JPH059385A - Polyarylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To provide a polyarylene sulfide resin composition having excellent impact strength and heat-resistance. CONSTITUTION:The objective resin composition is produced by melting and mixing (A) a polyarylene sulfide resin with (B) a resin composed mainly of a polyorganosiloxane graft copolymer obtained by the graft-polymerization of an epoxy-containing vinyl monomer to a composite rubber containing a polyorganosiloxane rubber and a polyalkyl (meth)acrylate rubber in an inseparably interlocked state. It has excellent impact resistance, gives a molding having good appearance and expanded applications.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyarylene sulfide resin composition having excellent impact strength and heat resistance.

[0002]

2. Description of the Related Art A composition having improved impact resistance of polyarylen sulfide resin is disclosed in JP-A-60-12075.
No. 3 discloses polyarylene sulfide resin with silicone rubber, ethylene-acrylic rubber, EP rubber, EPDM.
And a butyl acrylate rubber compounded composition
No. 3-27559 discloses a composition in which a graft acrylic rubber is blended with a poly (arylene sulfide) resin, and JP-A-2-138360 discloses a silicone in which a specific vinyl monomer is grafted to a poly (arylene sulfide) resin.
A composition containing rubber has been proposed.

[0003]

However, JP-A-60-
The compositions proposed in No. 120753 and JP-A No. 63-27559 have extremely poor compatibility with both the polyarylen sulfide resin and the above-mentioned rubber, and the heat resistance originally possessed by the polyarylen sulfide resin is high. There is a problem that it is difficult to improve the impact strength without significantly impairing the mechanical properties and mechanical properties. In addition, JP-A-2-13
Although the composition proposed in Japanese Patent No. 8360 is relatively excellent among these, it has a problem that the improvement of impact strength is still insufficient and the surface appearance of the molded product is poor.

[0004]

SUMMARY OF THE INVENTION In view of such a situation, the present inventors have made polyarynes having improved impact strength without significantly impairing the heat resistance and mechanical properties originally possessed by polyarylen sulfide resins. As a result of diligent studies to obtain a rensulfide resin composition, as a result, at least an epoxy resin was added to a composite rubber in which a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber are intertwined inseparably into a polyarylen sulfide resin. It was found that the above object can be achieved by blending a polyorganosiloxane-based graft copolymer resin obtained by graft-polymerizing one or more vinyl-based monomers including a group-containing vinyl-based monomer, and the present invention Reached

That is, the gist of the present invention is that (A) a polyarylene sulfide resin, and (B) a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber are entwined with each other inseparably from each other and integrated. The main resin component is a polyorganosiloxane-based graft copolymer obtained by graft-polymerizing one or more vinyl-based monomers containing at least one epoxy-group-containing vinyl-based monomer to the compounded rubber It is a polyarylene sulfide resin composition obtained by melt-mixing materials. The present invention will be described in detail.

(A) Poly (arylene sulfide) resin The poly (arylene sulfide) resin used in the present invention is a repeating unit represented by the general formula-(-Ar-S-)-[wherein Ar is

[0007]

[Chemical 1]

[0008]

[Chemical 2]

(However, X is --SO _2- , --CO--,-
It represents an alkylene group having 1 to 5 carbon atoms in the main chain, which may have an O- or lower alkyl side chain. ) And those having 1 to 8 substituents such as halogen and methyl groups on these aromatic rings. ] As a main structural unit, may be composed of only a linear structure or a branched chain, as long as it has a melt processability, it has a cross-linked structure. Good. As the polyarylene sulfide resin used in the present invention, polyphenylene sulfide resin is preferable.

(B) Polyorganosiloxane-based graft copolymer The polyorganosiloxane-based graft copolymer used in the present invention is a composite rubber composed of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber, and at least one epoxy compound. One or more vinyl-based monomers including a group-containing vinyl-based monomer are graft-polymerized.

(1) Polyorganosiloxane Rubber The polyorganosiloxane rubber constituting the composite rubber in the present invention is a crosslinker for organosiloxane and polyorganosiloxane rubber [hereinafter referred to as crosslinker (I)] and, if desired, for polyorganosiloxane rubber. It can be obtained as fine particles by emulsion polymerization of a graft crossing agent [hereinafter referred to as graft crossing agent (I)].

As the organosiloxane used for preparing the polyorganosiloxane rubber, a cyclic organosiloxane having 3 or more membered rings is used, and those having 3 to 6 membered rings are preferably used. Examples of such cyclic organosiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
Examples thereof include trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, etc. These may be used alone or in combination of two or more.

As the crosslinking agent (I) used for preparing the polyorganosiloxane rubber, a trifunctional or tetrafunctional one, that is, a trialkoxyalkyl or arylsilane or tetraalkoxysilane is used. Specific examples of the agent include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. As the cross-linking agent (I) used in the present invention, tetraalkoxysilane is preferable, and tetraethoxysilane is particularly preferably used among the above.

The graft crossing agent (I) used for preparing the polyorganosiloxane rubber has the following formula:

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017]

[Chemical 5]

[0018]

[Chemical 6]

(In each formula, R ¹ represents a methyl group, an ethyl group, a propyl group or a phenyl group, R ² represents a hydrogen atom or a methyl group, n represents 0, 1 or 2, and p represents 1 to 6). The compound etc. which can form the unit represented by these are used.

A unit represented by Chemical formula 3 can be formed (meta).
Acryloyloxyalkyl siloxane is preferable because it has a high grafting efficiency and can efficiently form a graft chain, and the composition of the present invention using the same has more excellent impact resistance. Among the (meth) acryloyloxyalkylsiloxanes, methacryloyloxyalkylsiloxanes are preferred, and β-
Methacryloyloxyethyldimethoxymethylsilane,
γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethoxysilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyl Examples include oxybutyldiethoxymethylsilane and the like.

Examples of the vinyl siloxane capable of forming the unit represented by Chemical formula 4 include vinylmethyldimethoxysilane and vinyltrimethoxysilane, and the mercaptosiloxane capable of forming the unit represented by Chemical formula 5 is γ-mercapto. Examples thereof include propyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyldiethoxyethylsilane and the like. Further, as the compound capable of forming the unit represented by Chemical formula 6,
Examples thereof include p-vinylphenylmethyldimethoxysilane.

In the polyorganosiloxane rubber, the amount of the component derived from the cyclic organosiloxane is 60% by weight or more, preferably 70% by weight or more, and the amount of the component derived from the crosslinking agent (I) is 0.1 to 30% by weight. And the amount of the component derived from the graft crossing agent (I) is 0 to 10% by weight. In producing the latex of the polyorganosiloxane rubber component, for example, the method described in US Pat. Nos. 2,891,920 and 3,294,725 can be used. In carrying out the present invention, an organosiloxane, a cross-linking agent (I) and a mixed solution of a graft crossing agent (I) are mixed with, for example, a homogenizer in the presence of a sulfonic acid emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid. It is preferably produced by a method of shear mixing with water. As the sulfonic acid-based emulsifier, alkylbenzene sulfonic acid is preferably used because it acts as an emulsifier of organosiloxane and at the same time acts as a polymerization initiator. At this time, it is preferable to use a metal salt of alkylbenzene sulfonic acid, a metal salt of alkyl sulfonic acid, or the like, because it is effective in maintaining the emulsion state of the polymer stably during the graft polymerization.

(2) Polyalkyl (meth) acrylate rubber The polyalkyl (meth) acrylate rubber component constituting the composite rubber is the alkyl (meth) acrylate shown below,
Crosslinking agent for polyalkyl (meth) acrylate rubber (hereinafter referred to as crosslinking agent (II)) and graft crossing agent for polyalkyl (meth) acrylate rubber (hereinafter graft crossing agent (I
I)) can be used for the synthesis. This synthesis is preferably carried out by emulsion polymerization in the presence of the above polyorganosiloxane rubber latex. As a result, a composite rubber is obtained in which the polyorganosiloxane rubber and the polyalkyl (meth) acrylate rubber are intertwined inseparably from each other and integrated.

Examples of the alkyl (meth) acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and other alkyl acrylates and hexyl. Methacrylate, 2-ethylhexyl methacrylate
And alkyl methacrylate such as n-lauryl methacrylate, and n-butyl acrylate is preferably used as the alkyl (meth) acrylate.
A polyfunctional (meth) acrylate can be used as the crosslinking agent (II), and ethylene glycol dimethacrylate can be used.
Propylene glycol dimethacrylate, 1,3-
Specific examples thereof include butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and allyl methacrylate.

As the graft crossing agent (II), compounds having two kinds of unsaturated groups having different reactivities are used. Examples of such compounds are allyl methacrylate, triallyl cyanurate and triallyl. Isocyanate and the like can be mentioned. Triallyl cyanurate and triallyl isocyanurate appear to have the same reactivity of the three allyl groups, but the second and third allyl groups react after the reaction of the first allyl group. Since the reactivity at this time is different from the reactivity at the time when the first allyl group reacts, it can be regarded as having an unsaturated group having different reactivity. In the case of allyl methacrylate, among the two unsaturated groups,
The less reactive one also acts as a crosslinking site by reacting during part of the polymerization, and since these do not react at all during the polymerization, the remaining unsaturated groups act as a graft site during the subsequent graft polymerization. is there. These cross-linking agents (II) and graft cross-linking agents (II) can be used alone or in combination of two or more, and it is preferable that allyl methacrylate serves both functions.

The amounts of the cross-linking agent (II) and the graft cross-linking agent (II) used are polyalkyl (meth) acrylate.
It is 0.1 to 10% by weight in the rubber component. Cross-linking agent (II)
In the case where allyl methacrylate is used as the graft crossing agent (II), 0.2 to 20% by weight of the polyalkyl (meth) acrylate rubber component is used to obtain other crosslinking agents (I
It is not necessary to further use I) or the graft crossing agent (II).

(3) Composite Rubber The composite rubber as a constituent of the present invention is a composite rubber in which a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber are inseparably entangled with each other and integrated. This composite rubber comprises 1 to 99% by weight of a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate.
The rubber component is 99 to 1% by weight (however, the total amount of both rubber components is 100% by weight). If the polyorganosiloxane rubber component exceeds 99% by weight as the composite rubber, the surface appearance of the resulting composition is deteriorated, and the polyalkyl (meth) acrylate rubber component is 99% by weight.
If the content of the compound exceeds the weight percentage, the resulting composition has low impact resistance. Therefore, as the composite rubber used in the present invention, both of the two rubber components constituting the composite rubber must be in the range of 1 to 99% by weight (however, the total amount of both rubber components is 100% by weight). It is preferable that the polyorganosiloxane rubber component is 5 to 80% by weight and the polyalkyl (meth) acrylate rubber component is 95 to 20% by weight.

The composite rubber as a constituent of the present invention is preferably produced by an emulsion polymerization method. First, a polyorganosiloxane rubber is prepared by an emulsion polymerization method, and then in the presence of this polyorganosiloxane rubber latex. It is preferable to emulsion-polymerize a monomer for synthesizing an alkyl (meth) acrylate rubber. The polyalkyl (meth) acrylate rubber component is polymerized by adding the above alkyl (meth) acrylate, the crosslinking agent (II) and the graft crossing agent (II) to the polyorganosiloxane rubber latex. These may be added all at once or may be added dropwise to the polymerization system. As the polymerization progresses, the polyalkyl (meth) acrylate rubber component forms a cross-linked network in which the polyorganosiloxane rubber component and the polyorganosiloxane rubber component are intertwined with each other at the interface between them, and the graft cross-linking agent (I) is used for the polymerization of the polyorganosiloxane rubber component If so, grafting of the polyalkyl (meth) acrylate rubber component onto the polyorganosiloxane rubber component also occurs, and in any case, a composite rubber latex in which both rubber components are substantially inseparable from each other is obtained.

In this composite rubber, the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are partially entangled with each other and crosslinked in that state, and therefore cannot be extracted and separated with a normal organic solvent such as acetone or toluene. It is a thing. In the composite rubber used in the present invention, the component derived from the cyclic organosiloxane of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane, and the alkyl (meth) acrylate of the polyalkyl (meth) acrylate rubber component is n. -Butyl acrylate is preferred. The composite rubber thus obtained can be graft-copolymerized with a vinyl monomer.

(4) Graft Copolymer The polyorganosiloxane-based graft copolymer used in the present invention is obtained by graft-polymerizing one or more vinyl-based monomers containing an epoxy group-containing vinyl single monomer onto this composite rubber. When the component derived from the epoxy group-containing vinyl monomer is contained in the graft copolymer in an amount of 1 to 40% by weight, preferably 5 to 30% by weight, the epoxy group-containing vinyl is obtained. A vinyl-based monomer other than the system-based monomer may be graft-polymerized together. If the proportion of the component derived from the epoxy group-containing vinyl-based monomer in the graft copolymer is less than 1% by weight, the compatibility of the polyarylene sulfide resin and the polyorganosiloxane-based graft copolymer will be poor. This is not preferable because it tends to occur, and if it exceeds 40% by weight, gelation may occur during melt-kneading, which is also not preferable.

As the epoxy group-containing vinyl monomer,
Glycidyl methacrylate, glycidyl acrylate,
Vinyl glycidyl ether, allyl glycidyl ether, hydroxyalkyl (meth) acrylate glycidyl ether, polyalkylene glycol (meth) acrylate glycidyl ether, glycidyl itacone
The glycidyl methacrylate is more preferably used among these. These may be used alone or in combination of two or more.

As the vinyl-based monomer copolymerizable with the epoxy group-containing vinyl-based monomer, methyl methacrylate,
Methacrylic acid esters such as 2-ethylhexyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate; styrene,
Examples thereof include aromatic alkenyl compounds such as halogen-substituted styrene, α-methylstyrene and vinyltoluene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more. The proportion of the component derived from the grafted vinyl-based monomer in the graft copolymer is preferably 5 to 50% by weight, and 10 to 30% by weight when the weight of the graft copolymer is 100% by weight. Is more preferable.

The polyorganosiloxane-based graft copolymer used in the present invention has an average particle size of 0.
It is preferable to be in the range of 08 to 0.6 μm, and when the average particle size is smaller than 0.08 μm, it is difficult to obtain sufficient impact strength, and when it is larger than 0.6 μm, a molded product from the composition obtained The surface appearance may deteriorate. The polyorganosiloxane-based graft copolymer having such an average particle diameter contains an epoxy group-containing vinyl monomer in the presence of the above composite rubber latex.
It can be obtained by one-step or multi-step emulsion graft polymerization of one or more kinds of monomers. In addition, when a monomer other than the epoxy group-containing vinyl-based monomer is also used as the one or more kinds of monomers including the epoxy group-containing vinyl-based monomer, and the graft polymerization is performed in multiple stages, the epoxy group-containing vinyl group is included in the final stage. It is preferable to add a vinyl monomer.

In the graft polymerization, a component which is a branch of the graft copolymer (here, a component derived from one or more monomers including an epoxy group-containing vinyl monomer) is a trunk component (here, a composite rubber). In the present invention, a so-called free polymer obtained by polymerizing only a branch component without grafting to () is obtained as a mixture of a graft copolymer and a free polymer. In the present invention, both are combined. It is called a graft copolymer.

The blending ratio of the polyarylene sulfide resin and the polyorganosiloxane-based graft copolymer used in the present invention is such that the polyarylene sulfide resin is 100 parts by weight based on the impact strength of the resulting composition. The siloxane-based graft copolymer is preferably 1 to 70 parts by weight, more preferably 5 to 40 parts by weight. If the amount of the polyorganosiloxane-based graft copolymer is less than 1 part by weight, the effect of improving the impact resistance of the polyarylene sulfide resin is poor, and if it exceeds 70 parts by weight, the strength, rigidity and heat resistance of the molded product from the composition are impaired. Tend to be.

As long as the resin component of the composition of the present invention is as described above, a filler can be further added to the composition in order to further improve the heat resistance and mechanical strength of the composition. As such a filler, various shapes such as fibrous particles and powder can be used. Examples of the filler include glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, metal fiber, silicon nitride, aramid fiber, barium sulfate, calcium sulfate, calcium silicate, calcium carbonate, magnesium carbonate, antimony trioxide. , Zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, mica,
Talc, kaolin, pyrophyllite, bentonite,
Examples thereof include sericite, zeolite, wollastonite, other clay, ferrite, graphite, gypsum, glass beads, glass balun, and quartz.

When a filler is used, it is preferable that the amount of the filler is 10 to 300 parts by weight based on 100 parts by weight of the resin component. If it is less than 10 parts by weight, the effect of improving heat resistance, mechanical strength, etc. is small, and if it exceeds 300 parts by weight, the melt fluidity of the composition is deteriorated and the appearance of the molded product may be impaired. The resin composition of the present invention may contain a plasticizer, a flame retardant, a lubricant, a pigment, etc., if necessary.

The composition of the present invention may be prepared by any means as long as it is obtained by melt-mixing at least a polyarylene sulfide resin and a polyorganosiloxane-based graft copolymer. The polyorganosiloxane-based graft copolymer dry powder and polyary obtained by throwing the siloxane-based graft copolymer latex into an aqueous solution of a metal salt such as calcium chloride or magnesium sulfate, salting out, coagulating, separating and collecting, and drying. Melt kneading the lensulfide resin and the filler as necessary in the extruder,
Pelletization is preferred. The pellets thus obtained can be molded at a wide range of temperatures and can be molded using a normal injection molding machine.

The preferred embodiments of the present invention are as follows. (1) 10 to 300 parts by weight of a filler is added to 100 parts by weight of the total amount of the polyarylene sulfide resin and the polyorganosiloxane-based graft copolymer, and the polyarylen sulfide resin composition according to claim 1. object. (2) Alkyl (meth) in the presence of a polyorganosiloxane rubber in which a polyorganosiloxane-based graft copolymer is obtained by emulsion-polymerizing an organosiloxane, a crosslinking agent for polyorganosiloxane rubber, and optionally a graft crossing agent for polyorganosiloxane. Containing at least one epoxy group-containing vinyl monomer in a composite rubber obtained by polymerizing an acrylate, a cross-linking agent for polyalkyl (meth) acrylate rubber and a graft crossing agent for polyalkyl (meth) acrylate rubber. The resin composition according to claim 1, which is a graft copolymer obtained by graft-polymerizing one or more vinyl-based monomers.

(3) The resin composition according to claim 1, wherein the proportion of the component derived from the epoxy group-containing vinyl monomer in the polyorganosiloxane-based graft copolymer is 1 to 40% by weight. (4) The graft branch component in the polyorganosiloxane-based graft copolymer is 5 to 50% by weight.
The resin composition described.

[0041]

The present invention will be specifically described with reference to the following examples. In each description, "part" means "part by weight". In each of Examples and Comparative Examples, various physical properties were measured by the following methods under absolutely dry conditions. Average particle size: Quasi-elastic light scattering method (MALVERN SYS
The latex was diluted with water by TEM 4600, measurement temperature 25 ° C., scattering angle 90 °) to measure as a sample solution. Izod impact strength: ASTM D 256 method (1
/ 8 ", notched). Heat distortion temperature: ASTM D 648 method (high load 1)
It was measured at 8.6 Kg / cm ² . Surface appearance: By visual inspection, those having no pearly gloss were evaluated as ◯, and those having pearly gloss as x.

Reference Example 1 Polyorganosiloxane-based graft copolymer (S-1)
Preparation of 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts of ortamethylcyclotetrasiloxane were mixed to obtain 100 parts of a siloxane mixture. 200 parts of distilled water in which 0.67 parts of sodium dodecylbenzene sulfonate and 0.67 parts of dodecylbenzene sulfonic acid were dissolved respectively were added to 100 parts of the above-mentioned mixed siloxane, and a homomixer was used to obtain 10,0.
After pre-stirring at 00 rpm, 2 with a homogenizer.
It was emulsified at a pressure of 00 Kg / cm ² to obtain an organosiloxane latex. This latex was placed in a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours while stirring and mixing, and allowed to stand at 20 ° C., and after 48 hours, the pH of this latex was adjusted with an aqueous sodium hydroxide solution. The polymerization was completed by neutralizing to 7.2 to obtain polyorganosiloxane rubber latex-1 (hereinafter this latex is referred to as PDMS-1). The conversion rate to polyorganosiloxane rubber was 89.1%, and the average particle size of polyorganosiloxane rubber was 0.1.
It was 9 μm.

35 parts of this PDMS-1 was sampled, placed in a separable flask equipped with a stirrer, 175 parts of distilled water was added, and after nitrogen substitution, this was heated to 50 ° C. and n-butyl acrylate 78 was added. .4 parts, allyl methacrylate 1.
A mixture of 6 parts and tert-butyl hydroperoxide 0.3 part was added. Then add ferrous sulfate 0.00
2 parts, ethylenediaminetetraacetic acid disodium salt 0.00
A mixed solution of 6 parts, 0.3 parts of sodium formaldehyde sulfoxylate and 10 parts of distilled water was added to carry out radical polymerization and kept at an internal temperature of 70 ° C. for 2 hours to obtain a composite rubber latex. A mixed solution of 10 parts of glycidyl methacrylate and 0.024 part of tert-butyl hydroxyperoxide was added dropwise to this composite rubber latex over 15 minutes, and the mixture was kept at an internal temperature of 60 ° C. for 2 hours to graft onto the composite rubber. Polymerization was carried out. The polymerization rate of glycidyl methacrylate was 98.5%, and the average particle size of the graft polymer was 0.2.
It was 4 μm. This latex was added to a 5% calcium chloride aqueous solution at 40 ° C. so that the ratio of the latex and the aqueous solution was 1: 2, and then the temperature was raised to 90 ° C. to coagulate. After cooling it, the solid content is separated by filtration,
The powder was dried overnight at 0 ° C. to obtain a powdery dry powder of a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-1).

Reference Examples 2 to 3 Polyorganosiloxane-based graft copolymer (S-2 to
Production of S-3) PDMS-1 obtained in the production process of S-1 was sampled in the amount shown in Table 1, and the amount of distilled water added to this was taken as the amount shown in Table 1, and n
A composite rubber latex was obtained in the same manner as in Reference Example 1, except that the amounts of butyl acrylate and allyl methacrylate used were those shown in Table 1. A mixed solution of 10 parts of methyl methacrylate and 0.03 part of cumene hydroperoxide was added dropwise to this composite rubber latex over 20 minutes, the internal temperature was kept at 60 ° C. for 1 hour after completion of the addition, and then glycidyl methacrylate. A mixed solution of 5 parts of water and 0.015 parts of cumene hydroperoxide was added dropwise over 10 minutes, and the graft polymerization was completed by maintaining the internal temperature at 60 ° C. for 2 hours after the completion of the addition. Then, coagulation and drying were performed in the same manner as in Reference Example 1 to obtain a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-2 to S-3). Table 1 shows the average particle size of the above graft copolymer latex.

[0045]

[Table 1]

Reference Examples 4 to 6 Polyorganosiloxane-based graft copolymer (S-4 to
Production of S-6) Each of the composite rubber latexes obtained in the production process of S-1 was 27
After 4 parts were collected and placed in a separable flask equipped with a stirring blade and replaced with nitrogen, the temperature was raised to 60 ° C., and 7.5 parts of glycidyl methacrylate and the monomers and cumene shown in Table 2 were added. A mixed solution with 0.04 part of hydroperoxide was added dropwise over 20 minutes, and after the completion of the addition, the internal temperature was kept at 60 ° C. for graft polymerization to the polyorganosiloxane rubber, and the same operation as in Reference Example 1 was performed. Coagulation and drying were performed to obtain a dry powder of a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-4 to S-6). Table 2 shows the average particle size of the above graft copolymer latex.

[0047]

[Table 2]

Reference Example 7 Polyorganosiloxane-based graft copolymer (S-7)
Preparation of A graft copolymer latex was obtained in the same manner as in Reference Example 1 except that 10 parts of glycidyl acrylate was used instead of 10 parts of glycidyl methacrylate. The polymerization rate of glycidyl acrylate was 97.9%, and the average particle size of the graft copolymer latex was 0.23 μm. This was coagulated, filtered, and dried to obtain a dry powder of a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-7).

Reference Example 8 Polyorganosiloxane-based graft copolymer (S-8)
Preparation of a graft copolymer latex in the same manner as in Reference Example 1 except that a mixture of 5 parts of diglycidyl itaconate and 5 parts of methyl methacrylate was used instead of 10 parts of glycidyl methacrylate. It was The polymerization rate of diglycidyl itaconate and methyl methacrylate was 98.1%, and the average particle size of the graft copolymer latex was 0.23 μm.
This was coagulated, filtered, and dried to obtain a dry powder of a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-8).

Reference Example 9 Polyorganosiloxane-based graft copolymer (S-9)
Preparation of PDMS-1 under the same operation and reaction conditions as in PDMS-1 of Reference Example 1, except that 100 parts of a mixture of 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 99.5 parts of octamethylcyclotetrasiloxane was used as the siloxane mixture. Polyorganosiloxane rubber latex-2 (hereinafter P
DMS-2) was obtained. The conversion rate of the polyorganosiloxane rubber was 91.1%, and the average particle size of the polyorganosiloxane rubber was 0.19 μm.

After 283 parts of PDMS-2 was sampled and placed in a separable flask equipped with a stirring blade and replaced with nitrogen,
This was heated to 60 ° C. and ferrous sulfate 0.002 was added thereto.
Parts, ethylenediaminetetraacetic acid disodium salt 0.006
Parts, sodium formaldehyde sulfoxylate 0.
A mixed solution of 3 parts and 10 parts of distilled water was added, and a mixed solution of 10 parts of methyl methacrylate and 0.03 part of cumene hydroperoxide was added dropwise over 20 minutes, and the internal temperature was adjusted to 60 ° C for 1 hour after completion of the addition. Hold, then add 1 part of a mixed solution of 5 parts of glycidyl methacrylate and 0.015 part of cumene hydroperoxide.
The mixture was added dropwise over 0 minutes, and the graft polymerization was completed by maintaining the internal temperature at 60 ° C. for 2 hours after completion of the addition. The number average particle diameter of the obtained graft copolymer latex was 0.22 μm. Then, coagulation and drying were carried out in the same manner as in Reference Example 1 to carry out polyorganosiloxane-based graft copolymer (hereinafter referred to as S-9).
Called) dry powder.

Reference Example 10 Polyacrylate rubber graft copolymer (S-10)
Production of distilled water 200 in a separable flask equipped with a stirring blade
Parts and 1 part of dodecylbenzenesulfonic acid soda were added and the atmosphere was replaced with nitrogen, then the temperature was raised to 50 ° C., and 83.5 parts of n-butyl acrylate and 1.5 parts of allyl methacrylate were added thereto. And a mixture of 0.3 parts of cumene hydroperoxide was added. Then add 0.002 of ferrous sulfate to it.
Parts, ethylenediaminetetraacetic acid disodium salt 0.006
Parts, sodium formaldehyde sulfoxylate 0.
A mixture of 3 parts and 10 parts of distilled water was added to carry out radical polymerization, and kept at an internal temperature of 70 ° C. for 2 hours to obtain a polyacrylate rubber latex.

Methyl methacrylate was added to this rubber latex.
A mixture of 10 parts of cumene hydroperoxide and 0.03 part of cumene hydroperoxide was added dropwise over 20 minutes, and the internal temperature was adjusted to 60 hours for 1 hour after completion of the addition.
C., then a mixed solution of 5 parts of glycidyl methacrylate and 0.015 part of cumene hydroperoxide was added dropwise over 10 minutes, and after the completion of the addition, the internal temperature was maintained at 60.degree. C. for 2 hours to complete the graft polymerization. did. Then, coagulation and drying were carried out in the same manner as in Reference Example 1 to obtain a polyacrylate rubber graft copolymer (hereinafter referred to as S-10).

Reference Example 11 Polyorganosiloxane-based graft copolymer (S-1
Production of 1) Polyorganosiloxane-based graft was carried out in the same manner as in Reference Example 1 except that the same amount of methyl methacrylate was used instead of glycidyl methacrylate as a monomer to be grafted to the polyorganosiloxane-based composite rubber. A dry powder of a copolymer (hereinafter referred to as S-11) was obtained.

Examples 1 to 13 and Comparative Examples 1 to 7 As polyarylene sulfide resin, Toprene T
-4 (trade name, cross-linked polyphenylene sulfide manufactured by Topren) or Rydon M2588 (trade name, linear polyphenylene sulfide manufactured by Toray Phillips), and the polyorganosiloxane-based grafts obtained in each of the reference examples. The copolymers S-1 to S-8 were blended in the proportions shown in Table 3, and the twin-screw extruder (manufactured by Toshiba Machine Co., TEM-3
5B) was used and pelletized at a cylinder temperature of 300 ° C. After drying the pellets, a cylinder with a temperature of 30 was used using an injection molding machine (Sumitomo Heavy Industries, Promat injection molding machine).
A test piece was molded at 0 ° C. and a mold temperature of 140 ° C., and impact resistance was evaluated. The results are shown in Table 3.

On the other hand, when only each polyarylene sulfide resin was used for comparison (Comparative Examples 1 and 2), the polyorganosiloxane-based graft copolymer was used instead of the polyorganosiloxane-based graft copolymer in the production process of S-1 of Reference Example 1. When a rubber obtained by coagulating and drying the obtained polyorganosiloxane rubber latex PDMS-1 (hereinafter referred to as S-12) is used (Comparative Example 3),
When the composite rubber latex obtained in Reference Example 1 was coagulated and dried (hereinafter referred to as S-13) (Comparative Example 4), a polyorganosiloxane-based polymer was used instead of the graft copolymer used in the present invention. When a copolymer obtained by grafting a monomer containing an epoxy group-containing vinyl monomer to a homo rubber (Comparative Example 5) is used, a polyacrylate rubber containing an epoxy group-containing vinyl monomer is used. In the case of using the copolymer grafted with (Comparative Example 6) and in the case of using the copolymer grafted with methyl methacrylate instead of the vinyl monomer containing the epoxy group-containing vinyl monomer. Also in (Comparative Example 7), a test piece was molded in the same manner, and the impact resistance was evaluated. The results are also shown in Table 3.

[0057]

[Table 3]

In Table 3, T4 is Toprene T4, M
25 is an abbreviation for Ryton M2588.

Examples 14 to 20 and Comparative Examples 8 to 10 A polyarylene sulfide resin, a polyorganosiloxane-based graft copolymer S-1 and a filler having the types and blending ratios shown in Table 4 were blended and carried out. In the same manner as in Example 1, pelletization and injection molding were performed to obtain a test piece for evaluation, and the impact resistance was evaluated. The results are shown in Table 4. For comparison, various polyarylene sulfide resins blended with glass fiber and toprene T-4 blended with S-11 and glass fiber were also evaluated in the same manner. The results are also shown in Table 4.

[0060]

[Table 4]

In Table 4, T4 is Toprene T4, M
25 is Ryton M2588, GF is glass fiber, and CF is carbon fiber.

[0062]

INDUSTRIAL APPLICABILITY The poly (arylene sulfide) resin composition of the present invention has excellent impact resistance, good appearance of molded articles, and can be a thermoplastic resin which can be used in a wider range of applications.

Claims (1)

Claims: 1. A polyarylenene sulfide resin (A),
And (B) at least one compound containing at least one epoxy group-containing vinyl monomer in the composite rubber in which the polyorganosiloxane rubber and the polyalkyl (meth) acrylate rubber are intertwined inseparably from each other and integrated. A polyarylene sulfide resin composition obtained by melt-mixing a polyorganosiloxane-based graft copolymer obtained by graft-polymerizing the vinyl-based monomer as described above, which is a main resin component.