JPH02206646A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent impact resistance and solvent resistance by blending polyphenylene oxide with a polyorganosiloxane graft copolymer resin and impact resistant polystyrene resin at a specific ratio. CONSTITUTION:The aimed composition obtained by blending (A) 15-80wt.% polyphenylene oxide resin [e.g. poly(2,6-dimethyl-1,4-phenylene) oxide] with (B) 4-40wt.% polyorganosiloxane based graft copolymer resin obtained by subjecting a polyorganosiloxane rubber obtained by subjecting an organosiloxane to emulsion polymerization with a crosslinking agent and graft crossing agent or obtained by subjecting a compound rubber consisting of the above-mentioned rubber and polyalkyl (meth)acrylate rubber to graft polymerization with a vinyl based monomer and having 0.08-0.6mum number-average granule size and (C) 10-80wt.% impact resistant polystyrene resin consisting of a matrix polystyrene component and 1-20wt.% polybutadiene.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition comprising a polyphenylene ether resin, a polyorganosiloxane graft copolymer resin, and a high-impact polystyrene resin.

The resin composition of the present invention is useful as a molded article with excellent impact resistance and solvent resistance.

[Prior Art] Polyphenylene ether provides molded products with excellent heat resistance, rigidity, etc., so its use as an engineering plastic is expanding. However, it has poor impact resistance,
Its use is restricted.

A common method for improving the impact resistance of polyphenylene ether is to blend it with impact-resistant polystyrene, but sufficient impact resistance cannot be obtained.

[Means for Solving the Problems] The above object is to add vinyl-based monomers to (A) polyphenylene ether resin, (B) polyorganosiloxane rubber, or a composite rubber in which the rubber and polyalkyl (meth)acrylate rubber are intertwined with each other. This is achieved by a resin composition characterized by comprising a polyorganosiloxane-based graft copolymer resin obtained by graft polymerization of polymers, and (C) a high-impact polystyrene resin.

A Phol Phenylene Ether The polyphenylene ether resin (A) used in the present invention has the following formula [Problem to be solved by the invention] The purpose of the present invention is to maintain the excellent properties of polyphenylene ether and An object of the present invention is to provide a resin composition that provides a molded article with excellent properties and solvent resistance.

(In the formula, Q'-Q' are each independently selected from the group consisting of hydrogen and hydrocarbon groups, and m represents a number of 30 or more.) A homopolymer or copolymer having the structure represented by .

Specific examples of such polyphenylene ether resins include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-dinityl-1°4-phenylene) ether, and poly(2,6-diprobyl-1,4-phenylene) ether. phenylene) ether, poly(2-methyl-6-ethyl-1,4-
phenylene) ether, poly(2-methyl-6-propyl-1°4-phenylene) ether, poly(2-ethyl-6-broby-1,4-phenylene) ether, (2
,6-dimethyl-1.4phenylene)ether and (2,
Copolymer with (3,6-)dimethyl-1,4-phenylene)ether, (2,3-dimethyl-1,4-phenylene)ether and (2,3.

Copolymer with 6-drimethyl-1,4-phenylene)ether, (2,6-dimethyl-1,4-phenylene)ether and (2,3,6-triethyl=1.4-)unisine)ether Examples include copolymers of. Among them, poly(2,6-dimethyl-1,4-phenylene) ether, and (2,6-dimethyl-1,4-phenylene) ether and (2,3,6-)dimethyl-1,4-phenylene) ether. A copolymer of poly(2°6
-Simethyl-1,4-phenylene) ether is most preferred. These polyphenylene ether resins are compatible with polystyrene resins at all blending ratios. The degree of polymerization of the polyphenylene ether resin used in the present invention is not particularly limited, but the reduced viscosity in a 25"C chloroform solvent is 0.3 to 0.7 d1/g.
Those are preferably used. Those with a reduced viscosity of less than 0.3 dR/g tend to have poor thermal stability, while those with a reduced viscosity of more than 0.7 dl/g tend to impair moldability. These polyphenylene ether resins may be used alone or in combination of two or more.

The polyorganosiloxane graft copolymer resin (B) used in the present invention is produced by graft polymerizing a vinyl monomer onto polyorganosiloxane rubber, or by graft polymerizing polyorganosiloxane rubber with polyalkyl (meth).
It is a product obtained by graft polymerizing a vinyl monomer to a composite rubber in which acrylate rubber and acrylate rubber are intertwined with each other.

Generally, polyorganosiloxane rubber can be obtained in the form of fine particles by emulsion polymerization using an organosiloxane, a crosslinking agent, and a grafting agent. Composite rubber of polyorganosiloxane rubber and polyalkyl (meth)acrylate rubber is obtained by emulsion polymerization using organosiloxane, a crosslinking agent, and optionally a grafting agent to obtain a polyorganosiloxane rubber component as fine particles. It can be obtained by impregnating a rubber component with (meth)acrylate, a crosslinking agent, and a grafting agent and then polymerizing it.

The number average particle diameter of the polyorganosiloxane graft copolymer is preferably in the range of 0.08 to 0.61. If the average particle size is less than 0.08μ, the impact resistance of the molded product obtained from the resin composition will deteriorate, and if the average particle size exceeds 0.6μ, the impact resistance of the molded product obtained from the resin composition will deteriorate. Not only does the impact resistance deteriorate, but the appearance of the molded surface also deteriorates. Emulsion polymerization is optimal for producing a polyorganosiloxane graft copolymer having such an average particle size.

The organosiloxane used for preparing the polyorganosiloxane rubber includes various cyclic bodies having 3 or more membered rings, and 3- to 6-membered rings are preferably used. Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trinotyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, etc. These can be used alone or in combination of two or more.

The amount of these used is 5% in the polyorganosiloxane rubber component.
It is 0% by weight or more, preferably 70% by weight or more.

As the crosslinking agent used for preparing the polyorganosiloxane rubber, trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane,
Tetra-n-propoxysilane, tetrabutoxysilane, etc. are used. Particularly preferred are tetrafunctional crosslinking agents, and among these, tetraethoxysilane is particularly preferred. The amount of crosslinking agent used is 0.1 to 0.1 in the polyorganosiloxane rubber component.
It is 30% by weight.

As a graft cross-agent, the following formula (% formula %) (In each formula, R' is a methyl group, ethyl group, propyl group or phenyl group, ' Rt is a hydrogen atom or a methyl group,
n represents 0.1 or 2, and p represents a number from 1 to 6. ) Formula 0 (1-
(Meth)acryloyloxysiloxane, which can form the unit 1), has a high grafting efficiency and can form effective graft chains, which is advantageous in terms of impact resistance. Note that methacryloyloxysiloxane is particularly preferred as a compound capable of forming units of formula Cl-1). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, T-
Methacryloyloxypropylmethoxydimethylsilane, T-methacryloyloxypropyldimethoxymethylsilane, T-methacryloyloxypropyltrimethoxysilane, T-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyljethoxymethylsilane, δ-methacryloyloxybutylsilane Examples include toxymethylsilane.

The amount of the grafting agent used is 0 to 10% by weight in the polyorganosiloxane rubber component.

The latex of this polyorganosiloxane rubber component can be produced using, for example, the method described in U.S. Pat. No. 2,891,920, U.S. Pat. It is preferable to produce by a method in which a mixed solution of a crosslinking agent and, if desired, a grafting agent is mixed with water in the presence of a sulfonic acid emulsifier such as an alkylbenzenesulfonic acid or an alkylsulfonic acid using, for example, a homogenizer or the like. , alkylbenzenesulfonic acid is suitable because it acts as an emulsifier for organosiloxane and also serves as a polymerization initiator. At this time, it is preferable to use an alkylbenzenesulfonic acid metal salt, an alkylsulfonic acid metal salt, or the like in combination, since this is effective in maintaining the polymer stably during graft polymerization.

A vinyl monomer can be graft-polymerized onto the polyorganosiloxane rubber component.

Alternatively, a composite rubber can be prepared from the rubber component and a polyalkyl (meth)acrylate rubber component, and then a vinyl monomer can be graft-polymerized onto the composite rubber.

The polyalkyl (meth)acrylate rubber component constituting the above composite rubber can be synthesized using the alkyl (meth)acrylate, crosslinking agent, and grafting agent shown below.

Examples of alkyl (meth)acrylates include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl acrylate. Examples include alkyl methacrylates such as methacrylate, with n-butyl acrylate being particularly preferred.

Examples of the crosslinking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1
, 3-butylene glycol dimethacrylate, 1,4-
Examples include butylene glycol dimethacrylate.

Examples of the grafting agent include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and the like. Allyl methacrylate can also be used as a crosslinking agent.

These crosslinking agents and grafting agents may be used alone or in combination of two or more. The total amount of these crosslinking agents and grafting agents used is 0.1 to 20% by weight in the polyalkyl (meth)acrylate rubber component.

The polymerization of the polyalkyl (meth)acrylate rubber component is
The above alkyl (
After adding meth)acrylate, a crosslinking agent, and a grafting agent and impregnating them into polyorganosiloxane rubber particles, a conventional radical polymerization initiator is applied. As the polymerization progresses, a crosslinked network of polyalkyl (meth)acrylate rubber is formed that is intertwined with the crosslinked network of polyorganosiloxane rubber, and the polyorganosiloxane rubber component and polyalkyl (meth)acrylate rubber component are virtually inseparable. A composite rubber latex is obtained. In this composite rubber, the main skeleton of the polyorganosiloxane rubber component has repeating units of dimethylsiloxane, and the main skeleton of the polyalkyl (meth)acrylate rubber component has n-
Composite rubbers having repeating units of butyl lacquer and rylate are particularly preferred.

The ratio of the polyorganosiloxane rubber component and the polyalkyl (meth)acrylate rubber component in the composite rubber is such that the former is 10% by weight or more and the latter is 90% by weight or less. If the proportion of the polyalkyl (meth)acrylate rubber component exceeds 90% by weight, impact resistance will be insufficiently expressed.

The polyorganosiloxane rubber or composite rubber thereof prepared by emulsion polymerization in this manner can be graft copolymerized with a vinyl monomer. Vinyl monomers to be graft polymerized include styrene, α-methylstyrene,
Aromatic alkenyl compounds such as vinyltoluene; Methacrylic acid esters such as methyl methacrylate and 2-ethylhexyl methacrylate; Acrylic acid esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, etc. Examples include various vinyl monomers. These vinyl monomers may be used alone or in combination. Among these vinyl monomers, aromatic alkenyl compounds are preferred, and styrene is particularly preferred.

The ratio of the rubber component to the vinyl monomer is preferably 30 to 95% by weight of the former and 5 to 70% by weight of the latter. If the vinyl monomer content is less than 5% by weight, the dispersibility of the polyorganosiloxane graft copolymer resin (B) in the resin composition will be poor, while if it exceeds 70% by weight, the impact strength will not be developed. descend.

As the C-rich styrene impact-resistant polystyrene resin (C), polystyrene containing 1 to 20% by weight of the total weight of a polymer having a conjugated diene polymer structure derived from butadiene as a rubber component is advantageously used.

If the rubber component is less than 1%, the impact resistance will be poor, and if it is more than 20%, the polymerization will have a particularly high viscosity.Also, it is preferable that the dispersed particle size of the elastic body is 2 or more, and if it is smaller than 2Jna, the impact resistance will be poor. It has poor solvent properties and cracks occur when it comes into contact with a solvent.If it exceeds 8, the surface appearance of the resin molded product will deteriorate significantly.In this polystyrene, at least 5
Although it is essential to have a polymer structure derived from 0% by weight or more of styrene monomer, there is no problem in including a polymer structure derived from chlorostyrene monomer or α-methylstyrene monomer. do not have. Each of the above structures may be in the form of a polymer mixture or a copolymer.

However, the weight average molecular weight of the polystyrene component serving as the matrix is preferably 150,000 to 500,000; if it is smaller than iso or ooo, the solvent resistance will be poor;
Cracks are more likely to occur due to solvents. soo,o
If it is larger than oo, molding is difficult and impractical.

High impact polystyrene is produced as follows.

First, polybutadiene is dissolved in styrene monomer, and then this starting solution is polymerized. The amount of polybutadiene used is preferably 1 to 20% by weight, particularly 2 to 15% by weight, based on the weight of the solution. Polymerization of the starting solution takes place in at least two stages. In this process, the styrene monomer with dissolved polybutadiene is initially polymerized in bulk under the action of shearing forces in the first stage, and then in one or more subsequent stages under weaker shearing or no shearing. Polymerized in suspension without the action of force. The first stage of initial polymerization is usually carried out at a temperature in the range of 50 to 110°C. Polymerization is initiated by heating or by free radical generating initiators.

As the free radical generation initiator, commonly used initiators,
For example, alkyl peroxide, acyl peroxide,
Hydrogen peroxide, perester, carbonate peroxide, azo compound, etc. are used, and initiators showing grafting activity, such as benzoyl peroxide, are particularly preferred.The initiator concentration is 0.001 to 0.001 to styrene monomer. 1.0 mol%, preferably 0
．． 0.005 to 0.5 mol%. A decomposition accelerator for the initiator may be used in combination.

The reaction product obtained in the initial polymerization may contain known water-soluble suspending agents such as methylcellulose, oxypropylcellulose, polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinylpyrrolidone, etc., and inorganic dispersants such as sulfuric acid. Barium is added (these are generally added in an amount of 0.1 to 5% by weight relative to the organic layer) and suspended in water, and the polymerization is completed, usually at a temperature of 40 to 160°C. At this time, 0.01 to 0.2% by weight of a polymerization initiator was added to adjust the molecular weight of the polystyrene matrix.
, preferably 0.03 to 0.15% by weight.

The target product obtained has a weight average molecular weight of 150.000.
It may be mechanically kneaded with polystyrene having a molecular weight of 500,000 to 500,000 using an extruder or the like.

■Two stars on the bottom of the base plate 1 Resin components used in the present invention (A), (B), (C
) can vary over a wide range. In particular, (A) component 15-80! Amount %, (B) component 4
~40% by weight (C) component 10-80% by weight, (A),
It is preferable that the total amount of (B) and (C) is 100% by weight.

When component (A) is less than 15% by weight, heat resistance is insufficient, and when it exceeds 80% by weight, molding becomes difficult. (B)
If the component is less than 4% by weight, the effect of improving impact resistance will be poor, and if it exceeds 40% by weight, heat resistance and impact resistance will decrease. When the amount of component (C) is less than 10% by weight, there is no effect on improving solvent resistance. If it exceeds 80% by weight, heat resistance will be insufficient.

As a method for preparing the resin composition of the present invention, resin components (A), (B), and (C), and optionally a phosphate ester flame retardant represented by triphenyl phosphate and/or glass fibers are added to the pan. The mixture may be mechanically mixed using a known device such as a burr mixer, a roll mill, or a twin-screw extruder, and then shaped into a pellet.

Furthermore, stabilizers, plasticizers, lubricants, pigments, fillers, etc. may be added to the resin composition of the present invention, if necessary. Specifically, stabilizers such as triphenyl phosphite; lubricants such as polyethylene wax and polypropylene wax; pigments such as titanium oxide, zinc sulfide, and zinc oxide; fillers such as asbestos, wollastonite, mica, and talc. It will be done.

〔Example〕

Hereinafter, the resin composition of the present invention will be specifically explained with reference to Examples. In the examples, "part" and "1%" mean parts by weight and % by weight unless otherwise specified.

The physical properties of the obtained sample were measured in the following manner.

Izot Impact Strength: As per ASTM 256 method (1/4" molded, with 1/4" edge) Solvent Resistance: Kerosene resistance measured by cantilever method, i.e. 6" long, 1/2" wide, 1/8 thick A specimen of `` was supported at three points at room temperature so that the maximum stress was 200 kg/c+a, kerosene was applied to the surface of the molded specimen on the elongated side, and the time until the specimen broke was measured. It is judged that 5 hours or more can withstand practical use.

Flame retardancy: Based on tlL-94V vertical flammability test.

Kokokanjo Impact-resistant polystyrene (H5-1 to H5-6
) To a styrene monomer containing a predetermined amount of polybutadiene (molecular weight 180,000.1°, 2-vinyl content 10%), 0.088 mol% benzoyl peroxide (based on styrene) was added and the mixture was stirred. Initial polymerization was carried out in a reaction tank at a predetermined temperature until the styrene monomer conversion rate reached about 35%.

Next, add a predetermined amount of dicumyl peroxide (listed in Table 1)
was dissolved in a polymer solution, and 3 times the amount of water containing 0.64% by weight of sodium carboxymethylcellulose was added,
A polymer solution was suspended therein. Further, while stirring, the reaction was carried out at 120°C for 5 hours and then at 140'C for 5 hours.

The weight average molecular weight of the matrix is determined by extracting the soluble content from the obtained impact-resistant polystyrene with methyl ethyl ketone
Measured using PC.

The number average particle diameter of the elastic phase obtained from polybutadiene was determined from the average of 200 to 300 thin layer photographs taken using an electron microscope.

Table 1 shows the properties of impact-resistant polystyrene produced under various manufacturing conditions.

Table 1: Production of polyorganosiloxane-based graft copolymer (S-1) 2 parts of tetraethoxysilane, 0.5 parts of γ-methacryloyloxypropyldimethoxymethylsilane, and 97.5 parts of octamethylcyclotetrasiloxane were mixed to obtain 100 parts of a siloxane mixture. Add 100 parts of the above mixed siloxane to 200 parts of distilled water in which 1 part each of sodium dodecylbenzenesulfonate and dodecylbenzenesulfonic acid were dissolved, and mix with a homomixer at 10.00 Orp.
After pre-stirring at m, 300 kg was prepared using a homogenizer.
The mixture was emulsified and dispersed at a pressure of /d to obtain an organosiloxane latex.

This mixed solution was transferred to a separable flask equipped with a condenser and stirring blades, heated at 80°C for 5 hours while stirring, and then left at 20°C. After 48 hours, the pH of the latex was adjusted with an aqueous sodium hydroxide solution. 6.9 to complete the polymerization to obtain polyorganosiloxane rubber latex-1. The polymerization rate of the obtained polyorganosiloxane rubber was 89.7%, and the number average particle diameter of the polyorganosiloxane rubber was 0.16-.

This polyorganosiloxane latex-1, 234
, 1 part was collected, placed in a separable flask equipped with a stirrer, 60 parts of distilled water was added, the temperature was raised to 60°C after purging with nitrogen, and 0.002 part of ferrous sulfate and disodium ethylenediaminetetraacetate were added. Salt 0.006 parts, Rongalit 0.26
A mixture of 0.1 part of cumene hydroperoxide and 30 parts of styrene was added dropwise over 30 minutes, and then maintained at 70°C for 3 hours.
Polymerization of styrene was completed. The polymerization rate of styrene is 92.
It was 1%. The obtained graft copolymer latex was dropped into 300 parts of hot water containing 1.5% by weight of calcium chloride, solidified and separated, and then dried at 80'C for 20 hours to form a polyorganosiloxane-based graft copolymer (hereinafter referred to as , referred to as S-1) was obtained.

Summary ■D Production of polyorganosiloxane-based graft copolymer (S-2) Polyorganosiloxane-based graft copolymer (S-1)
Collect 293 parts of polyorganosiloxane rubber latex-1 obtained in the manufacturing process, put it in a separable flask equipped with a stirrer, add 102 parts of distilled water, replace with nitrogen, and raise the temperature to 65 ° C. A mixed solution of 0.002 part of ferrous sulfate, 0.006 part of ethylenediaminetetraacetic acid disodium salt, 0.26 part of Rongalite, and 5 parts of distilled water was charged.

A mixture of 0.12 parts of tert-butyl hydroxyperoxide and 15 parts of methyl methacrylate was added dropwise to this latex at 65°C for 15 minutes, and then
The mixture was maintained at 5°C for 4 hours to complete graft polymerization to the polyorganosiloxane rubber. The polymerization rate of methyl methacrylate was 99.5%. The obtained graft copolymer latex was soaked in hot water containing 1.5% by weight of calcium chloride.
00 parts, coagulate, separate and wash, then heat at 75°C to 1
After drying for 6 hours, 97.0 parts of dry powder of a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-2) was obtained.

Manufacturing of polyorganosiloxane composite rubber-based graft copolymer (S-3) Polyorganosiloxane-based graft copolymer (S-1)
Collect 25 parts of polyorganosiloxane latex-1 prepared in the manufacturing process, put it in a separable flask equipped with a stirrer, add 53.3 parts of distilled water, replace it with nitrogen, and raise the temperature to 60 °C. and n-butyl acrylate 7.3
5 parts, allyl methacrylate 0.15 parts and tert
- A mixed solution of 0.038 parts of butyl hydroperoxide was infiltrated into polyorganosiloxane rubber particles.
Ferrous sulfate 0.00025 parts, ethylenediaminetetraacetic acid disodium salt 0. C) 0075 copies, Rongarit) 0.
A mixed solution of 0.6 parts of distilled water and 4.2 parts of distilled water was charged, radical polymerized, and then kept at an internal temperature of 70° C. for 2 hours to complete the polymerization and obtain a composite rubber latex.

A portion of this latex was sampled and the number average particle diameter of the composite rubber was measured and found to be 0.207/11. In addition, this latex was dried to obtain a solid substance, extracted with toluene at 90°C for 112 hours, and the gel content was determined to be 98.0.
% by weight.

A mixture of 0.048 parts of tert-butyl hydroperoxide and 10 parts of styrene was added dropwise to the composite rubber latex at 70"C for 60 minutes, and then at 70"C.
The mixture was held for 4 hours to complete the graft polymerization to the composite rubber. The weight percentage of styrene was 98.5%. The obtained graft copolymer latex was dropped into 200 parts of hot water containing 1.5% by weight of calcium chloride, coagulated, separated, washed, and then dried at 75°C for 16 hours to form a composite rubber-based graft copolymer ( 96.5 parts of dry powder of S-3) was obtained.

Production of polyorganosiloxane composite rubber-based graft copolymer (S-4) Polyorganosiloxane-based graft copolymer (S-1)
Collect 117 parts of polyorganosiloxane rubber latex-1 obtained in the manufacturing process, put it in a separable flask equipped with a stirrer, add 57.5 parts of distilled water, replace it with nitrogen, and raise the temperature to 60 ° C. Then, a mixed solution of 49 parts of n-butyl acrylate, 1.0 part of allyl methacrylate, and 0.26 parts of tert-butyl hydroperoxide was charged.
The mixture was stirred for a minute to infiltrate the polyorganosiloxane rubber particles, and then 0.002 part of ferrous sulfate was added.
0.006 part of ethylenediaminetetraacetic acid disodium salt,
A mixed solution of 0.26 parts of Rongalite and 5 parts of distilled water was charged to initiate radical polymerization, and then the internal temperature was maintained at 70''C for 2 hours to complete the polymerization, yielding a composite rubber latex.

A portion of this latex was sampled and the average particle size of the composite rubber was measured and found to be 0.19 m. Further, this latex was dried to obtain a solid substance, extracted with toluene at 90°C for 12 hours, and the gel content was measured and found to be 97.3% by weight. To this composite rubber latex, 0.12 parts of tert-butyl hydroperoxide and 1 part of methyl methacrylate were added.
5 parts of the mixture was added dropwise at 70'C over 15 minutes, and then maintained at 70'C for 4 hours to complete the graft polymerization to the composite rubber. The polymerization rate of methyl methacrylate is 9
It was 9.5%. The obtained graft copolymer latex was dropped into 200 parts of hot water containing 1.5% by weight of calcium chloride, coagulated, separated, washed, and then dried at 75°C for 16 hours to form a composite rubber-based graft copolymer ( 96.5 parts of dry powder (hereinafter referred to as S-4) was obtained.

1 to 4" using axial extrusion (manufactured by Werner Faudler, ZSK-30 type), the resin components shown in Table 2 were heated at a cylinder temperature of 27.
The mixture was melted and kneaded at 0°C and shaped into pellets. After drying the obtained pellet, the cylinder temperature was set to 260 to 280 using an injection molding machine (Promat injection molding machine manufactured by Jujuki Co., Ltd.).
A sample was molded at a mold temperature of 70°C. Samples were also obtained in the same manner in Examples and Comparative Examples described below.

Table 2 shows the impact strength and solvent resistance of each specimen.

table A
/g (25°C, Chloroform solvent) ) has poor impact resistance and solvent resistance, but when a polyorganosiloxane graft copolymer is further blended (Examples 1 to 3)
, impact resistance and solvent resistance are both significantly improved.

In particular, those in which the polybutadiene elastomer phase in the impact-resistant polystyrene resin has a large number average particle diameter (Examples 1 and 3) have superior solvent resistance compared to those with a small number average particle diameter (Example 4).

The resin composition was changed as shown in Table 3 (i.e., in Examples 5 and 6.7, high impact polystyrenes HS-4, H5-5 and H3-6 with different molecular weights of matrix polystyrene were used). In addition, in Example 8, polyorganosiloxane-based graft copolymer S-2 was used instead of S-1.) Samples were prepared under the same conditions as in Examples 1 to 4, and tested. did. The results are shown in Table-3.

Table 1. Characteristics Back 10, 11 Samples were prepared under almost the same conditions as Examples 1 to 4, except that the resin composition was changed as shown in Table 4 (that is, various additives were added). was created and its properties were tested. Table 4 shows the results.
Shown below.

5-2 (parts) C impact resistant polystyrene US-4 (parts) #) Is-5 (parts) H5-6 (parts) /MS-2 (parts) *1 Polyphenylene ether; reduced viscosity 0.49 dl/ g(
25°C, chloroform solvent) Table C Impact-resistant polystyrene) Is-2 (parts) Polystyrene 1 (parts) D1 Flame retardant plasticizer $3 (parts) D2 Wide carposi 94 (parts) D, Glass fiber *S (@I *3 Triphenyl phosphate *4 Aerosil R972 manufactured by Ueya Kaolin ■; Contains 99.8% silicon dioxide *5 EC5O3T-828 manufactured by Electric Glass ■ 6 L
Based on IL-94, the resin composition was changed as shown in Table 5 (i.e., polyorganosiloxane composite was used instead of polyorganosiloxane-based graft copolymer S-1). Samples were prepared under the same conditions as in Examples 1 to 4, except that rubber copolymer S-3 was used, and their properties were tested. The results are shown in Table-5.

Solvent resistance (cantilever) >24
11 >24 (hours) H flammability” VI-I VI-I
V-1*1 Polyphenylene ether; reduced viscosity 0.4
9 dl/g (25°C, chloroform as a container) Book 2 Nippon Polystyrene Co., Ltd. "Nisbrite 7" Table Is-2 (parts) Is-3 (parts) Zuristyreshi 0 1 Polyphenylene ether; reduced viscosity 0.49 dl
/g (25"c, chloroform solvent) Book 2 "Nisprite 7' manufactured by Nippon Polystyrene Co., Ltd. As shown in Table 2, polyphenylene nityl A was mixed with impact-resistant polystyrene (
HS-3) alone (Comparative Example 1), the impact resistance and solvent resistance are poor, but when the polyorganosiloxane composite rubber graft copolymer is further blended (Example 1), the impact resistance and solvent resistance are poor.
2 to 15), both impact resistance and solvent resistance are significantly improved. In particular, impact-resistant polystyrene resin with a large number average particle size of the polybutadiene elastomer phase (Example 1
2.14) has better solvent resistance than the smaller one (Example 15).

11■ The Kawafujikawa resin composition was changed as shown in Table 6 (i.e., in Examples 16, 17, and 18, impact-resistant polystyrene O54, HS-
5 and) Is-6, and in Example 19, polyorganosiloxane composite rubber-based graft copolymer S-
Samples were prepared under the same conditions as in Examples 12 to 15, except that S-4 was used instead of Sample No. 3, and their properties were tested. The results are shown in Table-6.

Polyphenylene ether (parts) Table 11 was prepared under almost the same conditions as Examples 12 to 15, except that the resin composition was changed as shown in Table 7 (that is, various additives were added). A specimen was prepared and its properties were tested. The results are shown in Table-7.

5-4 (parts) ) 1s-5 (parts) MS-6 (parts) HS-2 (parts) *1 Polyphenylene ether; reduced viscosity o, 49d/
g (25°C, chloroform solvent) Table *3 *4 *5 *6 Triphenylphosphate Aerosil R972 manufactured by Kaolin ■; Silicon dioxide 9
Based on BC5O3T-828 UL-94 manufactured by Electric Glass Co., Ltd. containing 9.8%. Sample thickness 16" Polystyrene thffi (parts) D1 Flame retardant plasticizer *3 (parts) D2 Newite carbon "4 (parts) Shima Glass foam T-ino "-8 (parts) Flame retardant Shima *1 *2 V-I Ll ν・1 polyphenylene ether; reduced viscosity 0.49 d/g (
25°C1 chloroform solvent) manufactured by Nippon Polystyrene Co., Ltd.
Varnish Bright 7'' [Effects of the Invention] The resin composition of the present invention exhibits excellent impact resistance and solvent resistance by having the composition as described above.

Claims (1)

[Claims] 1. Graft polymerization of a vinyl monomer to (A) a polyphenylene ether resin, (B) a polyorganosiloxane rubber, or a composite rubber in which the rubber is intertwined with a polyalkyl (meth)acrylate rubber. A resin composition comprising a polyorganosiloxane-based graft copolymer resin and (C) an impact-resistant polystyrene resin. 2. Polyorganosiloxane rubber is obtained by emulsion polymerization using organosiloxane, a cross-linking agent, and a grafting agent; A polyorganosiloxane rubber component obtained by emulsion polymerization using a crosslinking agent and optionally a grafting agent, and a polyalkyl obtained by impregnating the rubber component with an alkyl (meth)acrylate, a crosslinking agent, and a grafting agent and then polymerizing the rubber component. (meth)acrylate rubber component; and the number average particle diameter of the obtained polyorganosiloxane graft copolymer resin is 0.08 to 0.6.
The resin composition according to claim 1, which has a diameter of .mu.m. 3. The impact-resistant polystyrene resin consists of a matrix polystyrene component and polybutadiene, and the weight average molecular weight of the matrix polystyrene component is 150,000 to 5.
00,000, and the amount of polybutadiene is 1 to 20% by weight based on the weight of the high-impact polystyrene resin,
The resin composition according to claim 1, wherein the elastic phase has a number average particle diameter of 2 to 8 μm. 4. The proportion of each resin component is (A) 15 to 80% by weight, (B
) 4 to 40% by weight, and (C) 10 to 80% by weight.