JPH05186688A - Production of resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyarylene sulfide resin composition having excellent toughness and impact resistance by adding a specific copolymer to a polyarylene sulfide resin and kneading the mixture in molten state. CONSTITUTION:The objective composition suitable for a metal-inserted molding, a molding for sealing electronic parts, etc., liable to cause cracking defect is produced by adding (A) a copolymer produced by bonding (i) a rubbery polymer part composed of a diene polymer and/or an alpha-olefin polymer with (ii) a non-rubbery polymer part composed of a polyorganosiloxane, polyamide, polyarylene sulfide resin and/or an alpha-olefin polymer to (B) an arylene sulfide resin preferably consisting of a polyarylene sulfide (ketone) and/or a polyarylene sulfide sulfone and kneading the obtained mixture in molten state.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful method for producing a resin composition having excellent toughness such as impact resistance, crack resistance and flexibility. The resin composition can be used as an injection molding material, a compression molding material, and an extrusion molding material in various fields. The use of the resin composition is not necessarily limited, especially molded articles having a thin portion that was difficult to apply particularly in the conventional crack generation, cracks easily occur,
It is suitable for applications such as molded products with metal inserted and electronic component sealing molded products. Specifically, transistors, diodes, triodes, power modules, integrated circuits, IC regulators, hybrid ICs, light emitting diodes, photocouplers, photointerrupters, thermistors, varistors, thyristors, hall elements, various filters, fixed or variable. Resistors, resistors such as resistor networks, film capacitors, ceramic capacitors, aluminum electrolytic capacitors, tantalum electrolytic capacitors, conductive polymer capacitors such as polypyrrole, capacitors such as mica capacitors, various transformers and coils, relays, switch,
There are various electronic and electrical parts such as various sensors, thermostats, magnetic heads, motors, tuners, transducers, crystal units, fuses, rectifiers, power supplies, surge absorbers, connectors, printed circuit boards, etc., and their composite parts. There are, but are not necessarily limited to, automobile electric components, tubes, hoses, gears, industrial products such as cams, bearings, joints and casters.

[0002]

2. Description of the Related Art Polyarylene sulfide resins are engineering plastics having excellent heat resistance, chemical resistance, flame retardancy, electrical properties and mechanical properties and are used as molding materials for various purposes. However, since the resin itself lacks in toughness, it is reinforced with glass fiber or the like, but nevertheless, for example, the problem of microcracking in thin portions such as connectors occurs.
Further, in the use of encapsulating electronic parts, there is a problem that cracks occur during lead forming because the resin itself has a low molecular weight.

It has been proposed to blend various resins and elastomers in order to solve these drawbacks of polyarylene sulfide resins. For example, JP-A-58-58
No. 27740 discloses a block copolymer which is a copolymer of polyphenylene sulfide (hereinafter abbreviated as PPS), a vinyl aromatic compound modified with a carboxylic acid and an olefin compound, and whose degree of unsaturation does not exceed 20%. And the composition of PPS in JP-A-63-118369.
And a composition comprising a conjugated diene modified with an unsaturated carboxylic acid or a conjugated diene, a hydrogenated polymer of an aromatic vinyl hydrocarbon, and an epoxy resin are disclosed in JP-A-63-161057.
JP-A No. 63-275664 discloses a composition comprising PPS and a conjugated diene containing a glycidyl group or a conjugated diene and a hydrogenated polymer of an aromatic vinyl hydrocarbon. A composition comprising a polyolefin, a composition comprising PPS, silicone oil and silicone rubber in JP-A-2-229858 and a PPS in JP-A-63-219147.
And a synthetic rubber or a thermoplastic elastomer and a modified silicone oil are disclosed in JP-A-58-154757.
JP-A-64-26670 discloses a composition comprising PPS and an olefin-based copolymer having a glycidyl group. However, even if these compositions were used and melt-molded, the problem of cracks could not be solved yet.

Further, a block polymer of a PPS portion and a PPSS portion disclosed in JP-A-63-79259 and the like, and PPS disclosed in JP-A-2-229857 and JP-A-2-133428. The same problem occurs in the case of the block copolymer of the part and the PPSK part.

[0005]

The object of the present invention is to provide a PP
The toughness, which has greatly improved the weakness that is a drawback of S resin,
It is intended to provide a method for producing a polyarylene sulfide resin composition having excellent impact resistance.

[0006]

In view of the above situation, the present inventors have made earnest studies to obtain an excellent polyarylene sulfide-based resin composition having toughness, and as a result, specified to the polyarylene sulfide-based resin. Rubbery polymer part (b ₁ ) and specific non-rubbery polymer part (b ₂ ) of
In the resin composition obtained by adding the copolymer (B) obtained by binding and the above and melt-kneading them, the rubbery polymer and the non-rubbery polymer are directly added to the polyarylene sulfide resin and melted. It was found that a resin composition excellent in toughness and impact resistance as compared with the case of kneading can be obtained, and the present invention was completed.

That is, the present invention is a rubbery polymer portion (b ₁ ) comprising a polyarylene sulfide resin (A) and a diene polymer and / or an α-olefin polymer.
And a copolymer (B) formed by bonding polyorganosiloxane, polyamide, polyarylene sulfide resin, and at least one non-rubber polymer portion (b ₂ ) selected from α-olefin polymers. A method for producing a resin composition obtained by melt-kneading the resin composition.

The polyarylene sulfide resin (A) in the present invention has the general formula -φ-S- (provided that -φ-
Represents a p-phenylene group, and the same shall apply hereinafter. ) Having a repeating unit of
Polyphenylene sulfide ketone having a repeating unit of -S- (hereinafter abbreviated as PPSK), general formula -φ-
A polymer such as polyphenylene sulfide sulfone (hereinafter abbreviated as PPSS) having a SO ₂ -φ- repeating unit is included. Further, the PAS resin may be a substantially linear polymer, a partially crosslinked polymer, or a mixture thereof. The PAS-based resin also includes random, graft and block copolymers of PPS, PPSK and PPSS.

In the above PPS, PPSK and PPSS, a meta bond [-(m
-Phenylene) -S-], ether bond (-φ-O-φ
-S-), sulfone bond (-φ-SO ₂ -φ-S-),
Sulfide ketone bond (-φ-CO-φ-S-), biphenyl bond (-φ-φ-S-), substituted phenyl sulfide bond (Chemical formula 1) shown below, trifunctional phenyl sulfide bond (Chemical formula 2), Of course, it does not matter even if it contains a naphthyl bond (Chemical Formula 3).

[0010]

[Chemical 1]

[0011]

[Chemical 2]

[0012]

[Chemical 3]

The PPS can be polymerized by polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide in a polar solvent. Polymerization in the presence of p-chlorothiophenol, self-condensation of p-chlorothiophenol, and the like. Sodium sulfide and p-dichloro in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane. A method of reacting benzene is suitable. At this time, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid or to add an alkali hydroxide in order to control the degree of polymerization.

As a method for polymerizing PPSK, for example,
A method of reacting dihalobenzophenone and an alkali metal sulfide in an organic amide solvent (Japanese Patent Laid-Open No. 63-11302).
No. 0 and JP-A-64-54031).

The PPSS can be polymerized, for example, by reacting a dihaloaromatic sulfone and an alkali metal sulfide in an organic amide solvent (US Pat. No. 4,102,875).
No.).

On the other hand, the copolymer (B) comprising the rubbery polymer portion (b ₁ ) and the non-rubbery polymer portion (b ₂ ) used in the present invention is a diene polymer or ( Or) a rubbery polymer portion (b ₁ ) composed of an α-olefin polymer and polyorganosiloxane, polyamide,
It is a copolymer obtained by binding at least one non-rubber polymer portion (b ₂ ) selected from polyarylene sulfide resins and α-olefin polymers by the method described below.

The diene polymer which is one of the components constituting the rubbery polymer portion (b ₁ ) is a diene polymer containing a diene monomer as an essential component, for example, a diene polymer, a diene and an aromatic vinyl hydrocarbon. (Diene / aromatic vinyl hydrocarbon copolymer), a diene / acrylonitrile copolymer (diene / acrylonitrile copolymer), and the like.

The term "diene polymer" as used herein means a polymer derived from one or more diene monomers, that is, a single diene, for example, a homopolymer of 1,3-butadiene, or two or more diene, for example. 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3
-Dimethyl-1,3-butadiene, norbornene, and 1,3-pentadiene copolymers and hydrogenated products thereof, with hydrogenated products being preferred.

The diene / aromatic vinyl hydrocarbon copolymer is a block copolymer or random copolymer having various ratios of diene and aromatic vinyl hydrocarbon, and hydrogenated products thereof are preferable. In this case, a hydrogenated product of a diene / aromatic vinyl hydrocarbon block copolymer is particularly preferably used. The aromatic double bond is excluded from the target of unsaturated bond that is reduced by hydrogenation.

The diene / acrylonitrile copolymer is
Block copolymers or random copolymers having various ratios of dienes to acrylonitrile are preferable, and hydrogenated products thereof are preferable. In this case, hydrogenated diene / acrylonitrile block copolymer is particularly preferably used.

The conjugated diene used as a raw material in the above-mentioned diene / aromatic vinyl hydrocarbon copolymer and diene / acrylonitrile copolymer is 1,3-butadiene,
Isoprene (2-methyl-1,3-butadiene), 2,
Examples thereof include 3-dimethyl-1,3-butadiene and 1,3-pentadiene, and 1,3-butadiene and isoprene are preferably used. 1,4 as non-conjugated dienes
Examples include hexadiene, norbornene, and norbornene derivatives. As the aromatic vinyl hydrocarbon, styrene, α-methylstyrene, o-methylstyrene, p-
Methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene and the like, and styrene is preferably used.

The α-olefin polymer, which is another component constituting the rubbery polymer portion (b ₁ ), is a thermoplastic elastomer containing α-olefin as an essential component. For example, α-olefin and aromatic vinyl. Block copolymers or random copolymers with varying ratios of hydrocarbons or acrylonitrile or different α-olefins. A block copolymer is particularly preferable.

The α-olefin used in the above-mentioned α-olefin polymer includes ethylene, propylene, 1
Butene and isobutylene may be used, and one or more of these may be used.

Specific examples of preferable rubbery polymer portion (b ₁ ) include polybutadiene, polyisoprene,
Styrene / butadiene / styrene triblock copolymer, styrene / isoprene / styrene triblock copolymer, styrene / butadiene diblock copolymer, styrene / isoprene diblock copolymer and hydrogenated products thereof, styrene / ethylene / Styrene copolymer, styrene / polypropylene / styrene copolymer, styrene / ethylene copolymer, styrene / polypropylene copolymer, ethylene / propylene copolymer, ethylene / propylene /
Diene copolymers and the like.

On the other hand, in the copolymer (B), the polymer constituting the non-rubbery polymer portion (b ₂ ) bonded to the above-mentioned rubbery polymer portion (b ₁ ) is polyamide, polyorganosiloxane or polyarylene. At least one selected from sulfide resins and α-olefin polymers
It is a seed.

As the polyamide resin which constitutes the non-rubber polymer portion (b ₂ ), various known ones can be mentioned. For example, dicarboxylic acids such as adipic acid, speric acid, sebacic acid, terephthalic acid, isophthalic acid and dodecanoic acid, and diamines such as ethylenediamine, pentamethylenediamine, hexamethylenediamine, ethylenediamine, decamethylenediamine and 1,4-cyclohexyldiamine. A polyamide obtained by polycondensation of; a polyamide obtained by polymerizing a cyclic lactam such as caprolactam or laurinlactam; or a cyclic lactam,
Examples thereof include polyamides obtained by copolymerizing a salt of dicarboxylic acid and diamine t. Of these polyamides, preferably 6 nylon, 66 nylon, 6
・ 10 nylon, 66/6/10 nylon, 6/66 nylon, 12 nylon, 11 nylon, 11/12 nylon, 46 nylon, MXD6 nylon (copolymer of m-xylenediamine and adipic acid), etc. , And particularly preferably, 12 nylon, 6 nylon, 6
It is 6 nylon.

The polyorganosiloxane has the general formula

[0028]

[Chemical 4]

(Wherein Q and Q'are phenyl groups, vinyl groups, alkyl groups, hydrogen groups, epoxy groups, amino groups, carboxyl groups, mercapto groups) and other polydiorganosiloxanes having a diorganosiloxane basic unit. is there.

More specifically, among linear polydiorganosiloxanes obtained by polymerization of linear or cyclic diorganosiloxane oligomers produced by hydrolysis of (CH ₃ ) ₂ SiCl, oily ones having a relatively small molecular weight are used. (Silicone resin), a resin (silicone resin) having a loose three-dimensional stitch structure obtained by hydrolysis of chlorosilane containing a trifunctional component such as CH ₃ SiCl ₂ .

As the polyarylene sulfide resin, any of those described in the above PAS resin (A) can be applied.

The α-olefin polymer is ethylene, propylene, 1-butene, isobutylene, 4-methyl-1.
It is a non-rubber polymer mainly composed of hard segments, which is obtained by polymerizing one or more α-olefins such as -pentene. In particular,
High molecular weight or low molecular weight polyethylene obtained by homopolymerization of ethylene or decomposition of the polymer, high molecular weight or low molecular weight isotactic polypropylene or atactic polypropylene obtained by homopolymerization of propylene or decomposition of the polymer Polybutene containing isobutylene as a main constituent and a small amount of butene-1 copolymerized, but the content of aliphatic double bonds in the polymer is preferably 5 mol% or less, polyisobutylene, and 4-methyl-1-pentene are preferably 85 mol% or more. Is poly (4
-Methyl-1-pentene) and the like.

Copolymer (B) in which the rubbery polymer portion (b ₁ ) and the non-rubbery polymer portion (b ₂ ) are bonded together
To obtain the above, it is general to take a method of reacting a rubbery polymer having a functional group with a non-rubbery polymer having a functional group that reacts with the functional group in a solution or a molten state. Further, the present invention is not limited to this, and for example, a rubbery polymer having a functional group and a non-rubbery polymer having a functional group are bound to each other by using a third component such as an epoxy resin having a group that reacts with the functional groups. You can also

As the combination of functional groups in the reaction for bonding the rubbery polymer portion (b ₁ ) and the non-rubbery polymer portion (b ₂ ), an amino group and a carboxyl group or an epoxy group, an oxazoline group and a carboxyl group or a mercapto group can be used. Group, hydroxyl group, pyridyl group and carboxyl group, but not limited thereto.

To obtain a rubbery polymer (b ₁ ) containing a carboxyl group as a functional group, for example, a polymer of a carboxyl group-modified diene, the same modified diene / aromatic vinyl hydrocarbon copolymer, or the same modified α-olefin is used. In order to obtain an aromatic vinyl hydrocarbon copolymer, a modified conjugated diene / acrylonitrile copolymer, a modified α-olefin copolymer, etc., the rubbery polymer (b ₁ ) is reacted with an unsaturated carboxylic acid. And good. The unsaturated carboxylic acid used in this case is preferably acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, butenedicarboxylic acid, or the like. Alkyl esters, acid anhydrides, or imides which are derivatives thereof, such as maleic anhydride, itaconic anhydride, citraconic anhydride, maleic imide, itaconic imide, and citraconic imide, can also be used. , Maleic anhydride, itaconic anhydride, and maleic imide can be preferably used.

The glycidyl ester of an α, β unsaturated acid used to obtain an epoxy group-modified rubbery polymer containing an epoxy group in the same manner as described above has the general formula

[0037]

[Chemical 5]

(In the formula, Q ₁ represents a hydrogen atom or a lower alkyl group).

Specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylic acid, glycidyl itaconate, acrylic glycidyl ether, diglycidyl maleate, methyl glycidyl maleate, diglycidyl fumarate, and the like. Glycidyl acrylate, glycidyl methacrylate and acryl glycidyl ether are preferred.

Similarly, unsaturated oxazoline for obtaining a modified rubbery polymer containing an oxazoline group is
For example, the general formula

[0041]

[Chemical 6]

(In the formula, R ₁ represents a hydrogen atom or a methyl group, and R _{2 to} R ₅ represent a hydrogen atom or a lower alkyl group.).

Specifically, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-ethyl-2-oxazoline and the like can be mentioned. One kind or two or more kinds can be effectively used. Among these, 2-vinyl-2-oxazoline and 2-iiisopropenyl-2-oxazoline are preferable.

Unsaturated carboxylic acids or their derivatives, α,
It is necessary that the content (or reaction amount) of the glycidyl ester of β-unsaturated acid or unsaturated oxazoline is 0.01 to 30% by weight, preferably 0.05 to 30% by weight.

As a method for incorporating a carboxyl group, an epoxy group or an oxazoline group into the rubber-like polymer,
Method for coexisting in producing polymer, copolymer or preferably hydrogenated product thereof, polymer or copolymer, preferably unsaturated carboxylic acid or its derivative in the hydrogenated product, α, β- A method of adding a glycidyl ester of an unsaturated acid or an unsaturated oxazoline in the presence or absence of a radical initiator in a solution or a molten state, for example, using an extruder or a Banbury mixer. I can.

In carrying out these reactions, vinyl monomers copolymerizable with unsaturated carboxylic acids or their derivatives or glycidyl esters of α, β-unsaturated acids or unsaturated oxazolines, such as styrene, acrylonitrile, acrylic acid. Esters, methacrylic acid esters and the like can be used.

On the other hand, as the polyorganosiloxane which is a polymer constituting the non-rubber polymer part (b ₂ ) containing a functional group, commercially available products can be used, and examples thereof include epoxy modification, amino modification and mercapto modification. , Or carboxyl-modified silicone oil or silicone resin.

Similarly, when a functional group is contained in a polyarylene sulfide resin, for example, when a polyarylene sulfide, a polyarylene sulfide ketone, a polyarylene sulfide sulfone or the like is produced, a dihaloaromatic carboxylic acid and / or its alkali is used. Obtained by coexisting with a metal salt (Japanese Patent Laid-Open No. 63-3051).
31) Acid-modified products can be mentioned.

In order to obtain the copolymer (B) from the polymers (b ₁ ) and (b ₂ ) having a functional group, a method of reacting in a solution or a molten state is used. For example, by a single screw extruder, a twin screw extruder, a kneader, a Brabender, etc., the melting and kneading by heating is generally carried out at the melting points of (b ₁ ) and (b ₂ ) or higher, preferably at the melting point or higher and 370 ° C. or lower, Usually, it is used in a temperature range of 240 ° C to 330 ° C. It is preferable that neither (b ₁ ) nor (b ₂ ) remains as a functional group of an unreacted substance, but it may remain as long as it does not impair the spirit of the present invention.

In the production of the copolymer B, as mentioned above, the addition of a liquid or solid epoxy resin containing one or more epoxy groups as the third component is effective for smoothing the reaction. Is effective. For example, bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5, -trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4'-dihydroxybiphenyl, 1,5- Glycidyl ethers of bisphenols such as dihydroshiquinaphthalene, cashew phenol, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, glycidyl ethers such as halogenated bisphenols, butanediol, diglycidyl ether instead of bisphenol , Glycidyl ester type such as phthalic acid glycidyl ester, glycidyl epoxy resin such as glycidyl amine such as N-glycidyl aniline, epoxidized polyolefin, epoxidation Linear systems such as soybean oil and vinyl cyclohexene dioxide,
Examples include cyclic non-glycidyl epoxy resins such as dicyclopentadiene oxide. A preferred epoxy resin is a novolac type epoxy. The novolak type epoxy resin contains two or more epoxy groups and is usually obtained by reacting a novolak type phenol resin with epichlorohydrin. The novolac type phenol resin is obtained by the condensation reaction of phenols and formaldehyde. There is no particular limitation on the phenol as a raw material, but phenol, 0-cresol, m-cresol, p-cresol, bisphenol A, resorcinol, p-tert-butylphenol, bisphenol F, bisphenol S, and mixtures thereof are suitable. Used. Further, an epoxidized product of poly-p-vinylphenol can be used as well. Incidentally, these novolac type epoxy resins may have a halogen, a hydroxyl group or the like, and may be used alone or as a mixture of two or more kinds.

The mixing ratio of the polyarylene sulfide resin (A) and the copolymer (B) in the present invention is
(A) / (B) = 5/95 to 95/5. The ratio of the rubbery polymer portion (b ₁ ) to the non-rubbery polymer portion (b ₂ ) is in the range of (b ₁ ) / (b ₂ ) = 95/5 to 5/95 (weight ratio). When the ratio of each component is within such a range, the effects of improving toughness and impact resistance are exhibited. Among them, the preferable mixing ratio is (A) / (B) = 90/10 to 25/7.
5, (b ₁ ) / (b ₂ ) = 80/20 to 20/80.

To the composition of the present invention containing the polyarylene sulfide resin (A) and the copolymer (B), various inorganic and organic fillers may be added alone or in combination of two or more. It can be kneaded and melted.

Specifically, silica, diatomaceous earth, dolomite, γ-alumina, alumina other than γ, titanium oxide, iron oxide, zinc oxide, magnesium oxide, antimonic acid, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide. , Oxides such as pumice, pumice balloon, lead oxide, bismuth oxide, zirconium oxide; zinc hydroxide, aluminum hydroxide, magnesium hydroxide,
Hydroxides such as basic magnesium carbonate; carbonates such as lithium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, dawsonite; sulfuric acid or sulfites such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite; talc, clay, mica , Asbestos, glass fibers, glass balloons, glass beads, silicates such as calcium silicate, montmorillonite, bentonite, hydrosites; other carbon black, graphite, carbon fibers, carbon hollow spheres, iron powder, copper powder, lead powder ,
Particles of inorganic filler such as aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, brass fiber, potassium titanate, titanic acid, lead zirconate, zinc borate, barium metaborate, calcium borate, sodium borate, etc. , Fibrous, whisker-like, spherical, hollow materials, aromatic polyamide fibers, organic fillers such as polytetrafluoroethylene, and the like. Filler content is 0-8
It is 0% by weight and 0 to 70% by weight.

A silane coupling agent can also be added to the composition of the present invention. As the silane coupling agent used, known and commonly used ones such as aminosilane coupling agent, epoxysilane coupling agent, vinylsilane coupling agent, mercaptosilane coupling agent and chlorosilane coupling agent can be used.

In the present invention, other resins can be added within the range not impairing the object of the present invention. Examples of the resin include epoxy resin, polyphenylene ether, polyarylate, polybutylene terephthalate, polyethylene terephthalate, poly 1,4-cyclohexanedimethylene terephthalate, polycarbonate, various liquid crystal polymers, polysulfone, polyether sulfone, polyallyl. Sulfone, polyetherketone,
Polyetheretherketone, polyethylene, polypropylene, polymethylpentene, polystyrene, phenoxy resin, polyimide, polyamideimide, urea resin,
Thermoplastic or thermosetting resins such as phenol resin and DAP resin can be mentioned.

The composition of the present invention may also contain other known additives,
For example, titanate, zirconate, zircoaluminate, surface treatment agents such as aluminum chelate-based coupling agents, antioxidants, heat stabilizers, alkali metal or alkaline earth metal oxides, hydroxides or carbonates, etc. Corrosion inhibitors, lubricants, colorants, crystal nucleating agents and the like can be added in an amount of 0.01 to 10% by weight based on the composition.

The resin composition having the above composition is blended in various mixers and then melt-kneaded in various extruders. At this time, the above-mentioned epoxy resin can be added. Melt-kneading is performed at a melting point or higher and 370 ° C. or lower. The compound obtained can be injection molded, extruded, compression molded, or transferred.
Molded by various molding methods such as molding, it is used as insert parts, electronic parts, electrical equipment, and industrial products.

[0058]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these.

[0059] Reference Example 1 (glycidyl group-containing hydrogenated polymer: b ₁ -1, b ₁ -2 manufacturing) styrene / butadiene / styrene block copolymers in the ratio of butadiene and styrene 60/40 98% Hydrogenated block polymer 10 obtained by hydrogenation to a certain extent
4 parts by weight of glycidyl methacrylate and 0.1 part by weight of Perhexa 25B (manufactured by NOF CORPORATION) were mixed with 0 part by weight with a Henschel mixer and extruded with a 40 mm extruder at a cylinder temperature of 230 ° C. to obtain pellets. The glycidyl methacrylate of the pellets were crushed unreacted dried then extracted with methanol to obtain a glycidyl group-containing styrene / butadiene / styrene hydrogenated polymer (b ₁ -1). The reaction amount of glycidyl methacrylate with respect to the hydrogenated polymer is 1.1.
%Met.

Further, a glycidyl group-containing butadiene hydrogenated polymer (b _1-2 ) was obtained in the same manner except that styrene was not used in the step of producing the glycidyl group-containing styrene / butadiene / styrene hydrogenated polymer.

[0061] Reference Example 2 (acid-modified poly (4-methyl-1 Penten): Production of b ₂ -1) poly (4-methyl-1 Penten) (Mitsui Petrochemical Industries, Ltd. TPX DX over 820) maleic per 100 parts by weight 2.5 parts by weight of acid and 0.1 parts by weight of Perhexa 25B (manufactured by NOF CORPORATION) were uniformly mixed with a Henschel mixer, and this mixture was extruded at a cylinder temperature of 250 ° C. using a 40 mm extruder to give a maleic anhydride-modified poly (4 -methyl-yield 1 Penten) a (b ₂ -1). The reaction amount of maleic anhydride with respect to poly (4-methyl-1-pentene) was 1.5%.

Reference Example 3 (Acid-modified hydrogenated NBR: b _1-
3) Hydrogenated NBR (Zeon Paul 2000 manufactured by Zeon Corporation)
2.5 parts by weight of maleic anhydride and 0.1 parts by weight of Perhexa 25B (produced by NOF CORPORATION) were uniformly mixed with 100 parts by weight with a Henschel mixer, and this mixture was extruded at a cylinder temperature of 250 ° C. using a 40 mm extruder. to give a maleic acid-modified hydrogenated NBR anhydrous (b ₁ -3). Hydrogenated NBR
The reaction amount of maleic anhydride with respect to was 2.0%.

Reference Example 4 (Production of Oxazoline Group-Containing Hydrogenated Polymer: b ₁ -4) A styrene / butadiene / styrene block copolymer having a butadiene / styrene ratio of 70/30 was hydrogenated to about 98%. Hydrogenated block polymer 10 obtained by reduction
5 parts by weight of 2-vinyl-2-oxazoline and 0.1 parts by weight of Perhexa 25B (manufactured by NOF CORPORATION) were mixed with 0 parts by weight with a Henschel mixer and extruded with a 40 mm extruder at a cylinder temperature of 230 ° C. to give oxazoline group-containing styrene / butadiene. / Styrene hydrogenated polymer pellets (b ₁ −
4) was obtained. The reaction amount of 2-vinyl-2-oxazoline with respect to the hydrogenated polymer was 1.2%.

Reference Example 5 (Production of acid-modified PPS: b ₂ -2) N-methylpyrrolidone (NMP) was placed in a 2 L autoclave.
600 g, 73% pure sodium hydrosulfide (NaSH)
Water-NMP was prepared by charging 154.7 g and 88 g of sodium hydroxide and heating up to 200 ° C. under a nitrogen atmosphere.
The mixture was evaporated. Furthermore, 264.6 g of p-dichlorobenzene and 38.2 g of 2,4-dichlorobenzoic acid were added to this system.
Was added to 230 g of NMP, and the mixture was reacted at 220 ° C. for 5 hours and further at 240 ° C. for 1 hour under a nitrogen atmosphere. The reaction product was washed with hot water, methanol and acetone to obtain acid-modified PPS. (PP containing carboxyl group
Content of S structural unit: 4.0 mol%)

In addition to those obtained in Reference Examples, the following commercially available resins were used in Tables 1 to 3 below. (Group of b ₁ ) Acid-modified styrene ethylene butylene styrene copolymer (acid-modified SEBS); Tuftec M1913 Asahi Kasei Co., Ltd. Acid-modified styrene ethylene propylene styrene copolymer
(Acid-modified SEPS); Septon KL-03M-2 Kuraray Co., Ltd. Acid-modified styrene-ethylene propylene copolymer (acid-modified S
EP); Septon KL-01M-2 Kuraray Co., Ltd. Modified ethylene propylene copolymer; HA-102L Tonen Petrochemical Co., Ltd. (group of b ₂ ) Nylon 12; L25 Ems Japan Co., Ltd. Nylon 66; Leona 1300 Asahi Kasei Corporation Company Acid-modified polypropylene; Admer QF305 Mitsui Petrochemical Co., Ltd. Epoxy-modified silicone oil; KF-103 Shin-Etsu Chemical Co., Ltd. Amino-modified silicone oil; KF-861 Shin-Etsu Chemical Co., Ltd. Epoxy-modified polyethylene; Bond First E Sumitomo Chemical Co., Ltd. Acid-modified polyisobutylene; Isovan # 600 Kuraray Co., Ltd.

Reference Example 6 (Production of Copolymer B) A rubbery polymer (b ₁ ) having a functional group and a non-rubbery polymer (b ₂ ) having a functional group which reacts with the functional group are provided in predetermined ratios. After dry-blending with, the polymer was extruded at a cylinder temperature of 290 ° C. using a 40 mm extruder to obtain a copolymer B used in the following Examples and the like.

Examples 1 to 16 and Comparative Examples 1 to 4 Melt flow rate 150 g / 10 minutes (ASTM method D
According to -1238-74, 315.5 ° C., 5 kg load) PPS, melt flow rate is 100 g / 1
0 minutes (360 ° C. according to ASTM method D-1238-74,
PPSK, melt flow rate (measured under a load of 5 kg)
180g / 10 minutes (ASTM method D-1238-74
PPS which is 315.5 ° C. according to the above and measured with a load of 5 kg)
Copolymer (B), silane coupling agent (γ-glycidoxypropyltriethoxysilane;
A-187 Japan Unicar Co., Ltd.), reinforcing materials, etc.
The mixture was blended as in Example 1, then dry blended using a Henschel mixer, and melt-kneaded at 320 ° C. using a 60 mm extruder. This was extruded into a strand shape and cut into pellets. Cylinder temperature of 320 ° C (PPSK
At 360 ° C.) and a mold temperature of 150 ° C. to obtain a sample for measuring physical properties. The results are shown together in Tables 1 to 3.

In Comparative Example 4, without producing Copolymer B, pellets were obtained by dry-blending and melt-kneading the other components as they were, and then molding them in the same manner. For the mechanical properties in the table, the bending properties (AS
TM D-790 compliant), Izod impact strength (AS
According to TM D-256) was measured.

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[Table 1]

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[Table 2]

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[Table 3]

Examples 17 to 20, Comparative Examples 5 to 7 Copolymer B used in Examples 2 and 6 and fused silica (Toshiba Ceramics Glass Grain GR- 80), glass fibers (13 μ diameter, average 120 μ length) are uniformly mixed and 65
After melt-kneading at a cylinder temperature of 300 ° C with an mm extruder,
Alumina substrate with pellets and leads (Fig. 1)
Cylinder temperature 320 using 1 ounce injection molding machine
℃, mold temperature 150 ℃, injection pressure 100Kg / cm ² sealed under conditions of heat shock test (130 ℃ 5 minutes,
The condition of the molded product was observed at −30 ° C. for 5 minutes for 15 cycles.

Reference Example 1 in place of copolymer B for comparison
Using a glycidyl group-containing styrene / butadiene / styrene hydrogenated polymer of (b ₁ -1), and in the same manner observe the condition of the molded article.

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[Table 4]

[Brief description of drawings]

FIG. 1 shows a front view (a) and a partial side sectional view (b) of an alumina substrate with leads.

[Explanation of symbols] 1 sealing resin 2 alumina substrate 3 lead

Claims (7)

[Claims] 1. A polyarylene sulfide resin (A)
And at least one selected from a rubbery polymer portion (b ₁ ) composed of a diene polymer and / or an α-olefin polymer, and polyorganosiloxane, polyamide, polyarylene sulfide resin, and α-olefin polymer. A process for producing a resin composition, which comprises melt-kneading a resin composition containing a copolymer (B) formed by bonding a non-rubber polymer portion (b ₂ ) of a seed. 2. A rubbery polymer portion (b) of the copolymer (B).
₁ ) is a conjugated diene hydrogenated polymer, a hydrogenated copolymer of a conjugated diene and an aromatic vinyl hydrocarbon, a copolymer of an α-olefin and an aromatic vinyl hydrocarbon, a hydrogenated copolymer of a conjugated diene and acrylonitrile, The method for producing a resin composition according to claim 1, which is at least one selected from α-olefin copolymers. 3. A polyarylene sulfide resin (A)
The method for producing a resin composition according to claim 1, wherein is at least one selected from polyarylene sulfide, polyarylene sulfide ketone, and polyarylene sulfide sulfone. 4. The method for producing a resin composition according to claim 1, wherein the resin composition containing an inorganic filler is melt-kneaded. 5. The method for producing a resin composition according to claim 1, wherein the resin composition containing a silane coupling agent is melt-kneaded. 6. An electronic component coated or sealed with the resin composition obtained by the method according to any one of claims 1 to 5. 7. An insert and / or outsert molded article molded from the resin composition obtained by the method according to any one of claims 1 to 5.