JP2002146187A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyphenylene sulfide resin composition having excellent thermal conductivity without impairing fluidity. SOLUTION: This polyphenylene sulfide resin composition is characterized in that (a) 10-90 wt.% of a polyphenylene sulfide resin is mixed with (b) 90-10 wt.% of alumina having >=5 μm and <10 μm average particle diameter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene sulfide resin composition having excellent heat conductivity and fluidity, and particularly useful for electric parts such as electric parts, electronic parts and electric parts for automobiles.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin (hereinafter, referred to as polyphenylene sulfide resin)
Abbreviated as PPS resin) has excellent heat resistance, flame retardancy, rigidity,
Due to its chemical resistance, electrical insulation, and heat and moisture resistance, it has properties suitable for engineering plastics, and is suitable for use in various electrical and electronic parts, mechanical parts, and automotive parts, mainly for injection molding. Widely used.

However, since the PPS resin has a low thermal conductivity, for example, when encapsulating an electronic component that generates heat, the generated heat cannot be diffused efficiently, so that the resin component deteriorates and deforms. Such troubles may occur.

There have been several studies on attempts to improve the thermal conductivity of PPS resins.
For example, Japanese Patent Application Laid-Open No. 4-33958 discloses that alumina powder having an average particle size of 5 μm or less and a fibrous
It is disclosed that by adding to the resin, the thermal conductivity is improved, but in this case, there is an adverse effect on fluidity, and from the viewpoint of achieving a high degree of compatibility between thermal conductivity and fluidity, it is still satisfactory. It was not something.

Japanese Patent Application Laid-Open No. 10-158512 discloses that by blending α-alumina having an α crystal particle diameter of 5 μm or more with low-viscosity PPS resin, the thermal conductivity can be improved without impairing fluidity. Is disclosed,
In this case, there is room for improvement in terms of the balance between thermal conductivity and strength, and α-alumina having an α-crystal particle diameter of 5 μm or more needs to go through a step of low productivity such as a crystal growing step. The production cost is high, and the use of α-alumina having an α-crystal particle diameter of 5 μm or more alone is disadvantageous in terms of economy.

[0006]

SUMMARY OF THE INVENTION The present invention has been achieved as a result of studying to solve the problems in the prior art described above.

Accordingly, an object of the present invention is to provide a PPS resin composition having excellent heat conductivity without impairing fluidity.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that alumina having a specific particle size, particularly α-alumina having a specific particle size and α-crystal particle size, has been developed. By adding to PPS resin,
The inventors have found that the thermal conductivity is greatly improved while having good fluidity, and have reached the present invention.

That is, the present invention provides the following resin composition. 1. A polyphenylene sulfide resin composition comprising (a) 10 to 90% by weight of a polyphenylene sulfide resin and (b) 90 to 10% by weight of alumina having an average particle diameter of 5 μm or more and less than 10 μm. 2. (B) the alumina has an α crystal particle diameter of less than 5 μm;
2. The polyphenylene sulfide resin composition according to the above 1, which is alumina. 3. (B) the alumina is an isocyanate compound,
3. The polyphenylene sulfide resin composition according to the above item 1 or 2, which has been pretreated with a coupling agent selected from an organic silane compound, an organic titanate compound and an organic borane compound. 4. A total of 100 parts by weight of (a) polyphenylene sulfide resin and (b) alumina is further mixed with at least one filler selected from (c) non-fibrous fillers other than alumina and fibrous fillers. 4. The polyphenylene sulfide resin composition according to any one of the above items 1 to 3, which is mixed with 100 parts by weight. 5. (1) The above (1), wherein 5 parts by weight or less of (d) an olefin (co) polymer is further added to 100 parts by weight of the total of (a) polyphenylene sulfide resin and (b) alumina.
Item 5. The polyphenylene sulfide resin composition according to any one of Items 4 to 4.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The polyphenylene sulfide resin (a) used in the present invention includes a repeating unit represented by the following structural formula.

[0011]

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A polymer containing at least 70 mol%, preferably at least 90 mol%, wherein the repeating unit is 70 mol%
If it is less than 30, the heat resistance tends to be impaired. Also, PP
In the S resin, 30 mol% or less of the repeating unit can be constituted by a repeating unit having the following structural formula.

[0013]

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The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as melt kneading is possible.
0-5,000 poise (310 ° C, shear rate 1,0
00 / sec), more preferably in the range of 20 to 1,000 poise, and more preferably in the range of 50 to 600 poise.

Such a PPS resin can be prepared by a known method, that is, a method of obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368 or JP-B-52-1.
It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in JP-A-2240 and JP-A-61-7332.

In the present invention, the PPS resin obtained as described above is subjected to a heat treatment in an atmosphere of inert gas such as nitrogen or under reduced pressure, an organic solvent, hot water, or the like. Of course, it is also possible to use after subjecting to various treatments such as washing with an acid aqueous solution or the like, or activation with a functional group-containing compound such as an acid anhydride, an amine, an isocyanate, or a functional group-containing disulfide compound.

As a specific method for crosslinking / polymerizing the PPS resin by heating, a specific method may be used in an atmosphere of an oxidizing gas such as air or oxygen or a mixed gas of the oxidizing gas and an inert gas such as nitrogen or argon. A method in which heating is performed in a heating vessel at a predetermined temperature under an atmosphere until a desired melt viscosity is obtained can be exemplified. In this case, the heat treatment temperature is usually selected from the range of 150 to 280 ° C., preferably 200 to 270 ° C., and the treatment time is usually selected from the range of 0.5 to 100 hours, preferably 2 to 100 hours. Although it is about 50 hours, a target viscosity level can be obtained by controlling both. The heating device may be an ordinary hot-air dryer or a rotary heating device or a heating device with stirring blades. For efficient and more uniform treatment, a heating device with a rotary or stirring blade is used. Is more preferred.

When the PPS resin is heat-treated in an inert gas atmosphere such as nitrogen or under reduced pressure, a specific method is as follows.
Heat treatment temperature 150 to 280 ° C, preferably 200 to 2
70 ° C, heating time 0.5 to 100 hours, preferably 2 to 100 hours
A method of performing heat treatment under the condition of 50 hours can be exemplified. The heating device may be an ordinary hot air dryer or a rotary or a heating device with a stirring blade. However, if the treatment is to be performed efficiently and more uniformly, a heating device with a rotary or stirring blade may be used. More preferably, it is used.

As a specific method for washing the PPS resin with an organic solvent, the following method can be exemplified. That is, the organic solvent used for cleaning is PPS
There is no particular limitation as long as it does not have an action of decomposing the resin, for example, N-methylpyrrolidone, dimethylformamide, nitrogen-containing polar solvents such as dimethylacetamide, dimethylsulfoxide, sulfoxidesulfone-based solvents such as dimethylsulfone, acetone , Methyl ethyl ketone, diethyl ketone, ketone solvents such as acetophenone, dimethyl ether, dipropyl ether, ether solvents such as tetrahydrofuran, chloroform,
Methylene chloride, trichlorethylene, ethylene chloride,
Halogen solvents such as dichloroethane, tetrachloroethane and chlorobenzene, alcohol and phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol and polyethylene glycol, and benzene, toluene, Examples thereof include aromatic hydrocarbon solvents such as xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable. These organic solvents are used alone or in combination of two or more. As a method for washing with an organic solvent, there is a method such as immersing a PPS resin in an organic solvent, and it is also possible to appropriately stir or heat as necessary. The washing temperature when washing the PPS resin with an organic solvent is not particularly limited, and is from room temperature to 300 ° C.
Any temperature of about ° C can be selected. The higher the cleaning temperature, the higher the cleaning efficiency tends to be.
A sufficient effect can be obtained at a washing temperature of 50 ° C. The PPS resin that has been subjected to the organic solvent washing is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

As a specific method for treating the PPS resin with hot water, the following method can be exemplified. That is, it is preferable that the water to be used is distilled water or deionized water in order to exhibit a preferable effect of chemically modifying the PPS resin by washing with hot water. The operation of the hot water treatment is usually performed by adding a predetermined amount of PPS resin to a predetermined amount of water,
It is carried out by heating and stirring at normal pressure or in a pressure vessel. The proportion of the PPS resin and water is preferably as high as possible.
A bath ratio of less than or equal to 00 g is selected.

The following method can be exemplified as a specific method for treating the PPS resin with an acid. That is, there is a method of immersing the PPS resin in an acid or an aqueous solution of an acid, or the like, and if necessary, stirring or heating can be performed. The acid to be used is not particularly limited as long as it does not have a function of decomposing the PPS resin, and aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halo-substituted aliphatic acids such as chloroacetic acid and dichloroacetic acid are used. Saturated carboxylic acid, acrylic acid, aliphatic unsaturated monocarboxylic acid such as crotonic acid, benzoic acid, aromatic carboxylic acid such as salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, dicarboxylic acid such as fumaric acid, and Inorganic acidic compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid. Among these acids, acetic acid and hydrochloric acid are more preferably used. The acid-treated PPS resin is
It is preferable to wash several times with water or warm water to remove the remaining acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the PPS resin by the acid treatment is not impaired.

The average particle diameter of the alumina (b) used in the present invention is 5 μm or more and less than 10 μm. Further, α-alumina having an average particle diameter of 5 μm or more and less than 10 μm and an α-crystal particle diameter of less than 5 μm is preferable, and an α-crystal particle diameter of 4 μm or less.
α-alumina of less than μm is more preferred. If the average particle size is too large or too small, the fluidity of the resin composition tends to be impaired. It is needless to say that several kinds of alumina having different particle diameters may be used in combination, and alumina mixed so that the total average particle diameter is 5 μm or more and less than 10 μm may be used.

The average particle size in the present invention refers to the particle size with respect to 50% of the weight integrated distribution determined by the Sedigraph method. Note that α crystal particles are primary particles that form alumina particles. α-crystal particles are primary particles forming alumina particles, and usually have an average particle size ≧ α-crystal particle size.
The α crystal particle diameter is a measured average particle diameter determined by the Sedigraph method for those having a BET specific surface area of 3 m ² / g or less, and for those having a BET specific surface area of more than 3 m ² / g, It is a value calculated from the BET specific surface area by the following equation.

D = 6 / (Q × S) D: α crystal particle diameter (μm), Q: density (g / cm ² ), S: BET specific surface area (m ² / g) The ratio of the components (a) and (b) to the total of the component (b) is as follows: (a) 10 to 90% by weight of a polyphenylene sulfide resin;
The range is 10% by weight, preferably (a) 20 to 50% by weight of polyphenylene sulfide resin, and (b) 80 to 50% by weight of alumina. (B) If the amount of alumina falls below the above range, the thermal conductivity decreases, and if it exceeds the above range, the fluidity becomes insufficient and molding tends to be difficult.

The alumina (b) used in the present invention is pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, and an organic borane compound. It is preferable in terms of obtaining strength.

As the coupling agent, an organic silane compound is particularly preferably used. Specific examples of the organic silane compound include β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (amino Ethyl) γ-
Aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ
-Aminopropyltriethoxysilane, N-phenyl-
γ-aminopropyltrimethoxysilane and γ-chloropropyltrimethoxysilane. Among them, γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane are particularly preferably used.

The resin composition of the present invention may further contain (c) at least one filler selected from non-fibrous fillers other than alumina and fibrous fillers.

The shape of the filler may be either fibrous or non-fibrous, and both may be used in combination. Specific examples of the filler include, in addition to glass fiber, carbon fiber, potassium whisker, titanate whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone fiber, metal Fibrous fillers such as fibers, wallastite, zeolite, sericite, mica, talc, kaolin, clay, pyrophyllite, bentonite, asbestos, silicates such as alumina silicate, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide Metal compounds such as iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide, glass beads, Ceramic beads, nitriding C arsenide, silicon carbide, graphite, non-fibrous fillers such as carbon black and silica and the like, which may be hollow, it is also possible to further combination of these fillers 2 or more. In addition, when these fillers are pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound, a more excellent mechanical strength is obtained. Preferred in meaning. Among them, fibrous fillers are preferred, and the use of glass fibers and glass milled fibers is particularly preferred.

The compounding amount of at least one filler selected from the above (c) non-fibrous filler other than alumina and fibrous filler is 100 parts by weight of the total of (a) PPS resin and (b) alumina. On the other hand, it is preferably 5 to 100 parts by weight, more preferably 5 to 50 parts by weight.

In the resin composition of the present invention, (d) an olefin (co) polymer can be further blended, whereby the effects of improving toughness, good fluidity, and adhesion to metals can be improved. You can expect.

Next, (d) the olefin (co) polymer will be described.

Examples of preferred (d) olefin (co) polymers in the present invention include at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic ester group. The functional group-containing olefin (co) polymer to be contained can be exemplified first.

The epoxy group-containing olefin (co) polymer, which is one of the functional group-containing olefin (co) polymers, includes olefin copolymers having glycidyl ester or glycidyl ether in the side chain, Epoxy-oxidized double bond portions of an olefin copolymer having a double bond may be mentioned.

The epoxy group-containing olefin (co)
More specific embodiments of the polymer include an olefin copolymer in which a monomer having an epoxy group is copolymerized, and in particular, at least one α-olefin and at least one α, β-unsaturated acid. Epoxy group-containing olefin copolymers obtained by copolymerizing glycidyl esters of the above are preferably used.

Specific examples of such α-olefin include:
Ethylene, propylene, butene-1, 4-methylpentene-1, hexene-1, decene-1 and octene-1
And the like, and two or more of these can be used simultaneously. Among them, ethylene is particularly preferably used.

On the other hand, glycidyl esters of α, β-unsaturated acids are represented by the general formula

[0037]

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Wherein R represents a hydrogen atom or a lower alkyl group, and specific examples include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate. Among them, methacrylic acid Glycidyl is preferably used.

The epoxy group-containing olefin-based copolymer obtained by copolymerizing the α-olefin and the glycidyl ester of an α, β-unsaturated acid is obtained by mixing the α-olefin with the glycidyl ester of an α, β-unsaturated acid. Random,
Any of alternating, block and graft copolymers may be used.

The amount of the glycidyl ester of the α, β-unsaturated acid in the epoxy group-containing olefin copolymer obtained by copolymerizing the glycidyl ester of the α-olefin and the α, β-unsaturated acid depends on the purpose. Impact on the effect of
From the viewpoints of effects on polymerization, gelation, heat resistance, fluidity, strength, and the like, the content is preferably 0.5 to 40% by weight, particularly preferably 3 to 30% by weight.

In the present invention, α-olefin and α, β-olefin are used as the epoxy group-containing olefin copolymer.
In addition to the glycidyl ester of an unsaturated acid, an epoxy group-containing olefin copolymer containing a monomer represented by the following general formula as a copolymer component is also preferably used.

[0042]

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(Where R ¹ represents hydrogen or a lower alkyl group, X represents a group selected from a —COOR ² group, a —CN group or an aromatic group. Further, R ² represents a group having 1 to 1 carbon atoms.
Specific examples of this monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, and isobutyl acrylate. Α, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate and isobutyl methacrylate;
β-unsaturated carboxylic acid alkyl ester, acrylonitrile, styrene, α-methylstyrene, styrene in which the aromatic ring is substituted with an alkyl group, acrylonitrile-styrene copolymer, and the like. Can also.

The epoxy group-containing olefin copolymer is a copolymer of α-olefin, glycidyl ester of α, β-unsaturated acid, and the above monomer in any of random, alternating, block and graft modes. For example, two or more copolymerization modes such as the above-mentioned monomer being graft-copolymerized with a random copolymer of glycidyl ester of α-olefin and α, β-unsaturated acid are combined. It may be a copolymer.

The copolymerization ratio of the epoxy group-containing olefin copolymer obtained by copolymerizing the α-olefin, the glycidyl ester of α, β-unsaturated acid and the monomer represented by the above general formula is as follows: From the viewpoint of effects on the intended effects, polymerizability, gelation, heat resistance, fluidity, and effects on strength, α-olefins and α, β-unsaturated acid glycidyl esters are added to the total amount of α-olefins. 60 to 99% by weight of olefin, 40 to 1 glycidyl ester of α, β-unsaturated acid
A weight percent range is preferably selected. The copolymerization ratio of the monomer is 5 to 60% by weight based on the total amount of the α-olefin, the glycidyl ester of an α, β-unsaturated acid and the monomer represented by the general formula. Is preferably selected.

Another preferred embodiment of the epoxy group-containing olefin (co) polymer of the present invention is an epoxidized diene block copolymer.

The epoxidized diene-based block copolymer is obtained by epoxidizing a double bond derived from a conjugated diene compound of a block copolymer or a partially hydrogenated block copolymer. The copolymer is
A block copolymer composed of at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound, for example, AB, A -B-A, B-A-B-
An aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as A, (A-B-) _4- Si, or ABABA. Further, the partially hydrogenated block copolymer is obtained by hydrogenating the above block copolymer. Hereinafter, the block copolymer and the partially hydrogenated block copolymer will be described in more detail.

This block copolymer contains the aromatic vinyl compound in an amount of 5 to 95% by weight, preferably 10 to 95% by weight.
60% by weight, more preferably 10 to 50% by weight,
Polymer block A mainly composed of an aromatic vinyl compound,
It has a structure of a homopolymer block of an aromatic vinyl compound or a copolymer block of an aromatic vinyl compound containing more than 50% by weight, preferably 70% by weight or more of an aromatic vinyl compound and a conjugated diene compound. And a conjugated diene compound and / or an aromatic vinyl compound in which the polymer block B mainly composed of a conjugated diene compound is a homopolymer block of the conjugated diene compound or contains a conjugated diene compound in an amount of more than 50% by weight, preferably 70% by weight or more. Having the structure of a copolymer block. Further, the polymer block A mainly composed of an aromatic vinyl compound and the polymer block B mainly composed of a conjugated diene compound are formed by the distribution of the conjugated diene compound or the aromatic vinyl compound in the molecular chain in each polymer block. May be random, tapered (the monomer component increases or decreases along the molecular chain), may be partially block-shaped or any combination thereof, and may be a polymer block mainly composed of an aromatic vinyl compound; When there are two or more polymer blocks each containing a conjugated diene compound as a main component,
Each polymer block may have the same structure or different structures.

The aromatic vinyl compound constituting the block copolymer is, for example, one or two of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and 1,1-diphenylethylene. The above can be selected, and among them, styrene is preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene and 2,3-dimethyl-
One or more kinds are selected from 1,3-butadiene and the like, and among them, butadiene, isoprene and a combination thereof are preferable. The polymer block mainly composed of a conjugated diene compound can arbitrarily select a microstructure in the block. For example, in a polybutadiene block, the 1,2-vinyl bond structure is 5 to 5.
A range of 65% is preferred, especially preferred is 10-50%
Range.

The number average molecular weight of the block copolymer having the above structure is usually from 5,000 to 1,000,000.
0, preferably 10,000 to 800,000, more preferably 30,000 to 500,000, and a molecular weight distribution [ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn). )] Is 10 or less.
Furthermore, the molecular structure of the block copolymer is linear, branched,
It may be radial or any combination of these.

As a method for producing these block copolymers, any method may be used as long as it has the above-mentioned structure. For example,
According to the method described in JP-B-40-23798, an aromatic vinyl compound-conjugated diene compound block copolymer can be synthesized in an inert solvent using a lithium catalyst.

The partially hydrogenated block copolymer is obtained by hydrogenating the above aromatic vinyl compound-conjugated diene compound block copolymer. Examples of the method include JP-B-42-8704 and JP-B-43-6-6.
Although the method described in JP-A-636 can be adopted, it was synthesized using a titanium-based hydrogenation catalyst exhibiting particularly excellent performance in weather resistance and heat deterioration resistance of the obtained hydrogenated block copolymer. Hydrogenated block copolymers are most preferred. For example, JP-A-59-133203 and JP-A-6-133203
According to the method described in JP-A-0-79005, a block copolymer having the above structure is hydrogenated in an inert solvent in the presence of a titanium-based hydrogenation catalyst to synthesize a hydrogenated block copolymer. be able to. At this time, 0 to 99% of the aliphatic double bond based on the conjugated diene compound of the aromatic vinyl compound-conjugated diene compound block copolymer is hydrogenated, and preferably 0 to 70% is hydrogenated. . These block copolymers and partially hydrogenated block copolymers are already on the market and can be easily obtained.

Next, the epoxidized diene-based block copolymer which can be used as one of the components (d) of the present invention is obtained by adding an epoxidizing agent to a block copolymer having the above structure or a partially hydrogenated block copolymer. Is reacted to epoxidize the aliphatic double bond based on the conjugated diene compound. Epoxidized diene block copolymer used in the present invention,
It can be obtained by reacting the above block copolymer or partially hydrogenated block copolymer with an epoxidizing agent such as hydroperoxides and peracids in an inert solvent. To obtain a catalytic effect by using a mixture of formic acid, peracetic acid, and perbenzoic acid with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. Can be. Also, the optimal amount of epoxidizing agent can be determined by such variables as the particular epoxidizing agent used, the desired degree of epoxidation, the particular block copolymer used, and the like. The obtained epoxidized diene-based block copolymer can be isolated by an appropriate method, for example, a method of precipitating with a poor solvent, a method of throwing the polymer into hot water with stirring and distilling off the solvent, and It can be performed by a direct desolvation method or the like.

The degree of epoxidation of the epoxidized diene-based block copolymer is not particularly limited, but the oxirane oxygen concentration is preferably 0.1% by weight or more and 7% by weight or less, particularly preferably 1.0% by weight or more. It is preferably at most 5% by weight.

In the present invention, examples of (d) an olefin (co) polymer containing a carboxyl group and a salt thereof, a carboxylic acid ester group, and an acid anhydride group which can be used as an olefin (co) polymer component are given below. Is a copolymer of ethylene and α-olefin such as polyethylene, polypropylene, ethylene-butene copolymer, ethylene-octene copolymer, ethylene-hexene copolymer, polyethylene, polypropylene, polystyrene, ethylene-propylene copolymer , Polybutene, ethylene-propylene-
Diene copolymer, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer (SB
S), styrene-isoprene-styrene block copolymer (SIS), polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, styrene-ethylene / butylene-styrene block copolymer (SEBS), Styrene-ethylene
Polyolefin (co) polymers such as propylene-styrene block copolymers (SEPS), acid anhydrides such as maleic anhydride, succinic anhydride, fumaric anhydride, acrylic acid, methacrylic acid, vinyl acetate, etc. Carboxylic acid and salts thereof such as Na, Zn, K, Ca, Mg, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, etc. And the like. Olefin-based copolymers obtained by copolymerizing a carboxylic acid ester of, for example, ethylene-
Methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-n-propyl acrylate copolymer, ethylene-isopropyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-acryl T-butyl acid copolymer, ethylene-isobutyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-n-propyl methacrylate copolymer, ethylene-methacrylic acid Olefin- (meth) acrylate copolymers such as isopropyl copolymer, ethylene-n-butyl methacrylate copolymer, ethylene-t-butyl methacrylate copolymer, ethylene-isobutyl methacrylate copolymer, acrylic Acid-acrylonitrile copolymer, methacrylic acid Chill - acrylonitrile copolymer, propyl acrylate - acrylonitrile copolymer,
Propyl methacrylate-acrylonitrile copolymer,
(Meth) acrylate-acrylonitrile copolymers such as butyl acrylate-acrylonitrile copolymer, butyl methacrylate-acrylonitrile copolymer,
Ethylene- (meth) acrylic acid copolymer and its N
a, Zn, K, Ca, metal salts such as Mg, ethylene-maleic anhydride copolymer, ethylene-butene-maleic anhydride copolymer, ethylene-propylene-maleic anhydride copolymer, ethylene- Hexene-maleic anhydride copolymer, ethylene-octene-maleic anhydride copolymer, propylene-maleic anhydride copolymer or maleic anhydride-modified SBS, SIS, SEBS, S
EPS, ethylene-ethyl acrylate copolymer and the like can be exemplified.

The copolymerization mode of the olefin (co) polymer is not particularly limited, and any copolymerization mode such as a random copolymer, a graft copolymer, and a block copolymer may be used.

In the present invention, as the component (d), a functional group-containing olefin (copolymer) containing at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylate group. When the polymer is used, it is of course possible to use two or more kinds of the above functional group-containing olefin copolymers in combination.

In the present invention, (d) an olefin (co)
As the polymer, an olefin (co) polymer which does not contain any functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group is also used, and particularly excellent flow characteristics. , Is effective in obtaining toughness, in which case an epoxy group, an acid anhydride group,
It is preferable to use a functional group-containing olefin (co) polymer containing at least one functional group selected from a carboxyl group, a salt thereof, and a carboxylic acid ester group in combination.

As a specific example of such an olefin (co) polymer containing no functional group selected from epoxy groups, acid anhydride groups, carboxyl groups and salts thereof, and carboxylic acid ester groups, ethylene / α- Olefin-based copolymers can be exemplified, such α-olefins are α-olefins other than ethylene, and specific examples of such α-olefins are propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-
Nonene, 1-decene, 1-undecene, 1-dodecene,
1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3- Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene,
4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-
Decene, 11-methyl-1-dodecene, 12-ethyl-
1-tetradecene and combinations thereof.

In the present invention, ethylene / α-olefin
When using a copolymer, the density is 0.880 g
/ Cm^ThreeBelow, preferably 0.830 to 0.880 g /
cm ^Three, More preferably 0.850 to 0.875
g / cm^ThreeTylene / α-olefin copolymer in the range of
Are particularly favorable for obtaining excellent adhesion and toughness with metals.
Good.

The ethylene / α-olefin copolymer preferably has an α-olefin content of preferably 4 to 25 mol%, more preferably 7 to 25 mol%, and still more preferably 12 to 22 mol%. % Range. Ethylene having an α-olefin content in the above range.
By using an α-olefin copolymer, it is possible to obtain a resin composition having excellent adhesion to metal and toughness.

As such an ethylene / α-olefin-based copolymer, those polymerized using a metallocene-based catalyst can also be used. The metallocene catalyst is composed of a cyclopentadienyl derivative of a Group IV metal such as titanium or zirconium and a co-catalyst. Metallocene catalysts are highly active, and the molecular weight distribution of the resulting polymer is narrower than conventional catalysts represented by Ziegler catalysts,
The copolymer is characterized by having excellent toughness due to uniform distribution of α-olefin which is a comonomer component of the copolymer.
The blending amount of the (d) olefin (co) polymer is as follows:
The amount is preferably 5 parts by weight or less, more preferably 4 parts by weight or less, from the viewpoint of moldability, based on 100 parts by weight of the total of (a) the PPS resin and (b) alumina. In order to sufficiently exert the effect of improving the metal / resin adhesion at the time of metal insert molding by the blending of the olefin (co) polymer, it is preferable to blend 0.5 parts by weight or more.

Further, an alkoxysilane having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group and a ureide group is further added to the resin composition of the present invention. The thing is
It is effective for improving mechanical strength and toughness. Specific examples of such compounds include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Compounds, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl A) ureido group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ
Amino-containing alkoxysilane compounds such as-(2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-hydroxypropyltrimethoxy Hydroxy group-containing alkoxysilane compounds such as silane and γ-hydroxypropyltriethoxysilane.

The preferable addition amount of the silane compound is 0.1 to 100 parts by weight of the polyphenylene sulfide resin.
A range of from 0.5 to 5 parts by weight is selected.

In the PPS resin composition of the present invention, it is preferable to further mix a non-crystalline thermoplastic resin having a glass transition temperature of 120 ° C. or higher from the viewpoint of obtaining a more excellent dimensional stabilizing effect.

Examples of the non-crystalline thermoplastic resin having a glass transition temperature of 120 ° C. or higher include, for example, polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyethersulfone resins, polyarylate resins, and polyetherimide resins. Resin, polyamideimide resin or cyclic polyolefin resin ("TOPAS" manufactured by Ticona, "APEL" manufactured by Mitsui Chemicals, "ZEONEX", "ZEONOA" manufactured by Zeon Corporation, "ARTON" manufactured by Nippon Synthetic Rubber Co., Ltd.) And the like.

Further, the PPS resin composition of the present invention may be any polyester, polyamide, polytetrafluoroethylene, polyether ketone, polythioether ketone, polyether ether ketone, epoxy resin, phenol resin within the range not impairing the effects of the present invention. And resins such as polyethylene, polystyrene, polypropylene, ABS resin, polyamide elastomer, polyester elastomer, and polyalkylene oxide.

In the present invention, further, the glass transition temperature is 12
When compounding an amorphous thermoplastic resin of 0 ° C. or higher,
(A) PPS resin and (b) α-alumina total 100
5 to 80 parts by weight, more preferably 5 to 80 parts by weight,
It is preferable to mix in a range of 40 parts by weight from the viewpoint of obtaining a more excellent dimensional stabilizing effect.

In the resin composition of the present invention, plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organic phosphorus compounds, talc, kaolin, and organic compounds are used as long as the effects of the present invention are not impaired. Antioxidants for crystal nucleating agents such as phosphorus compounds, release agents such as polyolefin compounds, silicone compounds, long-chain aliphatic ester compounds and long-chain aliphatic amide compounds, hindered phenol compounds and hindered amine compounds Ordinary additives such as lubricants, heat stabilizers, lubricants such as calcium stearate, aluminum stearate, and lithium stearate, UV inhibitors, coloring agents, flame retardants, and foaming agents can be further added.

The method for preparing the resin composition of the present invention is not particularly limited, but the mixture of the raw materials is fed to a conventionally known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll. 280-3
A typical example is a method of kneading at a temperature of 80 ° C. The order of mixing the raw materials is also not particularly limited, and is a method in which all the raw materials are blended and then melt-kneaded by the above-mentioned method. Any method may be used, such as a method of mixing some raw materials and then mixing the remaining raw materials using a side feeder during melt-kneading by a single-screw or twin-screw extruder. Further, as for the small amount of the additive component, it is of course possible to knead the other component by the above-mentioned method and the like to form a pellet, and then add it before molding to provide for molding.

The resin composition obtained according to the present invention comprises PP
Without significantly impairing the fluidity, thermal stability, mechanical strength, electrical insulation and low water absorption of the S resin,
It is a resin composition provided with new properties, which has been lacking in conventional PPS resins, that is, improved thermal conductivity.

The resin composition of the present invention can be applied to various known molding methods such as injection molding, extrusion molding, compression molding and injection compression molding, and is a resin composition suitable for injection molding. .

The molded article made of the resin composition of the present invention includes a generator, a motor, a transformer, a current transformer, a voltage regulator, a rectifier,
Especially suitable for electrical equipment parts such as inverters, relays, power contacts, switches, breakers, knife switches, other pole rods, electrical parts cabinets, etc., sensors, LED lamps, connectors, sockets, resistors, Relay case, small switch, coil bobbin, condenser, variable condenser case, optical pickup, oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, semiconductor , Liquid crystal, FDD carriage, FDD chassis, hard disk parts, DVD parts, motor brush holder, parabolic antenna, electronic parts represented by computer related parts; VTR parts, TV parts, iron, hair dryer, cooking Equipment, microwave oven parts, audio parts, audio equipment parts such as audio / laser disk (registered trademark) / compact disk, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Electrical product parts; office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, washing jigs, motor parts, machine-related parts represented by lighters, typewriters, etc .; microscopes, binoculars, cameras, Optical equipment such as watches, precision machinery related parts; alternator terminal, alternator connector, IC
Various valves such as regulators, potentiometer bases for light days, exhaust gas valves, fuel
Exhaust system / intake system various pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body,
Carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, air conditioner thermostat base, heating hot air flow control valve, Brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts,
Distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel-related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation board, step motor rotor, lamp socket, Lamp reflector,
It can be applied to various uses such as automobile and vehicle related parts such as a lamp housing, a brake piston, a solenoid bobbin, an engine oil filter, and an ignition device case.

Among them, the resin composition of the present invention makes use of its excellent thermal conductivity and fluidity to produce electric and electronic parts,
Alternatively, it can be very practically applied to electric parts such as automobile electric parts.

[0075]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the following physical property values were measured according to the following methods.

(1) Flexural strength and flexural modulus: AST
The measurement was performed according to MD790. Specifically, the measurement was performed as follows. The resin composition pellets of the present invention are supplied to an injection molding machine (SG75-HIPRO MIII) manufactured by Sumitomo-Nestal Co., Ltd., set at a cylinder temperature of 330 ° C.
Injection pressure = Injection molding = molding lower limit pressure + 5 kgf / cm ² Gauge pressure, injection width 12.7 mm × height 6.4 mm × length 1
A 27 mm test piece was obtained. Using this test piece, 23 ℃
The measurement was performed under an atmosphere of a relative humidity of 50% under the conditions of a span of 100 mm and a strain rate of 3 mm / min.

(2) Melt viscosity: 316 ° C., shear rate 1216 using “Capillograph” manufactured by Toyo Kiko Co., Ltd.
/ Melt viscosity was measured. The smaller this value is, the better the fluidity is.

(3) Thermal conductivity: The thermal conductivity λ was obtained by calculating the thermal diffusivity α and the heat capacity ρCp and calculating the product by the following equation.

Λ = αρCp λ: Thermal conductivity (w / mk) α: Thermal diffusivity (m ² / s) ρCp: Heat capacity (J / m ³ · K) Density is immersion liquid water, mass analysis is electronic analysis Using a balance 23
The thermal diffusivity measured by the Archimedes method at ℃ was obtained by using a sample cut from an ASTM No. 1 dumbbell piece injection-molded under the same conditions as the above bending test piece as a sample, and using a TC- manufactured by Vacuum Riko Co., Ltd. as a measuring device. 70
The measurement was performed by a laser flash method under the condition of 80 ° C. using a 00 (ruby laser).

The specific heat was measured using a Perkin Elmer D
The measurement was performed by the DSC method under the conditions of a heating rate of 10 ° C./min and a measuring temperature of 80 ° C. using SC-2.

(A) The following two types of PPS resins were prepared.

PPS-A: linear PPS, melt viscosity 50
0 poise (310 ° C., shear rate 1000 / sec), ash content 0.08% by weight, PPS-B: M2900 (crosslinked type) manufactured by Toray Industries, Inc. (b) The following were prepared as α-alumina.

Alumina-A: average particle diameter 6.5 μm, α
Crystal grain size 3.2 μm (A-42 manufactured by Showa Denko KK)
6) Alumina-B: average particle size 6.5 μm, α crystal particle size 3.
2 μm (A-42-6 manufactured by Showa Denko KK) treated with γ-glycidoxypropyltrimethoxysilane.

Alumina-C: average particle size 6.5 μm, α
Crystal grain size 3.2 μm (A-42 manufactured by Showa Denko KK)
6) treated with N-phenyl-γ-aminopropyltrimethoxysilane.

Alumina-D: a product obtained by treating an average particle diameter of 58 μm and an α crystal particle diameter of 3.2 μm (A-12 manufactured by Showa Denko KK) with N-phenyl-γ-aminopropyltrimethoxysilane.

Alumina-E: average particle size 1.8 μm, α
Crystal particle diameter 1.7 μm (AL-45 manufactured by Showa Denko KK)
-1) treated with N-phenyl-γ-aminopropyltrimethoxysilane.

Alumina-F: average particle diameter 37 μm, α crystal particle diameter 37 μm (AS-10, manufactured by Showa Denko KK)
Treated with N-phenyl-γ-aminopropyltrimethoxysilane. (C) A glass fiber chopped strand (diameter 10 μm, length 3 mm) was prepared as a filler. (D) As an olefin copolymer, an ethylene / glycidyl methacrylate (88/12% by weight) copolymer was prepared.

Example 1 Melt kneading of a PPS resin, alumina, a filler and an olefin (co) polymer was carried out using a screw type twin screw extruder (Ikegai PCM-30).

PPS-A: 20% by weight, alumina-A:
Dry blend 80% by weight, cylinder temperature 32
The mixture was fed to a feeder of an operating extruder under the conditions of 0 ° C. and a screw rotation speed of 150 rpm to perform melt-kneading. The extruded gut was cooled and pelletized with a pelletizer.

The resin composition obtained here was injection molded into various test pieces, and the results of measurement of material strength and thermal conductivity were as shown in Table 1.

[Examples 2 and 3] Melt kneading, pelletizing and evaluation were carried out in the same manner as in Example 1 except that alumina subjected to coupling treatment (alumina-B, C) was used.

The results are shown in Table 1. As can be seen from the table, when alumina-B was used, superior strength and thermal conductivity were obtained.
It is understood that when C is used, more excellent fluidity can be obtained. [Examples 4 to 6] Melt kneading, pelletizing and evaluation were carried out in the same manner as in Example 1 by using the respective compounding agents shown in Table 1 in the mixing ratios shown in Table 1. The results are also shown in Table 1.

[Comparative Examples 1 and 2] Melt kneading, pelletizing and evaluation were performed in the same manner as in Example 1 except that alumina-D and E were used as alumina.

The results are as shown in Table 1.
When alumina-D having a large average particle diameter was used, the melt viscosity was significantly increased, and injection molding was difficult. When alumina-E having a small average particle diameter was used, the results were higher in melt viscosity and inferior in thermal conductivity than in Examples 1 to 3.

Comparative Example 3 Alumina-F as Alumina
, Melt kneading, pelletizing, and evaluation were performed in the same manner as in Example 1.

The results are as shown in Table 1.
When alumina-F having a large average particle diameter and an α crystal particle diameter was used, the bending strength was low and the results were also inferior in terms of thermal conductivity.

[0097]

[Table 1]

[0098]

As described above, since the resin composition of the present invention has excellent heat conductivity without impairing the fluidity, the resin composition of the present invention can be used for electric, electronic parts or automobile electric parts. It is particularly useful for electrical component applications and can be applied to various other fields.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // (C08L 81/02 (C08L 81/02 57:10) 57:10) F term (reference) 4J002 AC112 BB072 BB092 BB232 BG042 BG062 BG072 BG102 BP012 BP032 CD192 CL063 CN011 DA017 DA027 DA037 DA067 DE077 DE087 DE097 DE107 DE117 DE137 DE146 DE147 DE187 DE237 DG047 DG057 DJ007 DJ017 DJ027 DJ037 DJ047 DJ057 DK007 DL47 FA04166 FB007 FB007 FB007 FB007

Claims (5)

[Claims] 1. (a) Polyphenylene sulfide resin 1
A polyphenylene sulfide resin composition comprising 0 to 90% by weight and (b) 90 to 10% by weight of alumina having an average particle diameter of more than 5 μm and less than 10 μm. (B) the alumina has an α crystal particle diameter of 5 μm;
The polyphenylene sulfide resin composition according to claim 1, which is less than α-alumina. 3. The method according to claim 1, wherein (b) the alumina is pretreated with a coupling agent selected from isocyanate compounds, organic silane compounds, organic titanate compounds and organic borane compounds. The polyphenylene sulfide resin composition according to the above. 4. A polyphenylene sulfide resin,
(b) For a total of 100 parts by weight of alumina, (c)
The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein 5 to 100 parts by weight of at least one filler selected from non-fibrous fillers and fibrous fillers other than alumina is blended. object. (5) a polyphenylene sulfide resin;
(b) For a total of 100 parts by weight of alumina, (d)
The polyphenylene sulfide resin composition according to any one of claims 1 to 4, wherein the olefin (co) polymer is blended in an amount of 5 parts by weight or less.