisting of 30 to 30% by weight (however, the total amount of the rubber elastic body and the monomer mixture is 100 parts by weight) 20 to 100 parts by weight of a graft copolymer obtained by emulsion polymerization Component II: a monomer mixture consisting of 50 to 85% by weight of a vinyl cyanide monomer, 15 to 50% by weight of an aromatic vinyl monomer, and 0 to 30% by weight of a vinyl monomer copolymerizable therewith. Copolymer 0
-80 parts by weight (however, the total of the component I and the component II is 100 parts by weight, and the content of the rubber elastic body in this composition is 5 to 40% by weight) 2. The rubber elastic particles have an average particle size of 0.05 to.
The graft copolymer resin composition according to claim 1, which has a thickness of 0.50 μm.