JP4419529B2 - Resin composition and molded product obtained therefrom - Google Patents

Description

  Since the present invention has good fluidity during molding and the filling density of the obtained molded product is increased, it has excellent mechanical properties and thermal conductivity, and the properties even under conditions of use under high temperature and high humidity. The present invention relates to a resin composition excellent in retainability and a molded product comprising the same.

  In recent years, various electrical components have been electronically controlled by computers in order to improve fuel efficiency, weight reduction or safety, and comfort in the automobile field. In the electric / electronic field, as well as improving the performance of personal computers, household electrical appliances such as refrigerators and washing machines are being electronically controlled by computers for the purpose of energy saving.

  Electronic devices such as LSIs and CPUs that perform electronic control have problems such as damage to electronic devices due to increased power consumption due to increased integration of computers and faster operation, and increased heat generation.

  Therefore, heat dissipation measures are necessary for computers, and conventionally heat sinks made of aluminum or die-casting have been used to dissipate heat in electronic component packages that are heat sources, but the heat dissipation characteristics with respect to the amount of heat generated are limited. It is reaching an area beyond.

  However, in the future, when parts are further reduced in size, weight, or complicated shape, metal such as die-casting is not productive and the shape is limited. In view of this, studies have been made on improving the productivity by resinization and balancing the heat dissipation characteristics by adding a filler having high thermal conductivity such as graphite, alumina, and aluminum nitride to the thermoplastic resin.

  In particular, since aluminum nitride powder has high thermal conductivity among fillers, many proposals have been made to fill it with resin and use it as a heat radiating member for electric and electronic parts and electronic devices.

  Here, the heat radiating member is a material in which an insulating resin such as a thermoplastic resin, an epoxy resin, or silicone is filled with a heat conductive filler such as aluminum nitride powder, boron nitride powder, or alumina. It is a member having characteristics for efficiently removing heat generated from electronic and electrical components out of the system.

  For example, a method in which an aluminum nitride fine powder having an average particle size of 1 μm or less is blended with an organosiloxane composition (Patent Document 1), an aluminum nitride powder having an average particle size of 3 μm or less is dried, granulated, and sintered spherical aluminum nitride Method used (Patent Document 2, Patent Document 3, Patent Document 4). A method using a pulverized product of an aluminum nitride sintered body (Patent Documents 5 and 6) is disclosed.

  However, the aluminum nitride powder of Patent Document 1 undergoes hydrolysis in the presence of moisture, changes to aluminum hydroxide and generates ammonia gas. For this reason, the thermal conductivity is greatly lowered, and the interface with the resin component or the interfacial bondability between the fillers is lowered due to the generation of ammonia gas, so that the effect of adding aluminum nitride is not sufficiently exhibited.

In addition, the spherical aluminum nitride sintered body particles of Patent Document 2, Patent Document 3 and Patent Document 4 are prepared by adding a raw material aluminum nitride particle size in advance with a sintering aid such as calcium oxide and an organic binder such as polyacrylic acid. Is adjusted to a sintered particle size by granulation, and is fired in an inert atmosphere at 1600 to 1900 ° C. It is characterized by not undergoing a pulverization step, and by using the spherical particles produced in this way as a filler, the thermal conductivity of the resin is improved, and the high filling of the filler due to the good fluidity of the resin. Although it is possible, this spherical particle is also hydrolyzed with moisture, so that the wet heat resistance is not sufficient as in Patent Document 1. The aluminum nitride sintered bodies of Patent Document 5 and Patent Document 6 are obtained by removing lattice defects of the aluminum nitride particles by sintering at high temperature. As a result, the hydrolysis resistance is improved, but the target particle size is obtained in practical use. For this reason, lattice defects are generated again by the pulverization, so that the improvement effect is not sufficient.
Japanese Patent Laid-Open No. 3-14873 (first page, example) JP-A-3-295863 (first page, examples) JP-A-4-174910 (first page, examples) Japanese Patent Laid-Open No. 11-269302 (page 2, example) JP-A-6-164174 (second page, example) Japanese Patent Laid-Open No. 6-209057 (second page, examples)

  Therefore, in view of the above-described problems, the present invention eliminates the problem, that is, the fluidity at the time of molding processing is good, and the filling density of the obtained molded product is increased, so that it has excellent mechanical properties and thermal conductivity, It is another object of the present invention to provide a resin composition having excellent property retention even under conditions of use under high temperature and high humidity, and a molded product comprising the same.

  As a result of intensive studies to achieve the above object, the present inventors have reached the present invention.

That is, the present invention
(1) (A) 60 to 6% by weight of a thermoplastic resin that is at least one selected from a polyamide resin, a non-liquid crystal polyester resin, a liquid crystal polymer, and a polyarylene sulfide resin ;
(B) particles obtained by a solid phase reaction method in which aluminum nitride powder and silica are mixed and heated in a non-oxidizing atmosphere, or a reaction sintering method in which a mixed powder of metal aluminum powder and silica powder is heated in a nitrogen atmosphere A resin composition comprising 40 to 94% by weight of an aluminum nitride powder whose surface is coated with silica,
(2) The resin composition as described in (1) above, wherein a thermal conductivity measured by a laser flash method of a molded product obtained by melt molding the resin composition is 1 W / mK or more,
(3) The resin composition as described in (1) or (2) above, wherein 8% by volume or more of the particle size distribution of the aluminum nitride powder whose particle surface is coated with silica is particles of 30 μm or more. ,
(4) Further, (C) one or more of fatty acid metal salts, ester compounds, amide group-containing compounds, epoxy compounds, and phosphate esters, with respect to a total of 100 parts by weight of (A) and (B) The resin composition according to any one of (1) to (3) above, wherein 0.5 to 10 parts by weight are added,
(5) A molded product formed by injection molding the resin composition according to any one of (1) to (4 ) above,
(6) molded article is a molded article of the above (5), wherein the an electrical electronic component case.

  The resin composition of the present invention and a molded product obtained from the resin composition can be obtained as a resin composition highly filled with aluminum nitride, and are excellent in mechanical properties and thermal conductivity under high temperature and high humidity, and molded with good fluidity. Since a molded product with excellent product filling properties can be obtained, it is suitable for electrical and electronic equipment that requires moisture and heat resistance. Moreover, compared with a metal thing, it is lightweight and has very high shape selectivity, and since it can be injection-molded, productivity is high.

  Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

  In the present invention, the (A) thermoplastic resin is a synthetic resin that can be melt-molded.

As (A) a thermoplastic resin, the mechanical properties, the polyamide resin from the viewpoint of moldability, non-liquid crystal polyester resins, liquid crystal polymers such as a liquid crystal polyester resin, at least one selected from the polyarylene sulfide resin is used .

  Specific examples of the non-liquid crystalline semi-aromatic polyester include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, poly 1,4-cyclohexanedimethylene terephthalate and polyethylene-1,2-bis ( Copolymerization of polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / decane dicarboxylate and polycyclohexanedimethylene terephthalate / isophthalate in addition to phenoxy) ethane-4,4′-dicarboxylate Examples include polyester. Of the above, polybutylene terephthalate, polybutylene naphthalate, poly 1,4-cyclohexanedimethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene terephthalate, and the like can be preferably used in terms of mechanical properties, moldability, and the like. Of these, polybutylene terephthalate is preferable.

  Specific examples of the polyamide resin include, for example, ring-opening polymer of cyclic lactam, polycondensate of aminocarboxylic acid, polycondensate of dicarboxylic acid and diamine, and specifically nylon 6, nylon 4 and the like.・ 6, Nylon 6/6, Nylon 6/10, Nylon 6/12, Nylon 11, Nylon 12 and other aliphatic polyamides, poly (metaxylene adipamide), poly (hexamethylene terephthalamide), poly (hexamethylene) Isophthalamide), polynonanemethylene terephthalamide, poly (tetramethylene isophthalamide), poly (methylpentamethylene terephthalamide) and other aliphatic-aromatic polyamides, and copolymers thereof. Examples of the copolymer include Nylon 6 / poly (hexamethylene terephthalamide), nylon 6 / poly (hexamethylene terephthalamide), nylon 6 / nylon 6/6 / poly (hexamethylene isophthalamide), poly (hexamethylene isophthalamide) / poly (hexamethylene terephthalamide), nylon 6 / poly (hexamethylene) Examples thereof include isophthalamide) / poly (hexamethylene terephthalamide), nylon 12 / poly (hexamethylene terephthalamide), poly (methylpentamethylene terephthalamide) / poly (hexamethylene terephthalamide), and the like. The form of copolymerization may be either random or block, but is preferably random. Among the above-mentioned polyamide resins, nylon 6, nylon 6,6, nylon 12, nylon 4,6, polynonanemethylene terephthalamide, nylon 6 / poly (hexamethylene terephthalamide), nylon in terms of mechanical properties and moldability 6.6 / poly (hexamethylene terephthalamide), nylon 6 / nylon 6.6 / poly (hexamethylene isophthalamide), poly (hexamethylene isophthalamide) / poly (hexamethylene terephthalamide), nylon 6 / poly (hexa) Methylene isophthalamide) / poly (hexamethylene terephthalamide), nylon 12 / poly (hexamethylene terephthalamide), nylon 6 / nylon 6/6 / poly (hexamethylene isophthalamide), poly (methylpentamethylene terephthalamide) It can be preferably used polyamide resins such as poly (hexamethylene terephthalamide), among others nylon 6 is preferred.

  The liquid crystal polymer is a resin capable of forming an anisotropic molten phase, and preferably has an ester bond. For example, a liquid crystalline polyester resin comprising a structural unit selected from an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic and / or aliphatic dicarbonyl unit, an alkylenedioxy unit, etc., and forming an anisotropic melt phase Or a liquid crystalline polyester amide resin comprising a structural unit selected from the structural unit and an aromatic iminocarbonyl unit, an aromatic diimino unit, an aromatic iminooxy unit, etc., and forming an anisotropic melt phase. Specifically, a liquid crystalline polyester comprising a structural unit produced from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, a structural unit produced from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid Structural units, aromatic dihydroxy compounds and / or aliphatic dicals generated from A liquid crystalline polyester comprising a structural unit produced from an acid, a structural unit produced from p-hydroxybenzoic acid, a structural unit produced from 4,4′-dihydroxybiphenyl, an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid, and / or Or a liquid crystalline polyester comprising a structural unit produced from an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, a structural unit produced from p-hydroxybenzoic acid, a structural unit produced from ethylene glycol, or a structural unit produced from terephthalic acid A liquid crystalline polyester, a structural unit produced from p-hydroxybenzoic acid, a structural unit produced from ethylene glycol, a liquid crystalline polyester comprising a structural unit produced from terephthalic acid and isophthalic acid, and a structural unit produced from p-hydroxybenzoic acid , Ethylene A liquid crystalline polyester comprising a structural unit generated from cole, a structural unit generated from 4,4′-dihydroxybiphenyl, a structural unit generated from an aliphatic dicarboxylic such as terephthalic acid and / or adipic acid, sebacic acid, and p-hydroxybenzoic acid From structural units generated from acids, structural units generated from ethylene glycol, structural units generated from aromatic dihydroxy compounds, and structural units generated from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid In addition to structural units selected from aromatic oxycarbonyl units, aromatic dioxy units, aromatic and / or aliphatic dicarbonyl units, alkylenedioxy units, etc. P-aminophen It is a polyesteramide that forms an anisotropic melt phase containing p-iminophenoxy units formed from enol.

  Of the liquid crystalline polymers described above, liquid crystalline polyester resins are preferred, and liquid crystalline polyesters composed of structural units generated from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid in terms of mechanical properties, moldability, and the like, Structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from 4,4′-dihydroxybiphenyl, generated from aliphatic dicarboxylic acids such as terephthalic acid and / or adipic acid and sebacic acid Liquid crystalline polyester composed of structural units, structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from aromatic dihydroxy compounds, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid Aromatic dicarboxylic acids such as A liquid crystalline polyester comprising a structural unit produced from the above is preferably used, and in particular, a liquid crystalline polyester comprising a structural unit produced from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, produced from p-hydroxybenzoic acid. Structural units, structural units generated from ethylene glycol, structural units generated from aromatic dihydroxy compounds, structural units generated from aromatic dicarboxylic acids such as terephthalic acid, structural units generated from p-hydroxybenzoic acid, A liquid crystalline polyester having a structural unit generated from ethylene glycol and a structural unit generated from an aromatic dicarboxylic acid such as terephthalic acid is particularly preferably used.

  Among the above liquid crystalline polyester resins, specific examples of preferred structures include liquid crystalline polyesters comprising the structural units of the following (I), (II), (III) and (IV), or (I), (III) And liquid crystalline polyester comprising the structural unit (IV).

  Particularly preferred are liquid crystalline polyesters comprising the structural units (I), (II), (III) and (IV).

（ただし式中のＲ１は

(However, R1 in the formula is

から選ばれた１種以上の基を示し、Ｒ２は

One or more groups selected from R2

から選ばれた１種以上の基を示す。ただし式中Ｘは水素原子または塩素原子を示す。）。

1 or more types of groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. ).

  The structural unit (I) is a structural unit formed from p-hydroxybenzoic acid, and the structural unit (II) is 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4. '-Dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4'- A structural unit generated from one or more aromatic dihydroxy compounds selected from dihydroxydiphenyl ether, a structural unit (III) is a structural unit generated from ethylene glycol, a structural unit (IV) is terephthalic acid, isophthalic acid, 4, 4 '-Diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bi One or more selected from su (phenoxy) ethane-4,4′-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylic acid and 4,4′-diphenyl ether dicarboxylic acid Each structural unit generated from an aromatic dicarboxylic acid is shown. Of these, R1 is

であり、Ｒ２が

And R2 is

であるものが特に好ましい。

Are particularly preferred.

  The liquid crystalline polyester resin that can be preferably used in the present invention, as described above, is a copolymer comprising the structural units (I), (III), (IV) and the structural units (I), (II), (III). , (IV) and one or more selected from the copolymer, and the copolymerization amount of the structural units (I), (II), (III) and (IV) is arbitrary. However, in order to exhibit the characteristics of the present invention, the following copolymerization amount is preferable.

  That is, in the case of a copolymer consisting of the structural units (I), (II), (III), (IV), the sum of the structural units (I) and (II) is the structural units (I), (II ) And (III) is preferably 30 to 95 mol%, more preferably 40 to 85 mol%. The structural unit (III) is preferably 70 to 5 mol%, more preferably 60 to 15 mol%, based on the total of the structural units (I), (II) and (III). The molar ratio [(I) / (II)] of structural unit (I) to (II) is preferably 75/25 to 95/5, more preferably 78/22 to 93/7. The structural unit (IV) is preferably substantially equimolar to the total of the structural units (II) and (III).

  On the other hand, when the structural unit (II) is not included, the structural unit (I) is preferably 40 to 90 mol% based on the total of the structural units (I) and (III) from the viewpoint of fluidity. It is particularly preferably 60 to 88 mol%, and the structural unit (IV) is preferably substantially equimolar to the structural unit (III).

  Here, “substantially equimolar” means that the unit constituting the polymer main chain excluding the terminal is equimolar, but the unit constituting the terminal is not necessarily equimolar.

  The liquid crystalline polyesteramide resin is preferably a polyesteramide that forms an anisotropic melt phase containing a p-iminophenoxy unit generated from p-aminophenol in addition to the structural units (I) to (IV).

  The liquid crystalline polyester resin and liquid crystalline polyester amide resin that can be preferably used include 3,3′-diphenyldicarboxylic acid and 2,2′-diphenyldicarboxylic acid in addition to the components constituting the structural units (I) to (IV). Aromatic dicarboxylic acids such as acids, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, 3,4'-dihydroxybiphenyl, Aromatic diols such as 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfide, 4,4′-dihydroxybenzophenone, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl Glycol, 1,4-cyclohexanedio Liquid, aliphatic, alicyclic diol such as 1,4-cyclohexanedimethanol, aromatic hydroxycarboxylic acid such as m-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and p-aminobenzoic acid The copolymer can be further copolymerized within a range not impairing the properties.

  The method for producing a liquid crystal polymer such as the above-mentioned liquid crystalline polyester resin or liquid crystalline polyester amide resin used in the present invention is not particularly limited and can be produced according to a known polycondensation method.

For example, in the production of the liquid crystalline polyester resin, the following production method is preferably exemplified.
(1) Diacylated products of p-acetoxybenzoic acid and aromatic dihydroxy compounds such as 4,4′-diacetoxybiphenyl and diacetoxybenzene, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester resin by deacetic acid condensation polymerization reaction.
(2) Reaction of aromatic dihydroxy compounds such as p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, and isophthalic acid with acetic anhydride. Then, after acylating a phenolic hydroxyl group, a method for producing a liquid crystalline polyester resin by a deacetic acid polycondensation reaction.
(3) Phenyl ester of p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone and diphenyl esters of aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid Of producing a liquid crystalline polyester resin by dephenol polycondensation reaction.
(4) After reacting p-hydroxybenzoic acid and aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid and the like with a predetermined amount of diphenyl carbonate to obtain diphenyl ester, 4,4 ′ A method for producing a liquid crystalline polyester resin by dephenol polycondensation reaction by adding an aromatic dihydroxy compound such as dihydroxybiphenyl or hydroquinone.
(5) Polyester polymer such as polyethylene terephthalate, oligomer or liquid crystal by the method of (1) or (2) in the presence of bis (β-hydroxyethyl) ester of aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate For producing a conductive polyester resin.

  The liquid crystalline polyester resin used in the present invention preferably has a melt viscosity of 0.5 to 80 Pa · s, more preferably 1 to 50 Pa · s, in order to suppress a decrease in fluidity when the filler is highly filled. Moreover, when trying to obtain a composition with more excellent fluidity, the melt viscosity is preferably 40 Pa · s or less.

  The melt viscosity is a value measured by a Koka flow tester under the condition of melting point (Tm) + 10 ° C. and shear rate of 1,000 (1 / second).

  Here, the melting point (Tm) is the Tm1 +20 after the observation of the endothermic peak temperature (Tm1) observed when the polymer having been polymerized is measured from room temperature under the temperature rising condition at 20 ° C./min in the differential calorimetry. This is the endothermic peak temperature (Tm2) observed when the temperature is kept at a temperature of 5 ° C. for 5 minutes, then cooled to room temperature under a temperature drop condition of 20 ° C./minute, and then measured again under a temperature rise condition of 20 ° C./minute. .

  Typical examples of polyarylene sulfide resins include polyphenylene sulfide (hereinafter sometimes abbreviated as PPS), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers thereof, block copolymers, and mixtures thereof. Among them, polyphenylene sulfide is particularly preferably used. Such polyphenylene sulfide is a polymer containing preferably 70 mol% or more, more preferably 90 mol% or more of a repeating unit represented by the following structural formula. When the repeating unit is 70 mol% or more, the heat resistance is high. It is preferable at an excellent point.

また、かかるポリフェニレンサルファイド樹脂は、その繰り返し単位の３０モル％以下を、下記の構造式を有する繰り返し単位などで構成することが可能であり、ランダム共重合体、ブロック共重合体であってもよく、それらの混合物であってもよい。

Further, such polyphenylene sulfide resin can be composed of 30 mol% or less of the repeating units with repeating units having the following structural formula, and may be a random copolymer or a block copolymer. Or a mixture thereof.

かかるポリアリーレンサルファイド樹脂は、通常公知の方法、つまり特公昭４５−３３６８号公報に記載される比較的分子量の小さな重合体を得る方法あるいは特公昭５２−１２２４０号公報や特開昭６１−７３３２号公報に記載される比較的分子量の大きな重合体を得る方法などによって製造することができる。

Such polyarylene sulfide resins are generally known methods, that is, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or JP-B-52-12240 and JP-A-61-7332. It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in the publication.

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

  Specific methods for crosslinking / high molecular weight polyarylene sulfide resin by heating include an atmosphere of an oxidizing gas such as air or oxygen, or a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. Below, a method of heating until a desired melt viscosity is obtained at a predetermined temperature in a heating container can be exemplified. In this case, the heat treatment temperature is preferably 150 to 280 ° C., more preferably 200 to 270 ° C., and the treatment time is preferably 0.5 to 100 hours, more preferably 2 A range of ˜50 hours is selected, but by controlling both, a target viscosity level can be obtained. Such a heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary or stirring blade. However, in the case of efficient and more uniform treatment, a heating apparatus with a rotary or stirring blade is used. Is more preferable.

As a specific method for heat-treating polyarylene sulfide resin under an inert gas atmosphere such as nitrogen or under reduced pressure, an inert gas atmosphere such as nitrogen or under reduced pressure (preferably 7,000 Nm ⁻² or less), Examples of the heat treatment method include a heat treatment temperature of 150 to 280 ° C, preferably 200 to 270 ° C, and a heating time of 0.5 to 100 hours, preferably 2 to 50 hours. Such a heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary or stirring blade. However, in the case of efficient and more uniform treatment, a heating apparatus with a rotary or stirring blade is used. Is more preferable.

  When the polyarylene sulfide resin is washed with an organic solvent, the organic solvent used for washing is not particularly limited as long as it does not have an action of decomposing the polyarylene sulfide resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, sulfoxide sulfone solvents such as dimethyl sulfoxide, dimethylsulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, dimethyl ether, dipropyl ether , Ether solvents such as tetrahydrofuran, halogen solvents such as chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane, tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, Alcohol / phenolic solvents such as cresol and polyethylene glycol, benzene and toluene Ene, and aromatic hydrocarbon solvents such as xylene may be used. Of these organic solvents, N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like are particularly preferably used. These organic solvents are used alone or in combination of two or more.

  As a specific method of washing with such an organic solvent, there is a method of immersing a polyarylene sulfide resin in an organic solvent, and it is possible to appropriately stir or heat as necessary. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning polyarylene sulfide resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. The polyarylene sulfide resin that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent. The water washing temperature is preferably 50 to 90 ° C, and preferably 60 to 80 ° C.

  The following method can be illustrated as a specific method when the polyarylene sulfide resin is treated with hot water. That is, in order to express a preferable chemical modification effect of the polyarylene sulfide resin by hot water washing, the water used is preferably distilled water or deionized water. The operation of the hot water treatment is usually performed by adding a predetermined amount of polyarylene sulfide resin to a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The ratio of the polyarylene sulfide resin and water should be higher, and is preferably used at a bath ratio of 200 g or less of polyarylene sulfide resin per liter of water.

  The following method can be illustrated as a specific method in the case of acid-treating polyarylene sulfide resin. That is, there is a method of immersing the polyarylene sulfide resin in an acid or an aqueous solution of the acid, and it is possible to appropriately stir or heat as necessary. The acid used is not particularly limited as long as it does not have an action of decomposing polyarylene sulfide resin, and includes aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, chloroacetic acid, dichloroacetic acid and the like. Halo-substituted aliphatic saturated carboxylic acids, aliphatic unsaturated monocarboxylic acids such as acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, fumaric acid, etc. Dicarboxylic acid and inorganic acidic compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid and silicic acid are used. Of these acids, acetic acid and hydrochloric acid are particularly preferably used. The polyarylene sulfide resin that has been subjected to acid treatment is preferably washed several times with water in order to remove the remaining acid or salt. The water washing temperature is preferably 50 to 90 ° C, and preferably 60 to 80 ° C. The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the preferable chemical modification effect of the polyarylene sulfide resin by acid treatment.

  The melt viscosity of the polyarylene sulfide resin used in the present invention is preferably 80 Pa · s or less, more preferably 50 Pa · s or less, more preferably 20 Pa · s or less under conditions of 300 ° C. and a shear rate of 1000 / sec. More preferably. Although there is no restriction | limiting in particular about the minimum of melt viscosity, It is preferable that it is 5 Pa.s or more. Two or more polyarylene sulfide resins having different melt viscosities may be used in combination.

  When the melt viscosity of the polyarylene sulfide resin exceeds the above range, it tends to be disadvantageous in terms of melt fluidity.

  The melt viscosity of the polyarylene sulfide resin can be measured using a capillograph (manufactured by Toyo Seiki Co., Ltd.) apparatus under conditions of a die length of 10 mm and a die hole diameter of 0.5 to 1.0 mm.

(B) used in the present invention aluminum nitride powder the particle surfaces were coated with silica, mixtures of solid phase reaction method, metallic aluminum powder and silica powder is heated by mixing aluminum nitride powder and silica in a non-oxidizing atmosphere the powder can be used both like those made reaction sintering method or we heated in a nitrogen atmosphere.

  Among these, those manufactured by a reactive sintering method in which a mixed powder of metal aluminum powder and silica powder is heated in a nitrogen atmosphere are preferable from the viewpoint of manufacturing cost.

  In addition, (B) the silica coating thickness of the aluminum nitride powder whose particle surface is coated with silica is that the average coating thickness is 0.5 to 50% of the particle diameter, and the particles are sufficiently coated; and From the viewpoint of making use of the thermal conductivity inherent to the aluminum nitride powder.

  Further, (B) the average particle diameter of the aluminum nitride powder whose particle surface is coated with silica is preferably 1 to 80 μm, more preferably 3 to 70 μm, and further preferably 6 to 60 μm. . When the average particle size is less than 1 μm, (B) in the production of aluminum nitride powder whose particle surface is coated with silica, the particles are likely to aggregate, and it is difficult to obtain sufficient moisture resistance due to the exposure of aluminum nitride due to peeling of the agglomerated part. Tend to be. If the average particle diameter exceeds 80 μm, the production cost is not sufficient.

  As for the shape, a fibrous shape, a crushed shape, a spherical shape, and a spherical shape are used, but a spherical shape is preferable from the viewpoint of fluidity at the time of molding.

  Such (B) aluminum nitride powder whose particle surface is coated with silica may be further subjected to surface treatment with a surface treatment agent such as titanate, aluminum and silane.

The blending amount of (A) the thermoplastic resin used in the present invention and (B) the aluminum nitride powder whose particle surface is coated with silica exhibits heat dissipation characteristics, and from the viewpoint of the balance between melt processability and mechanical characteristics. The total amount of (A) thermoplastic resin and (B) aluminum nitride powder whose particle surface is coated with silica is 100% by weight , ( A) 60 to 6% by weight of thermoplastic resin, and (B) particle surface with silica. coated aluminum nitride powder 40-94 wt% der Ri, (a) a thermoplastic resin 50-7% by weight, better good it is 50 to 93 wt% aluminum nitride powder coated with silica (B) the particle surface Yes.

  The resin composition comprising (A) a thermoplastic resin used in the present invention and (B) an aluminum nitride powder whose particle surface is coated with silica has a thermal conductivity measured by a laser flash method in order to exhibit heat dissipation characteristics. The rate is preferably 1 W / mK or more, more preferably 2 W / mK or more, and further preferably 3 W / mK or more. The upper limit is not particularly limited and is preferably high, but a practical effect can be achieved at 20 W / mK or less. As a method for obtaining such a resin composition, although it cannot be generally said depending on the type of thermoplastic resin to be used, in general, by increasing the content of (B) the aluminum nitride powder whose particle surface is coated with silica. The thermal conductivity of the composition tends to be improved.

  In the present invention, it is preferable to include a considerable amount of particles having a large particle diameter in order to exhibit fluidity at the time of molding with high efficiency. Specifically, (B) the particle diameter of the aluminum nitride powder having the particle surface coated with silica. It is preferable to control the distribution. Specifically, it is preferable that 8% by volume or more of the particle size distribution measured by a laser diffraction method is a particle of 30 μm or more, more preferably 15% by volume or more. Is preferably 30% by volume or more. About an upper limit, it is preferable that it is 70 volume% or less from the point of productivity and cost.

  The particle size distribution measurement by the laser light diffraction method is performed using a laser diffraction particle size distribution analyzer SALD-3100 manufactured by Shimadzu Corporation at a concentration of 100 ppm using water as a dispersion medium.

  The aluminum nitride powder having the particle size distribution (B) whose particle surface is coated with silica can be selected from commercially available aluminum nitride powders.

   The resin composition in the present invention further includes an inorganic filler, for example, a fibrous or non-fibrous (plate-like, scale-like, granular, indeterminate shape, crushed product, etc.) filler, as long as the effects of the present invention are not impaired. Specifically, for example, glass fiber, PAN-based or pitch-based carbon fiber, stainless steel fiber, metal fiber such as aluminum fiber or brass fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina as fibrous filler Fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, barium strontium titanate whisker, aluminum borate whisker, silicon nitride whisker, zinc oxide whisker, etc., glass fiber Or the type of carbon fiber There is no limitation in particular if those used for reinforcement of resin, such as a long fiber type and short fiber type, chopped strands, may be selected from such milled fiber. The filler may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, a thermosetting resin such as an epoxy resin, a silane compound, a titanate compound, or an aluminum compound.

  Zinc oxide whiskers, mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, calcium polyphosphate, graphite, metal powder, metal flakes as non-fibrous filler Examples thereof include metal ribbons, metal oxides (alumina, zinc oxide, titanium oxide, etc.), carbon powder, graphite, carbon flakes, scaly carbon, carbon nanotubes and the like. Moreover, silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, tin etc. can be illustrated as a specific example of the metal seed | species of metal powder, metal flakes, and a metal ribbon.

  Also possible for non-fibrous fillers are surface treatment agents such as thermoplastic resins such as ethylene / vinyl acetate copolymers, thermosetting resins such as epoxy resins, silane compounds, titanate compounds, and aluminum compounds. It may be processed.

  In addition, for example, high heat conductive fillers are preferably used for applications requiring high heat dissipation, and specifically, metal powder, metal flakes, metal ribbons, metal fibers, metal oxides (alumina, zinc oxide, etc.) , Carbon powder, graphite, PAN-based or pitch-based carbon fiber, carbon flake, scaly carbon, carbon nanotube, boron nitride, aluminum nitride, silicon nitride, silicon carbide and the like.

  Here, specific examples of the metal species of the metal powder, metal flake, and metal ribbon include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

Specific examples of the metal oxide include SnO ₂ (antimony dope), In ₂ O ₃ (antimony dope), ZnO (aluminum dope), and the like. These include titanate, aluminum and silane. The surface treatment may be performed with the surface treatment agent.

The carbon powder is classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disc black, and the like based on the raw materials and the production method. The carbon powder that can be used in the present invention is not particularly limited in terms of its raw material and production method, and among them, acetylene black and furnace black are particularly preferably used. Further, as the carbon powder, various carbon powders having different characteristics such as particle diameter, surface area, DBP (dibutyl phthalate) oil absorption and ash content are manufactured and commercially available. The carbon powder that can be used in the present invention is not particularly limited with respect to these properties, but from the viewpoint of the balance between strength and electrical conductivity, the average primary particle size is 500 nm or less, particularly 5 to 100 nm, It is preferable that it exists in the range of 10-70 nm. The surface area (BET method) is preferably in the range of 10 m ² / g or more, more preferably 30 m ² / g or more. Furthermore, the DBP oil supply amount is preferably 50 ml / 100 g or more, particularly preferably 100 ml / 100 g or more. Furthermore, it is preferable that the ash content is 0.5% or less, particularly 0.3% or less.

  Such carbon powder may be surface-treated with a surface treatment agent such as titanate, aluminum, and silane. Moreover, it is also possible to use what was granulated in order to improve melt-kneading workability | operativity with resin.

  The present invention further includes the following (C) fatty acid metal salt, ester-based compound, amide group-containing compound, epoxy-based compound, and phosphate ester from the viewpoint of imparting bondability at the filler interface and improving flowability during processing. It is preferable to add one or more additives.

  Specifically, sodium stearate, calcium stearate, magnesium stearate, potassium stearate, lithium stearate, zinc stearate, barium stearate, aluminum stearate, sodium montanate, calcium montanate, magnesium montanate, montanic acid Fatty acid metal salts such as potassium, lithium montanate, zinc montanate, barium montanate and aluminum montanate, and derivatives thereof, stearates such as methyl stearate and stearate stearate, myristate such as myristyl myristate , Methacrylate esters such as montanate ester and behenyl methacrylate, pentaerythritol monostearate, cetyl 2-ethylhexanoate, coconut fat Methyl, methyl laurate, isopropyl myristate, octyldodecyl myristate, butyl stearate, 2-ethylhexyl stearate, isotridecyl stearate, methyl caprate, methyl myristate, methyl oleate, octyl oleate, lauryl oleate, olein Monohydric alcohol esters of fatty acids such as oleyl acid, 2-ethylhexyl oleate, decyl oleate, octidodecyl oleate, isobutyl oleate and their derivatives, distearyl phthalate, distearyl trimellitic acid, dimethyl adipate, adipic acid Dioleyl, adipate, ditridecyl phthalate, diisobutyl adipate, diisodecyl adipate, dibutyl glycol adipate, 2-ethylhexyl phthalate Fatty acid esters of polybasic acids such as diisononyl phthalate, didecyl phthalate, tri-2-ethylhexyl trimellitic acid, triisodecyl trimellitic acid, stearic acid monoglyceride, palmitic acid / stearic acid monoglyceride, stearic acid mono / diglyceride, stearic acid / olein Fatty acid esters of glycerin such as acid mono monoglyceride, behenic acid monoglyceride and their derivatives, sorbitan tristearate, sorbitan monostearate, sorbitan monostearate, sorbitan distearate, sorbitan monopalmitate, sorbitan monostearate, Polyethylene glycol monostearate, polyethylene glycol distearate, polypropylene glycol monostearate, penta Erythritol monostearate, sorbitan monolaurate, sorbitan trioleate, sorbitan monooleate, sorbitan sesquioleate, sorbitan monolaurate, polyoxymethylene sorbitan monolaurate, polyoxymethylene sorbitan monopalinate, polyoxymethylene sorbitan monostearate , Polyoxymethylene sorbitan monooleate, polyoxymethylene sorbitan tetraoleate, polyethylene glycol, polyethylene glycol monolaurate, polyethylene glycol monooleate, polyoxyethylene bisphenol A laurate, pentaerythritol, pentaerythritol monooleate, etc. Fatty acid esters, and derivatives thereof, ethylene bisstearyl Amido, ethylenebisoleylamide, amide group-containing compounds such as stearyl erucamide, novolac phenyl type, bisphenol type monofunctional and polyfunctional epoxy compounds, aromatic phosphate esters such as triphenyl phosphate, aromatic condensed phosphate esters, etc. Of phosphoric acid esters.

  Especially about phosphate ester, it is chosen from the monoester, diester, triester, and tetraester of phosphoric acid, Preferably, what is represented by following formula (1) is mentioned.

まず前記式（１）で表されるリン酸エステルの構造について説明する。前記式（１）の式中ｎは０以上の整数であり、好ましくは０〜１０、特に好ましくは０〜５である。上限は分散性の点から４０以下が好ましい。

First, the structure of the phosphate ester represented by the formula (1) will be described. In the formula of the formula (1), n is an integer of 0 or more, preferably 0 to 10, particularly preferably 0 to 5. The upper limit is preferably 40 or less from the viewpoint of dispersibility.

  K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less, preferably k or m is an integer of 0 or more and 1 or less, particularly preferably k or m. Is 1 respectively.

In the formula (1), R ^{3 to} R ¹⁰ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, neopentyl, and tert-pentyl. Group, etc. are mentioned, but hydrogen, methyl group and ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different aromatic groups or aromatic groups substituted with an organic residue containing no halogen. Examples of the aromatic group include aromatic groups having a benzene skeleton, a naphthalene skeleton, an indene skeleton, and an anthracene skeleton, and among them, those having a benzene skeleton or a naphthalene skeleton are preferable. These may be substituted with a halogen-free organic residue (preferably an organic residue having 1 to 8 carbon atoms), and the number of substituents is not particularly limited, but may be 1 to 3. preferable. Specific examples include phenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, naphthyl groups, indenyl groups, anthryl groups and the like, but phenyl groups, tolyl groups, xylyl groups, cumenyl groups, A naphthyl group is preferable, and a phenyl group, a tolyl group, and a xylyl group are particularly preferable.

Y represents a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, and Ph represents a phenyl group.

  Specific examples of such phosphate esters are selected from Daihachi Chemical Co., Ltd. PX-200, PX-201, PX-130, CR-733S, TPP, CR-741, CR-747, TCP, TXP, CDP. One or more selected from the group consisting of PX-200, TPP, CR-733S, CR-741, and CR-747, particularly preferably PX-200. , CR-733S and CR-741 can be used, but PX-200 is most preferable.

  In this invention, any 1 type of phosphate ester, or a mixture of 2 or more types may be sufficient.

  (C) Fatty acid metal salt, ester compound, amide group-containing compound, epoxy compound, and the addition amount of one or more additives of phosphate ester are (A) thermoplastic resin and (B) particle surface is silica. The amount is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, and still more preferably 0.3 to 6 parts by weight with respect to 100 parts by weight of the total amount of the coated aluminum nitride powder.

  (C) When the amount of one or more additives of fatty acid metal salt, ester compound, amide group-containing compound, epoxy compound, and phosphate ester is too much more than the range of the present invention, While bleeding out, it causes peeling of the interface between the thermoplastic resin and the filler, and the mechanical properties tend to decrease.

  In the resin composition in the present invention, other components, such as antioxidants and heat stabilizers (hindered phenol-based, hydroquinone-based, phosphite-based and substituted products thereof, etc.), as long as the effects of the present invention are not impaired. Weathering agents (resorcinols, salicylates, benzotriazoles, benzophenones, hindered amines, etc.), mold release agents and lubricants (montanic acid and its metal salts, esters, half esters, stearyl alcohol, stearamide, various bisamides, bisamides Urea and polyethylene wax), pigments (such as cadmium sulfide, phthalocyanine and coloring carbon black), dyes (such as nigrosine), crystal nucleating agents, plasticizers (such as octyl p-oxybenzoate and N-butylbenzenesulfonamide), Antistatic agent ( Ruyl sulfate type anionic antistatic agent, quaternary ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate and betaine amphoteric antistatic agent), flame retardant (for example, , Red phosphorus), melamine cyanurate, magnesium hydroxide, aluminum hydroxide and other hydroxides, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resins or their brominated flame retardants And a combination of antimony trioxide and the like) and other polymers.

  The resin composition of the present invention is usually produced by a known method. For example, the component (A) and the component (B) are prepared by premixing other necessary additives or supplying them to an extruder or the like without being premixed and sufficiently melting and kneading them. In addition, when adding a fibrous filler as other necessary additive, in order to suppress breakage of the fiber of the fibrous filler, it is preferable to add the component (A) and the additive from the extruder, ) Method of supplying component and fibrous filler and other filler to extruder using side feeder, or (A) component and (B) component, other non-fibrous filler and additives from the origin of the extruder It is adjusted by feeding and supplying a fibrous filler to an extruder using a side feeder.

  Specifically, for example, a composition obtained by melt-kneading at 180 to 350 ° C. using a single-screw extruder, twin-screw or tri-screw extruder equipped with a “unimelt” (R) type screw, a kneader type kneader, or the like. It can be a thing.

  When a large amount of the component (B) and other fillers are added, for example, the addition amount exceeds (A) and (B), and the total amount of other fillers exceeds 100% by weight. As a method for obtaining a highly filled resin composition in which a filler is added, for example, as disclosed in JP-A-8-1663, a method of extruding by extruding the head of an extruder, or compression-molding a raw material to form a tablet A method is mentioned. In particular, the method of tableting by compressing the raw material is preferable from the viewpoint of the quality stability of the obtained composition. The compression molding for tableting is preferably performed in a solid state. The solid phase state means a state where the resin powder is not melted.

Specific tableting methods include, for example, (A) thermoplastic resin powder and (B) aluminum nitride powder whose particle surface is coated with silica, and other fillers such as Banbury mixer, kneader, roll, uniaxial or biaxial It can be obtained by uniformly blending in a solid phase state using an extruder or the like and tableting with a tableting machine or a molding machine having a compression roll. Also, (A) a thermoplastic resin, (B) an aluminum nitride powder whose particle surface is coated with silica, and other fillers are dry-blended in advance using a Banbury mixer, kneader, or roll, or do not dry-blend. Alternatively, it is also possible to melt and knead once using a twin-screw extruder, etc., cool and pulverize to form a powder, and then form tablets (tablets) with a tableting machine or a molding machine having a compression roll. In this case, the thermoplastic resin (A) used for melt kneading is not particularly limited as long as it can be melt kneaded, either in powder form or pellet form, but (B) aluminum nitride whose particle surface is coated with silica. From the viewpoint of reducing variation in characteristics due to poor dispersion of powder and other fillers, powder or a pulverized product is preferable. In addition, when a composition previously melt-kneaded using a single-screw or twin-screw extruder is made into powder, (B) aluminum nitride powder whose particle surface is coated with silica, and other fillers used in large amounts, However, in this case, as shown in JP-A-8-1663, the head portion of the extruder is opened. It is also possible to knead and extrude. (B) When the amount of the aluminum nitride powder and the filler whose particle surfaces are coated with silica is large, a flaky composition may be obtained. In the present invention, if necessary, a pellet or flake composition obtained by melt-kneading in advance by these methods is cooled and pulverized to form a powder and then tableted. In addition, these methods can be combined into tablets. That is, a raw material selected from the following (A) to (E) can be adjusted to have a desired content and tableted.
(A) (A) Thermoplastic resin, preferably powder (A) Thermoplastic resin (B) (B) Aluminum nitride powder whose particle surface is coated with silica, other filler (C) (A) or (B ) Powder of a composition obtained by melt-kneading a component essential to the component Among the above methods, the raw materials of (a) and (b) above and (c) A method in which a mixture obtained by uniformly blending raw materials in a solid phase is tableted by a tableting machine or a molding machine having a compression roll is preferred.

  As said (A) component, when it can obtain in powder form, such as a thermoplastic resin, it can be used. Further, the powder can be obtained by pulverizing the pellet at room temperature or by freeze pulverization. The freeze pulverization can be carried out by using a generally known hammer type pulverizer, cutter type pulverizer, or stone mill type pulverizer after being frozen with dry ice or liquid nitrogen. The thermoplastic resin powder used in the present invention includes particles obtained by measurement based on a laser diffraction particle size distribution measurement method from the viewpoint of making the composition uniform between the obtained tablets and improving the handleability of the obtained tablets. The number average particle diameter of the maximum major axis is preferably 1000 μm or less, more preferably 800 μm or less, and even more preferably 500 μm or less. In order to obtain a powder having such a particle size, the powder obtained by pulverization or the like may be appropriately sieved using a sieve having a desired size.

  As the tablet shape of the resin composition of the present invention, when considering shape retention during transportation and easy crushability during molding, for example, cylindrical shape, elliptical column shape, truncated cone shape, spherical shape, elliptical spherical shape, egg shape , Macek type, disc shape, cubic shape, prismatic shape. Among these, a cylindrical shape, an elliptical column shape, a truncated cone shape, a spherical shape, an elliptic spherical shape, an egg shape, and a Macek shape are preferable from the viewpoint of measurement stability during processing.

  Further, the tablet size of the tablet is preferably a bottom surface of 15 mm diameter or less × length of 20 mm or less, in particular, the maximum value of the bottom surface diameter or length (height) is preferably less than 15 mm, and the minimum value is 1 mm or more. It is preferable that As for the method of defining the maximum diameter and the minimum diameter with respect to those having a bottom surface that is not circular, when the maximum diameter of the circumscribed circle is specified, the maximum diameter is preferably less than 15 mm, 1 mm or more, more preferably 12 mm. Hereinafter, it is good that it is 1.5 mm or more.

  In addition, in order to keep the shape stable during transportation, the compression fracture strength value (crush strength value) when pressure is applied perpendicularly to the side of the tableting surface of the tablet or the compression surface of the compression roll, Preferably it is 5-100N, More preferably, it is 15-80N. As a method for obtaining a preferable crushing strength value, for example, it is most dependent on the raw material composition. (C) Addition of one or more of fatty acid metal salt, ester compound, amide group-containing compound, epoxy compound, and phosphate ester In the tableting process, by adding the agent, a method of uniformly supplying the raw material to the raw material supply pocket, a method of reducing the rotation speed of the compression roll and extending the pressurization time of the material on the compression roll, in the hopper A high tablet density and high crushing strength can be obtained by using a feed screw and effectively degassing and pre-compressing before roll compression with the screw. The crushing strength value is measured by placing a tablet on a strain gauge such as a load cell, and lowering the indenter at a low speed (preferably 0.1 to 2.0 mm / sec), and straining the tablet at the time of compressive fracture. A method of measuring the pressure indicated by the gauge can be used.

  By using such a method, it becomes possible to obtain (B) a resin composition in which the particle surface is coated with silica and highly filled with other fillers.

  The molding method for molding the resin composition of the present invention is a three-dimensional molded article, sheet, or the like by a normal molding method (injection molding, press molding, injection press molding, etc.), gas injection molding, musel molding method, or the like. Although it can be processed into a case (housing) or the like, when considering productivity, injection molding or injection press molding is preferably employed. Moreover, when it has a welding part, it is possible to use general welding methods, such as a hot plate, a vibration, an ultrasonic wave, and a laser. The molded product thus obtained has good fluidity at the time of molding processing, and the filling density of the obtained molded product is increased, so that it has excellent mechanical properties and thermal conductivity, and under use conditions under high temperature and high humidity. It is advantageous for high heat dissipation applications, metal replacement applications, ceramic replacement applications, electromagnetic wave shielding applications, high precision parts (low dimensional change), high conductivity applications, etc. Specifically, various cases, gear cases, LED lamp related parts, connectors, relay cases, switches, variable capacitor cases, optical pickup lens holders, optical pickup slide bases, various terminal boards, transformers, printed wiring boards, liquid crystal panels Frame, power module and its housing, plastic magnet, semiconductor, liquid crystal display component, projector, etc. Lamp cover, FDD carriage, FDD chassis, actuator, HDD parts such as chassis, electrical / electronic parts such as computer related parts, VTR parts, TV parts, iron, hair dryer, rice cooker parts, microwave oven parts, acoustics Parts, audio equipment parts such as audio / laser disc (registered trademark) / compact disc / digital video disc, lighting parts, refrigerator parts, air conditioner parts, office electrical product parts, office computer parts, telephones Parts, facsimile related parts, printer / copier related parts such as print heads and transfer rolls, cleaning jigs, motor parts, optical equipment such as microscopes, binoculars, cameras, watches, precision machine related parts; alternators Tami , Alternator connector, IC regulator, potentiometer base for light dimmer, motor core sealant, insulator member, power seat gear housing, thermostat base for air conditioner, air conditioner panel switch board, horn terminal, electrical component insulation plate, lamp housing, Automotive and vehicle-related parts such as ignition device cases, personal computer housings, mobile phone housings, and other fields such as chip antennas, installation antennas that require shielding properties such as electromagnetic waves, etc. , High dimensional accuracy, electromagnetic shielding properties, partition plates that require barrier properties such as gas and liquid, applications that require heat and electrical conductivity, outdoor installation equipment or building materials, especially heat dissipation ,Weight saving, It is useful for cases such as sockets, covers, and housings for electrical and electronic parts that require flexibility in shape and are eager to replace metals.

  Hereinafter, although an example is given and the present invention is explained in detail, the gist of the present invention is not limited only to the following examples.

Reference Example 1 Thermoplastic resin PPS (polyphenylene sulfide): M3910 (manufactured by Toray Industries, Inc .: linear type) (310 ° C., melt viscosity at a shear rate of 1000 sec ⁻¹ is 15 Pa · s), a sample mill (manufactured by Kyoritsu Riko Co., Ltd.) SK-M type) and classified by a sieve with 80 mesh pass and 150 mesh on to obtain a number average particle size of 150 μm.
PA6 (nylon 6): CM1001 (manufactured by Toray Industries, Inc.) is immersed in liquid nitrogen, pulverized with a sample mill (SK-M type, manufactured by Kyoritsu Riko Co., Ltd.), and classified with a sieve at 42 mesh pass and 80 mesh on. A number average particle diameter of 300 μm was obtained.
PBT (polybutylene terephthalate): 1100S (manufactured by Toray Industries, Inc.) is immersed in liquid nitrogen, pulverized with a sample mill (SK-M type manufactured by Kyoritsu Riko Co., Ltd.), and classified with a sieve at 42 mesh pass and 80 mesh on. And a number average particle diameter of 300 μm was obtained.
LCP (Liquid Crystalline Polyester): “Siberus” L201E (manufactured by Toray Industries, Inc.) is immersed in liquid nitrogen, pulverized with a sample mill (SK-M type, manufactured by Kyoritsu Riko Co., Ltd.), 80 mesh pass, 150 mesh on with a sieve And a number average particle diameter of 150 μm was obtained.

  In the above, the number average particle diameter was measured using a laser light diffraction particle size distribution analyzer SALD-3100 manufactured by Shimadzu Corporation.

Reference Example 2 Filler ALNS-1: FLE (manufactured by Toyo Aluminum Co., Ltd.) An average particle diameter of 17.4 μm, an accumulation ratio of 53.7% by volume of 30 μm or more, and an aluminum nitride powder whose particle surface is coated with silica.
ALNS-2: Aluminum nitride powder with FLC (manufactured by Toyo Aluminum Co., Ltd.) average particle size 6.6 μm, 30 μm or more, cumulative ratio 6.6 vol%, particle surface coated with silica.
ALN-1: FLG (manufactured by Toyo Aluminum Co., Ltd.) An average particle diameter of 17.7 μm, an accumulation ratio of 43.8% by volume of 30 μm or more, and an untreated aluminum nitride powder.
ALN-2: US (manufactured by Toyo Aluminum Co., Ltd.) Average particle diameter 1.6 μm, 30 μm or more, cumulative volume 0 volume%, particle surface untreated aluminum nitride powder.
AL-1: AL-32B (manufactured by Sumitomo Chemical Co., Ltd.) An average particle size of 2.9 μm, 30 μm or more, an accumulation ratio of 0% by volume or more, and an untreated alumina powder.

  In the above, the particle size distribution was measured using a laser diffraction type particle size distribution analyzer SALD-3100 manufactured by Shimadzu Corporation. The cumulative ratio of 30 μm or more shown in the table is calculated by calculating the volume percentage of particles having a particle diameter of 30 μm or more based on the cumulative particle size distribution curve measured by the laser light diffraction particle size distribution analyzer SALD-3100. It is. The average particle size is a particle size with a cumulative degree of 50% calculated from the cumulative particle size distribution curve.

Reference Example 3 Additive HWE: Montanate ester wax, “Lico Wax” E (manufactured by Clariant Japan).
PX: PX-200 (Powdered aromatic condensed phosphate ester, CAS No. 139189-30-3, manufactured by Daihachi Chemical Industry Co., Ltd.) Melting point 95 ° C. (uses 42 mesh pass through sieve).
EBS: Ethylene bisstearylamide, “Armo wax EBS powder” (manufactured by Lion Akzo).
BPD: Polyoxyethylene bisphenol A lauric acid ester, “Exepar” BP-DL (manufactured by Kao Corporation), viscosity at 25 ° C. 280 mPa · s.

  The viscosity is measured at 25 ° C. using a rotary viscometer (B-type viscometer).

Comparative Example 1 and Example 1
The thermoplastic resin of Reference Example 1 and the aluminum nitride powder whose particle surface shown in Reference Example 2 was coated with silica were blended in the amount shown in Table 1 with a Henschel mixer, and PCM30 with a 3-hole strand die head (biaxial extruder; Ikekai (Made by Steel) and melt kneaded at the resin temperatures shown in Table 1 to obtain pellets. Subsequently, after drying with a hot air dryer at 140 ° C. for 3 hours, the following evaluation was performed.

Examples 2-10
The thermoplastic resin of Reference Example 1, the aluminum nitride powder whose particle surface shown in Reference Example 2 was coated with silica, alumina powder, and a predetermined amount of the additive of Reference Example 3 were blended in the amount shown in Table 1 with a Henschel mixer, and the automatic A 7 mm diameter × 3 mm long cylindrical tablet (tablet) (maximum value 7 mm, minimum value 3 mm) was obtained by tableting at room temperature using a rotary tableting machine manufactured by Tsukishima Machine equipped with a raw material supply feeder. Subsequently, each tablet obtained was vacuum-dried in an 80 ° C. vacuum dryer for 5 hours, and then the following evaluation was performed.

Comparative Example 2
The thermoplastic resin of Reference Example 1, the aluminum nitride powder whose particle surface shown in Reference Example 2 was coated with silica, and the aluminum nitride powder were blended in the amount shown in Table 1 with a Henschel mixer, and PCM30 with a 3-hole strand die head (biaxial) Melting and kneading were performed at the resin temperature shown in Table 1 using an extruder (manufactured by Ikekai Steel Co., Ltd.) to obtain pellets. Subsequently, after drying with a hot air dryer at 140 ° C. for 3 hours, the following evaluation was performed.

Comparative Examples 3-8
The thermoplastic resin of Reference Example 1, the aluminum nitride powder coated with silica on the particle surface shown in Reference Example 2, the aluminum nitride powder, the alumina powder and the additive of Reference Example 3 in the amounts shown in Table 1 using a Henschel mixer. Blending was carried out at room temperature using a Tsukishima machine rotary tableting machine equipped with an automatic raw material supply feeder to obtain a cylindrical tablet (tablet) 7 mm in diameter x 3 mm long (maximum value 7 mm, minimum value 3 mm). . Subsequently, each tablet obtained was vacuum-dried in an 80 ° C. vacuum dryer for 5 hours, and then the following evaluation was performed.

(2) Molded product filling rate Using a UH1000 (80t) injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.), a square-shaped product (50 mm x 50 mm x 3 mm thick) under the temperature conditions of the resin temperature and mold temperature shown in Table 1 ( Film gate) was measured, the density of the obtained molded product was measured, and the filling rate was calculated by the following formula (a) (the higher the molded product filling rate, the better the filling property).
Molded product filling rate (%) = (Molded product density / theoretical density) × 100. . (A)
(3) Bending strength Using a UH1000 (80t) injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.), a corner forming shape of 100 × 100 × 3 mm thickness (film gate) under the temperature conditions of the resin temperature and mold temperature shown in Table 1 The product was molded at a minimum pressure of +5 MPa, two sheets were cut from the center in the flow direction to a width of 12.7 mm, and the bending strength was measured according to ASTM D790.

(4) High pressure and high humidity heat (PCT; pressure cooker test) post-bending strength Using a UH1000 (80t) injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.), the resin temperature and mold temperature shown in Table 1 are 100. A test piece obtained by forming a square-shaped product of × 100 × 3 mm thickness (film gate) at a minimum pressure of +5 MPa and cutting two pieces from the center in the flow direction to a width of 12.7 mm using TPC-411 (manufactured by Tabay Espec) PCT treatment was performed at 121 ° C. × 2 atm × 100% RH for 50 hours, and bending strength was measured in accordance with ASTM D790.

(5) Strength retention (Bending strength retention after PCT)
The strength retention was calculated from the bending strength and post-PCT bending strength obtained in the above (3) and (4) by the following formula (b) (if the retention is 80% or more, the practicality is excellent). ).
Strength retention (%) = (Bending strength after PCT / Bending strength) × 100. . (B)
(6) Thermal conductivity Using a UH1000 (80t) injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.), a square-shaped product (50 mm x 50 mm x 3 mm thick) under the temperature conditions of the resin temperature and mold temperature shown in Table 1 Film Flash) Constant laser measuring instrument (LF / TCM-FA8510B manufactured by Rigaku Corporation) using a test piece with a thickness of 2 mm by cutting both surfaces of this molded product to a depth of 0.5 mm Was used to measure the thermal conductivity.

(7) Thermal conductivity after high-pressure and high-humidity heat (PCT; pressure cooker test) Using a UH1000 (80t) injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.), under the temperature conditions of the resin temperature and mold temperature shown in Table 1, A square-shaped product (film gate) of 50 mm × 50 mm × thickness 3 mm was molded, and both surfaces of this molded product were cut to a depth of 0.5 mm, and a test piece having a thickness of 2 mm was TPC-411 (manufactured by Tabay Espec) Was subjected to PCT treatment at 121 ° C. × 2 atm × 100% RH for 50 hours, and the thermal conductivity was measured with a laser flash method constant measuring apparatus (LF / TCM-FA8510B manufactured by Rigaku Corporation) using the test piece.

(8) Thermal conductivity retention rate (post-PCT thermal conductivity retention rate)
The thermal conductivity retention after PCT was calculated from the following formula (c) for the values of thermal conductivity and post-PCT thermal conductivity obtained in (6) and (7) above (if the retention is 80% or more) Is highly practical)
Thermal conductivity retention (%) = (thermal conductivity after PCT / thermal conductivity) × 100. . (C)
As is apparent from the results in Table 1, according to the resin composition of the present invention, the fluidity at the time of molding was excellent, and the obtained molded product was excellent in thermal conductivity and mechanical strength, and was a problem in the past. It can be seen that a material having significantly improved characteristics deterioration can be obtained even when used in a humid heat atmosphere. Moreover, since it is excellent in moldability (fluidity) and can be injection-molded, it is possible to develop the electrical and electronic components that require moisture and heat resistance to cases, covers, and sockets.

Claims (6)

(A) 60 to 6% by weight of a thermoplastic resin that is at least one selected from a polyamide resin, a non-liquid crystal polyester resin, a liquid crystal polymer, and a polyarylene sulfide resin ;
(B) particles obtained by a solid phase reaction method in which aluminum nitride powder and silica are mixed and heated in a non-oxidizing atmosphere, or a reaction sintering method in which a mixed powder of metal aluminum powder and silica powder is heated in a nitrogen atmosphere A resin composition comprising 40 to 94% by weight of an aluminum nitride powder whose surface is coated with silica. 2. The resin composition according to claim 1, wherein the molded product obtained by melt-molding the resin composition has a thermal conductivity of 1 W / mK or more measured by a laser flash method. (B) according to claim 1 or 2 resin composition according least 8% by volume of the particles size distribution of the aluminum nitride powder the particle surfaces were coated with silica characterized in that it is a more particles 30 [mu] m. Further, (C) one or more of fatty acid metal salts, ester compounds, amide group-containing compounds, epoxy compounds, and phosphate esters are added in an amount of 0.5 to 100 parts by weight of the total of (A) and (B). The resin composition according to any one of claims 1 to 3, wherein 10 to 10 parts by weight are added. Claim 1 molded article obtained by injection-molding the resin composition according to any one of the four. 6. The molded product according to claim 5 , wherein the molded product is a case of an electric / electronic component.