JPH04306259A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject thermoplastic resin composition maintaining heat resistance, flame retardant properties, etc., having impact resistance in combination therewith and useful for an automobile component, etc., by blending a specified polyphase-structured thermoplastic resin with a polyarylene sulfide- based resin. CONSTITUTION:A resin composition composed of (A) 50-99wt.% polyarylene sulfide (preferably polyphenylene sulfide) and (B) 50-1wt.% thermoplastic resin consisting of a graft polymer composed of (B1) 5-95wt.% acid group-containing olefin copolymer (preferably ethylene-ethyl acrylate-maleic acid copolymer, etc.) and (B2) 95-5wt.% vinyl-based (co)polymer. In this resin composition, the above-mentioned thermoplastic resin is a polyphase-structured thermoplastic resin in which one (co)polymer component of (B1) and (B2) is a dispersed phase having 0.001-10mum particle size and dispersed in the other (co)polymer component and obtained, preferably by suspending (B1) in water, separately preparing a solution composed of a radically polymerizable organic peroxide and a radical- polymerization-initiator respectively dissolved in a vinyl monomer, subsequently adding the solution to the above-mentioned suspension, giving a grafted precursor by heating, then melting and kneading it.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a thermoplastic resin composition that has excellent heat resistance, impact resistance, moldability, oil resistance, water resistance, etc., and is used in automobile parts, electrical and electromechanical parts, and industrial parts. It is effectively used in a wide range of fields such as

0002

BACKGROUND OF THE INVENTION Polyarylene sulfide resins are recognized for their excellent mechanical properties, heat resistance, chemical resistance, etc., and are used in many fields. In addition, in recent years automobile parts, electrical
Thermoplastic resins with high heat resistance and chemical resistance are required for electronic parts and chemical equipment, and polyarylene sulfide resins are recognized for their excellent heat resistance and chemical resistance and are used in many fields. ing. However, although polyarylene sulfide resins have excellent heat resistance and flame retardancy, they have the drawbacks of poor ductility and brittleness.

[0003] In order to improve this drawback, a method of blending various elastomers with polyarylene sulfide has been proposed, and this method is relatively effective for improving impact resistance. For example, JP-A-1-198664
The publication discloses a method of adding an ethylene/glycidyl methacrylate-polymethyl methacrylate graft copolymer.

0004

[Problems to be Solved by the Invention] However, in order to improve the impact resistance, it is sufficient to increase the amount of elastomer, but this results in a decrease in the properties of polyarylene sulfide such as heat resistance. I'm still not satisfied with it.

[0005]

[Means for Solving the Problems] As a result of intensive research to solve the above problems, the present invention provides a polyarylene sulfide composition obtained by blending a polyarylene sulfide resin with a specific multiphase thermoplastic resin. It was discovered that the material has impact resistance while maintaining heat resistance, flame retardancy, etc., and the present invention was completed.

That is, the present invention comprises (I) 50 to 99% by weight of a polyarylene sulfide resin, and (II)
A graft polymer consisting of 5 to 95% by weight of an acid group-containing olefin copolymer and 95 to 5% by weight of a vinyl-based (co)polymer, in which one (co)polymer is present in the other (co)polymer. The present invention relates to a thermoplastic resin composition comprising 50 to 1% by weight of a multiphase thermoplastic resin in which a dispersed phase with a particle size of 0.001 to 10 μm is formed.

The polyarylene sulfide used in the present invention has the general formula (1)

This is a polymer represented by the following formula. Here, Ar is, for example, the general formulas (2) to (7)

[Case 2]

[Chemical formula 3]

[C4]

[C5]

[C6]

It is a divalent aromatic residue containing at least one carbon 6-membered ring such as
Substituents such as H may also be introduced. Particularly typical polyarylene sulfide is represented by the general formula (8).

Polyphenylene sulfide (hereinafter referred to as PP) represented by [Chemical 8]
(referred to as S). The manufacturing method was published in 1976-336.
No. 8 discloses that 1 in N-methylpyrrolidone solution
It can be produced by reacting paradichlorobenzene and sodium sulfide at 60 to 250°C under pressurized conditions.

[0008] The acid group-containing olefin copolymer in the multiphase thermoplastic resin used in the present invention is, in part, a combination of an olefin and an unsaturated carboxylic acid monomer or its derivative by high-pressure radical polymerization. It is an original copolymer, or a ternary or multicomponent copolymer of an olefin, an unsaturated carboxylic acid monomer or its derivative, and other unsaturated monomers, and the olefin in the above copolymer is particularly ethylene. Preferably, a copolymer consisting of 60 to 99.5% by weight of ethylene, 0.5 to 40% by weight of an unsaturated carboxylic acid monomer or its derivative, and 0 to 39.5% by weight of other unsaturated monomers is preferred. .

Examples of the unsaturated carboxylic acid monomers or derivatives thereof include acrylic acid, methacrylic acid, maleic acid, crotonic acid, fumaric acid, itaconic acid, maleic acid monoester, fumaric acid monoester, and metal salts thereof. , maleic anhydride, itaconic anhydride, and the like.

[0010] The other unsaturated monomer is at least one monomer selected from olefins, vinyl esters, α,β-ethylenically unsaturated carboxylic acids or derivatives thereof, etc. is propylene; butene-1; hexene-1; decene-1; octene-1; olefins such as styrene, vinyl acetate; vinyl propionate; vinyl esters such as vinyl benzoate, acrylic acid; methacrylic acid; acrylic acid or Methyl methacrylate
, ethyl, propyl, butyl, 2-ethylhexyl, cyclohexyl, dodecyl, octadecyl
esters such as maleic acid; maleic anhydride; itaconic acid; fumaric acid; maleic acid mono- and di-esters; vinyl chloride; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; Among these, acrylic esters are particularly preferred.

Specific examples of the acid group-containing olefin copolymer include ethylene-maleic acid copolymer, ethylene-maleic acid copolymer, and ethylene-maleic acid copolymer.
Maleic anhydride copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate-maleic acid copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer, ethylene- Ethyl acrylate-acrylic acid copolymer, ethylene-ethyl acrylate-methacrylic acid copolymer, ethylene-butyl acrylate-maleic anhydride copolymer, ethylene-butyl acrylate-acrylic acid copolymer, ethylene-acrylic Examples include acid group-containing olefin copolymers such as acid butyl methacrylate copolymer, ethylene-vinyl acetate-maleic anhydride copolymer, and ethylene-methyl methacrylate-maleic anhydride copolymer. These acid group-containing olefin copolymers can also be used in combination.

[0012] A method for producing an acid group-containing olefin copolymer by high-pressure radical polymerization method is to use the above-mentioned ethylene 60 to 99.5
Weight %, one or more unsaturated carboxylic acid group monomers 0.5~
40% by weight, 0 at least one other unsaturated monomer
~39.5% by weight monomer mixture in the presence of 0.0001-1% by weight radical polymerization initiator based on the total weight of all those monomers at a polymerization pressure of 500-4000 kg/
cm2, preferably 1000-3500kg/cm2
, reaction temperature 50-400°C, preferably 100-35°C
This is a method in which the monomers are brought into contact and polymerized simultaneously or stepwise in a tank or tubular reactor in the presence of a chain transfer agent and, if necessary, an auxiliary agent under conditions of 0°C.

Examples of the above-mentioned radical polymerization initiators include conventional initiators such as peroxides, hydroperoxides, azo compounds, amine oxide compounds, and oxygen. In addition, as a chain transfer agent, hydrogen, propylene, butene-1, C1
~C20 or higher saturated aliphatic and halogen-substituted hydrocarbons, such as methane, ethane, propane, butane, isobutane, n-hexane, n-heptane, cycloparaffins, chloroform and carbon tetrachloride, C1 to C20 or higher saturated aliphatic alcohols such as methanol, ethanol, propanol and isopropanol, C1 to C20 or higher saturated aliphatic carbonyl compounds such as carbon dioxide,
Included are acetone and methyl ethyl ketone and aromatic compounds such as toluene, diethylbenzene and xylene.

Another example of the acid group-containing olefin copolymer of the present invention is a modified product obtained by adding the above-mentioned unsaturated carboxylic acid monomer or its derivative to a conventional olefin homopolymer or copolymer. . The above olefin polymers include homopolymers such as low density, medium density, and high density polyethylene; polypropylene; polybutene-1; poly-4-methylpentene-1; ethylene-propylene copolymers; ethylene-butene-1 Copolymers; ethylene-hexene-1 copolymers; ethylene-4-methylpentene-1 copolymers; copolymers with other α-olefins containing ethylene as the main component, such as ethylene-octene-1 copolymers Copolymers containing propylene as a main component with other α-olefins such as propylene-ethylene block copolymers; ethylene-vinyl acetate copolymers; ethylene-acrylic acid copolymers; ethylene-methacrylic acid copolymers Copolymer: Copolymer of ethylene and ester of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, isopropyl, butyl; Ethylene-maleic acid copolymer; Ethylene-propylene copolymer rubber; Ethylene -Propylene-diene-copolymer rubber; liquid polybutadiene; ethylene-vinyl acetate-vinyl chloride copolymer and mixtures thereof, or mixtures thereof with different synthetic resins or rubbers are also included in the present invention.

The vinyl (co)polymer in the multiphase thermoplastic resin used in the present invention specifically includes styrene, nuclear substituted styrene such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene,
Vinyl aromatic monomers such as chlorstyrene, α-substituted styrene such as α-methylstyrene, α-ethylstyrene;
C1-7 alkyl esters of acrylic acid or methacrylic acid, such as methyl (meth)acrylic acid,
(Meth)acrylic acid ester monomers such as ethyl, propyl, isopropyl, and butyl; (meth)acrylonitrile monomers such as acrylonitrile or methacrylonitrile; vinyl ester monomers such as vinyl acetate and vinyl propionate (meth)acrylamide monomers such as acrylamide and methacrylamide; maleic anhydride,
It is a (co)polymer obtained by polymerizing one or more vinyl monomers such as mono- and di-esters of maleic acid. Among these, vinyl aromatic monomers,
(Meth)acrylic acid ester monomers, (meth)acrylonitrile monomers and vinyl ester monomers are preferably used.

[0016] The multiphase thermoplastic resin referred to in the present invention is
A material in which a vinyl (co)polymer or acid group-containing olefin copolymer, which is a different component, is uniformly dispersed in a spherical shape in an acid group-containing olefin copolymer or vinyl (co)polymer matrix. means. The particle size of the dispersed polymer is 0.001 to 10 μm, preferably 0.0 μm.
It is 1 to 5 μm. If the dispersed resin particle size is less than 0.001 μm or more than 10 μm, the dispersibility when blended with polyarylene sulfide resin is poor, resulting in deterioration of appearance or lack of improvement effects such as impact resistance. Undesirable.

The number average degree of polymerization of the vinyl (co)polymer in the multiphase thermoplastic resin of the present invention is from 5 to 10,000, preferably from 10 to 5,000. If the number average degree of polymerization is less than 5, it is possible to improve the impact resistance of the thermoplastic resin composition of the present invention, but it is not preferable because the heat resistance decreases. Moreover, if the number average degree of polymerization exceeds 10,000, it is not preferable because the melt viscosity is high, the moldability is decreased, and the surface gloss is decreased.

[0018] The multiphase structured thermoplastic resin in the present invention is
The content of the acid group-containing olefin copolymer is 5 to 95% by weight, preferably 20 to 90% by weight. Therefore, the vinyl (co)polymer content is 95 to 5% by weight, preferably 80 to 10% by weight. If the amount of the acid group-containing olefin copolymer is less than 5% by weight, the effect of improving impact resistance will be insufficient, which is not preferable. Moreover, if the content of the acid group-containing olefin copolymer exceeds 95% by weight, although a sufficient effect of improving impact resistance can be obtained, it is not preferable because heat resistance decreases.

The grafting method for producing the multiphase thermoplastic resin of the present invention may be any of the generally well-known methods such as chain transfer method and ionizing radiation irradiation method, but the most preferred method is , by the method shown below. The reason for this is that the grafting efficiency is high and secondary aggregation due to heat does not occur, so performance is more effectively expressed.

The method for producing the thermoplastic resin composition of the present invention will be explained in detail below. That is, 100 parts by weight of an acid group-containing olefin copolymer is suspended in water, and 5 to 400 parts by weight of at least one vinyl monomer is added to the following formula (9) or formula (10). 1 or a mixture of two or more radically polymerizable organic peroxides represented by 10 in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the vinyl monomer.
parts by weight and a decomposition temperature of 4 to obtain a half-life of 10 hours.
Adding a solution of 0.01 to 5 parts by weight of a radical polymerization initiator at 0 to 90°C per 100 parts by weight of the vinyl monomer and radically polymerizable organic peroxide,
The acid group-containing olefin copolymer is impregnated with the vinyl monomer, radically polymerizable organic peroxide, and radical polymerization initiator by heating under conditions that do not substantially cause decomposition of the radical polymerization initiator, and the impregnation rate is When the initial concentration reaches 50% by weight or more, the temperature of the aqueous suspension is raised to copolymerize the vinyl monomer and the radically polymerizable organic peroxide in the acid group-containing olefin copolymer, Obtain a grafted precursor.

This grafting precursor is also a multiphase thermoplastic resin. Therefore, this grafted precursor may be directly melt-mixed with the polyarylene sulfide resin. Further, the multiphase thermoplastic resin of the present invention can also be obtained by kneading the grafted precursor while melting at 100 to 300°C. At this time, an acid group-containing olefin copolymer or a vinyl-based (
A multiphase thermoplastic resin can also be obtained by mixing co)polymers and kneading them while melting. Most preferred is a thermoplastic resin with a multiphase structure obtained by kneading a grafted precursor.

The radically polymerizable organic peroxide represented by the general formula (9) is:

[Formula 9] (wherein, R1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R2 is a hydrogen atom or a methyl group, R3 and R4 are each an alkyl group having 1 to 4 carbon atoms, and R5 is an alkyl group having 1 to 4 carbon atoms. 12 alkyl group, phenyl group, alkyl-substituted phenyl group, or cycloalkyl group having 3 to 12 carbon atoms. m is 1 or 2).

[0023] Furthermore, the radically polymerizable organic peroxide represented by the general formula (10) is

(In the formula, R6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R7 is a hydrogen atom or a methyl group, R8 and R9 are each an alkyl group having 1 to 4 carbon atoms, and R10 is an alkyl group having 1 to 4 carbon atoms. 12 alkyl group, phenyl group, alkyl-substituted phenyl group, or cycloalkyl group having 3 to 12 carbon atoms (n is 0, 1 or 2).

Examples of the radically polymerizable organic peroxide represented by the general formula (9) include t-butylperoxyacryloyloxyethyl carbonate; t-amylperoxyacryloyloxyethyl carbonate; t-hexylperoxy Acryloyloxyethyl carbonate;
1,1,3,3-tetramethylbutylperoxyacryloyloxyethyl carbonate; cumylperoxyacryloyloxyethyl carbonate; p-isopropylcumylperoxyacryloyloxyethyl carbonate;
t-Butylperoxymethacryloyloxyethyl carbonate; t-amylperoxymethacryloyloxyethyl carbonate; t-hexylperoxymethacryloyloxyethyl carbonate; 1,1,3,3-tetramethylbutylperoxymethacryloyloxyethyl carbonate; cumyl Peroxymethacryloyloxyethyl carbonate; p-isopropylcumyl peroxymethacryloyloxyethyl carbonate; t-butylperoxymethacryloyloxyethyl carbonate; t-amylperoxyacryloyloxyethoxyethyl carbonate; t-hexylperoxyacryloyloxyethoxyethyl carbonate ;1,1,3,3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate;cumylperoxyacryloyloxyethoxyethyl carbonate;p-isopropylcumylperoxyacryloyloxyethoxyethyl carbonate;t-butylperoxymethacryloyloxy Ethoxyethyl carbonate; t-amylperoxymethacryloyloxyethoxyethoxyethyl carbonate; t-hexylperoxymethacryloyloxyethoxyethyl carbonate; 1,1
,3,3-tetramethylbutylperoxymethacryloyloxyethoxyethyl carbonate; cumylperoxymethacryloyloxyethoxyethyl carbonate; p-
Isopropylcumylperoxymethacryloyloxyethoxyethyl carbonate; t-butylperoxyacryloyloxyisopropyl carbonate; t-amylperoxyacryloyloxyisopropyl carbonate; t
-hexylperoxyacryloyloxyisopropyl carbonate; 1,1,3,3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate; cumylperoxyacryloyloxyisopropyl carbonate; p-isopropylcumylperoxyacryloyloxyisopropyl carbonate; t- Butylperoxymethacryloyloxyisopropyl carbonate; t-amylperoxymethacryloyloxyisopropyl carbonate; t-hexylperoxymethacryloyloxyisopropyl carbonate; 1,1,3,3-tetramethylbutylperoxymethacryloyloxyisopropyl carbonate; cumylperoxymethacrylate Examples include loyloxyisopropyl carbonate; p-isopropylcumylperoxymethacryloyloxyisopropyl carbonate.

Further, as the compound represented by the general formula (10), t-butyl peroxyallyl carbonate;
t-Amylperoxyallyl carbonate; t-hexylperoxyallyl carbonate; 1,1,3,3-tetramethylbutylperoxyallyl carbonate; p-
Menthane peroxy allyl carbonate; cumyl peroxy allyl carbonate; t-butyl peroxy methallyl carbonate; t-amyl peroxy methallyl carbonate; t-hexyl peroxy methallyl carbonate; 1,1,3,3-tetramethylbutyl peroxy methallyl carbonate ; p-menthane peroxy methallyl carbonate; cumyl peroxy methallyl carbonate;
t-butylperoxyallyloxyethyl carbonate;
t-amylperoxyallyloxyethyl carbonate;
t-hexylperoxyallyloxyethyl carbonate; t-butylperoxymethallyloxyethyl carbonate; t-amylperoxymethallyloxyethyl carbonate; t-hexylperoxymethallyloxyethyl carbonate; t-butylperoxyallyloxyisopropyl carbonate; t-amylperoxy Allyloxyisopropyl carbonate; t-hexylperoxyallyloxyisopropyl carbonate; t-butylperoxymethallyloxyisopropyl carbonate; t-amylperoxymethallyloxyisopropyl carbonate; t-hexylperoxymethallyloxyisopropyl carbonate. Among them, preferably t-
Butylperoxyacryloyloxyethyl carbonate; t-butylperoxymethacryloyloxyethyl carbonate; t-butylperoxyallyl carbonate;
It is t-butylperoxymethallyl carbonate.

In the present invention, the polyarylene sulfide resin is required in an amount of 50 to 99% by weight, preferably 60 to 97% by weight. Therefore, the polyphase structure thermoplastic resin has 5
It is blended in a proportion of 0 to 1% by weight, preferably 40 to 3% by weight. If the polyarylene sulfide resin is less than 50% by weight, mechanical strength and heat resistance will deteriorate, which is undesirable. In addition, polyarylene sulfide resin is 99%
If it exceeds % by weight, the effect of improving impact resistance, which is the objective of the present invention, is undesirable.

In the present invention, less than 300 parts by weight of an inorganic filler can be blended with 100 parts by weight of the resin component containing (I) + (II). Examples of the above-mentioned inorganic fillers include powder-like, tabular, scaly, acicular, spherical or hollow, and fibrous fillers, and specific examples include calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, and silica sand. , glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black, etc.; mica, glass plate, sericite, pyrophyllite, aluminum flakes, etc. flat or scaly fillers such as metal foil and graphite; hollow fillers such as shirasu balloons, metal balloons, glass balloons, and pumice; glass fibers, carbon fibers,
Examples include graphite fibers, whiskers, metal fibers, silicone carbide fibers, and mineral fibers such as asbestos and wostonite. If the amount of filler added exceeds 300 parts by weight, the impact strength of the molded article will decrease, which is not preferable. In addition, the surface of the inorganic filler is treated using stearic acid, oleic acid, palmitic acid or a metal salt thereof, paraffin wax, polyethylene wax or a modified product thereof, organic silane, organic borane, organic titanate, etc. It is preferable to apply it.

In the present invention, other thermoplastic resins such as polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, polycarbonate resins, polyester resins, and polyphenylene resins may be used without departing from the gist of the present invention. Engineering plastics such as ether resins and polyamide resins, natural rubber, and EP
R, synthetic rubber such as EPDM, SBS, SEBS, inorganic flame retardants such as magnesium hydroxide, aluminum hydroxide, organic flame retardants such as halogen-based and phosphorus-based, organic fillers such as wood flour, antioxidants, ultraviolet rays. inhibitors, lubricants, dispersants,
Additives such as blowing agents, crosslinking agents, and coloring agents may be added.

[0029]

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto. Reference Example 1 (Manufacture of multiphase thermoplastic resin (IIa)) 2500 g of pure water was placed in a stainless steel autoclave with a volume of 5 L, and 2.5 g of polyvinyl alcohol was further dissolved as a suspending agent. 700 g of ethylene/ethyl acrylate/maleic anhydride copolymer "Bondine TX8030" (trade name, manufactured by Sumika CF Chemical) was added as a containing olefin copolymer and stirred and dispersed.Benzoyl peroxide as a radical polymerization initiator was added separately. 1.5 g of "Niper B" (trade name, manufactured by NOF Corporation) and 6 g of t-butylperoxymethacryloyloxyethyl carbonate as a radically polymerizable organic peroxide are dissolved in 300 g of styrene as a vinyl monomer, This solution was poured into the autoclave and stirred. Next, the temperature of the autoclave was raised to 60 to 65°C, and by stirring for 2 hours, the vinyl monomer containing the radical polymerization initiator and the radically polymerizable organic peroxide was acidified. It was impregnated into the group-containing ethylene copolymer.Next, it was confirmed that the total amount of the impregnated vinyl monomer, radically polymerizable organic peroxide, and radical polymerization initiator was 50% by weight or more of the initial amount. After confirmation, the temperature was raised to 80-85°C and maintained at that temperature for 7 hours to complete polymerization, washed with water and dried to obtain a grafted precursor.The styrene polymer in this grafted precursor was It was extracted with ethyl acetate and the number average degree of polymerization was measured by GPC and found to be 900.

[0030] Next, this grafted precursor was heated for 20 minutes using a Laboplast Mill single-screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.).
A multiphase thermoplastic resin (II a) was obtained by extrusion at 0° C. and grafting reaction. This multiphase structured thermoplastic resin was examined using a scanning electron microscope "JEOL JSM".
When observed using "T300" (manufactured by JEOL Ltd.), it was found to be a multiphase thermoplastic resin in which perfectly spherical resin with a particle size of 0.3 to 0.4 μm was uniformly dispersed. At this time, the grafting efficiency of the styrene polymer was 77.8% by weight.

Reference Example 2 (Production of multiphase thermoplastic resin (II b)) Reference Example 1
In , styrene monomer 300 as vinyl monomer
g to a monomer mixture of 210 g of styrene monomer and 90 g of acrylonitrile monomer, and 1.5 g of benzoyl peroxide to di-3,5,5-trimethylhexanoyl peroxide "Perloyl 355" (trade name, NOF). (
Reference Example 1 was repeated except that 3 g of α-methylstyrene dimer “Nofmar MSD” (trade name, manufactured by NOF Corporation) was used as the molecular weight regulator. A structural thermoplastic resin (II b) was obtained. At this time, the number average degree of polymerization of the styrene polymer was 1200, and the average particle size of the resin dispersed in this multiphase thermoplastic resin was 0.3 to 0.4 μm.

Reference Example 3 In Reference Example 2, the ethylene/ethyl acrylate/maleic anhydride copolymer "Bondine TX8030" (trade name, manufactured by Sumika CDF Chemical) was substituted with the ethylene/acrylic acid copolymer "Yukalon EAA- A multiphase structure thermoplastic resin (IIc) was obtained by repeating Reference Example 2, except that the resin was changed to "510W" (trade name, manufactured by Mitsubishi Yuka Co., Ltd.). Further, the average particle diameter of the resin dispersed in this multiphase structured thermoplastic resin was 0.3 to 0.4 μm.

Examples 1 to 6 Polyphenylene sulfide “Fortron KPS” (
Product name, manufactured by Kureha Chemical Industry Co., Ltd.) (hereinafter referred to as PPS) is a multiphase structure thermoplastic resin (II) obtained in the reference example.
a), (II b) or (II c) were melted and mixed in the proportions shown in Table 1. The melting/mixing method involves dry blending the resin pellets and then increasing the cylinder temperature to 31°C.
The mixture was supplied to a coaxially rotating twin-screw extruder with a screw diameter of 30 mm set at 0°C, and granulated after extrusion. The granulated resin was dried at 150°C for 3 hours. Then cylinder temperature 31
A test piece was prepared by injection molding at 0°C and a mold temperature of 90°C. The size of the test piece is as follows.

[0034] Izod impact test piece 13mm x 65
mm x 6 mm (with notch) Load deflection temperature test piece 13 mm x 130 mm x 6 m
m tensile test piece 13mm x 22
0 mm x 6 mm The test method is as follows. (1) Izod impact value (notched): JIS
K7110 (2) Weighted deflection temperature: JIS K7207
(3) Tensile strength test: JIS K711
3 (4) Layered peeling state Layered peeling state is achieved by attaching adhesive tape to the fractured surface of the molded product.
After performing a peel test using the method of later removal, the condition was observed with the naked eye and ranked as follows. ◎: No peeling at all ○: Slight peeling ×: Peeling

[0035]

[Table 1]

Comparative Examples 1 to 4 The multiphase thermoplastic resin used in Example 1 was combined with unmodified acid group-containing polyolefin copolymer "Bondine TX8030" (trade name, Sumika CDF), which is one of its constituent components. Evaluation was carried out in the same manner as in Example 1 except that the material was changed to (manufactured by Kagaku). The results are shown in Table 2.

[0037]

[Table 2]

Comparative Examples 5 to 9 Evaluations were made in the same manner as in Example 1, except that the amount of the multiphase thermoplastic resin added was changed. The results are shown in Table 3.

[0039]

[Table 3]

From the above, when the multiphase thermoplastic resin exceeds 50% by weight, the composition loses the properties of polyarylene sulfide resin, and furthermore, the amount of the multiphase thermoplastic resin added is less than 1% by weight. It was found that there was no effect of the addition.

Examples 5 to 8 Glass fibers (average fiber length 0.3 mm x diameter 1
0 μm) and calcium carbonate (average particle size 4 μm) were mixed in the proportions shown in Table 4 and evaluated in the same manner as in Example 1. Table 4 shows the results.

[0042]

[Table 4]

Comparative Examples 10 to 11 The amount of the multiphase thermoplastic resin used in Examples 5 to 8 was 0% by weight, and the multiphase thermoplastic resin was Table 5 shows the results of evaluation in the same manner as in Example 1 except that the group-containing polyolefin copolymer was used.

[0044]

[Table 5]

[0045]

[Effects of the Invention] The thermoplastic resin composition of the present invention is a resin composition that maintains the excellent properties of polyarylene sulfide resin, has no decrease in heat resistance, and has improved toughness, impact resistance, etc. be. Moreover, it has the characteristic that it can be easily manufactured simply by mixing under melting conditions. Therefore, it can be used in a wide range of applications such as automobile parts, electrical/electronic parts, and industrial parts.

Claims (1)

[Claims] Claim 1: (I) 50 to 99% by weight of polyarylene sulfide resin, and (II) 5 to 95% by weight of acid group-containing olefin copolymer and vinyl (co)polymer 9
5 to 5% by weight, one (co)polymer has a particle size of 0.0% in the other (co)polymer.
A thermoplastic resin composition comprising 50 to 1% by weight of a multiphase thermoplastic resin forming a dispersed phase of 01 to 10 μm.