WO2010084845A1 - Resin composition and molded article comprising the same - Google Patents

Abstract

Provided is a resin composition comprising a thermoplastic resin (A), a filler (B), and a predetermined amount of a melt viscosity reducing agent (C). The melt viscosity reducing agent (C) used in a predetermined amount is either the following (a) or (b): (a) The melt viscosity reducing agent (C) is a polyfunctional allyl compound (C1), and the content of polyfunctional allyl compound (C1) with respect to a total of 100 parts by mass of the thermoplastic resin (A) and filler (B) is 3 to 20 parts by mass, or (b) the melt viscosity reducing agent (C) is a dimer acid-based thermoplastic resin (C2), and the content of the dimer acid-based thermoplastic resin (C2) with respect to a total of 100 parts by volume of the thermoplastic resin (A) and filler (B) is 10 to 45 parts by volume.

Description

Resin composition and molded body comprising the same

The present invention relates to a resin composition and a molded body comprising the same, and more particularly to a resin composition having melt fluidity during molding and a molded body comprising the same.

Known thermoplastic resins used as raw materials for molding include polypropylene (PP), ABS, polyamide (PA6, PA66, etc.), polyester (PET, PBT, etc.), polycarbonate (PC), liquid crystal polyester (LCP), polyphenylene sulfide. (PPS). These resins are widely used in fields such as various electronic devices, electronic parts, and machine parts. These thermoplastic resins are improved in strength and heat resistance by blending reinforcing fillers such as talc and glass fiber, and various functions can be achieved by blending fillers having specific functions. Has been granted.

Amorphous thermoplastic resins such as polycarbonate resin and ABS resin, which are excellent in surface appearance and low warpage of molded products, have been used in the casings of portable electronic devices such as PDAs, mobile phones, and personal computers. In recent years, as electronic devices have become smaller and lighter, casings are also required to be thin molded products. For that purpose, talc, glass fiber, and the like have been blended as reinforcing materials in the aforementioned polycarbonate resin and ABS resin. However, in these reinforced resin compositions, the strength of the casing and the like is improved as the amount of the reinforcing material is increased, but the fluidity of the resin is lowered. For this reason, it is particularly difficult to form a thin and complex product such as a housing.

On the other hand, in recent electronic devices, with higher performance, smaller size and lighter weight, heat countermeasures that effectively dissipate heat generated in various electronic components to the outside have become very important issues. . For this reason, there is a growing demand for improvement in heat dissipation of resin molding materials that are constituent materials of electronic devices. As a well-known means to improve the heat dissipation of resin molding materials, fillers with high thermal conductivity (boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, silicon carbide, graphite, etc.) are included. There is a known technique to do this. For example, JP62-1331033A has a thermally conductive resin molded product in which a thermoplastic resin is filled with graphite powder, and JP2001-151905A has a resin heat sink in which polyphenylene sulfide resin is filled with magnesium oxide or aluminum oxide. Are listed. However, in order to obtain a highly heat conductive resin composition, it is necessary to add a large amount of filler. As a result, there is a problem in that the moldability is remarkably lowered and the use of the resin composition is limited.

It is known to add a plasticizer as a technique for improving the processability of a resin composition to which a large amount of filler is added in this way. However, when a plasticizer is added, there is a problem that the strength of the resin composition is remarkably lowered and the plasticizer volatilizes during melt kneading. There is also a problem that the plasticizer bleeds out.

Therefore, an object of the present invention is to provide a resin composition excellent in melt fluidity at the time of processing such as injection molding and a molded body comprising the same.

The gist of the present invention is as follows.

(1) A thermoplastic resin (A), a filler (B), and a predetermined amount of melt viscosity reducing agent (C), wherein the predetermined amount of melt viscosity reducing agent (C) includes: (B) and the resin composition characterized by the above-mentioned.

(A) The melt viscosity reducing agent (C) is a polyfunctional allyl compound (C1), and the polyfunctional allyl compound (C1) with respect to 100 parts by mass in total of the thermoplastic resin (A) and the filler (B). The content is 3 to 20 parts by mass.

(B) The melt viscosity reducing agent (C) is a dimer acid-based thermoplastic resin (C2), and the dimer acid-based thermoplastic resin (C2) for a total of 100 parts by volume of the thermoplastic resin (A) and the filler (B). ) Content is 10 to 45 parts by volume.

(2) The resin composition according to (1), wherein the polyfunctional allyl compound (C1) is a compound having isocyanurate in the skeleton.

(3) The polyfunctional allyl compound (C1) is obtained by reacting the primary amine compound (D) represented by the following formula (i) with the polyfunctional compound (E) having an allyl group and a glycidyl group. The resin composition according to (1), which is an allyl compound.

R- (NH ₂ ) _n (i)
Here, n = 1 to 4 and R represents an aromatic or aliphatic 1 to 4 substituted residue.

(4) The resin composition according to (3), wherein the polyfunctional compound (E) having an allyl group and a glycidyl group is a compound having an isocyanurate in the skeleton.

(5) The resin composition according to (2) or (4), wherein the compound having isocyanurate in the skeleton is monoglycidyl diallyl isocyanurate.

(6) The resin composition according to (1), wherein the dimer acid-based thermoplastic resin (C2) is a polyamide resin and / or a polyester resin.

(7) Any of (1) to (6), wherein the filler (B) is a thermally conductive filler (B1) having a thermal conductivity of 10 W / (m · K) or more. Resin composition.

(8) The resin composition according to (7), wherein the volume ratio (A / B1) between the thermoplastic resin (A) and the thermally conductive filler (B1) is 20/80 to 95/5 .

(9) The thermally conductive filler (B1) is composed of flaky graphite having an average particle diameter of 1 to 300 μm, graphitized carbon fiber having an average fiber diameter of 1 to 30 μm and an average fiber length of 1 to 20 mm, and a hexagonal crystal structure. Scaly boron nitride having an average particle size of 1 to 200 μm, aluminum oxide having an average particle size of 0.5 to 150 μm, magnesium oxide having an average particle size of 0.5 to 150 μm, and an average particle size of 0.5 to 150 μm The resin composition according to (7) or (8), which is at least one selected from magnesium carbonate and zinc oxide having an average particle diameter of 0.5 to 150 μm.

(10) The resin composition according to any one of (1) to (9), wherein the thermoplastic resin (A) is a polyamide resin.

(11) A molded product obtained by molding any of the resin compositions (1) to (10) above.

(12) A molded article obtained by molding one of the resin compositions (1) to (10) above and then irradiating with radiation.

According to the present invention, since it contains a predetermined amount of melt viscosity reducing agent (C), it is possible to provide a resin composition having excellent melt fluidity during processing and a molded product obtained thereby.

In particular, when the melt viscosity reducing agent (C) is a polyfunctional allyl compound (C1), the polyfunctional allyl compound (C1) has a large number of allyl groups in one molecule. In order to reinforce the mechanical properties of the molded product by crosslinking the allyl group with the resin, a resin composition having excellent mechanical properties and excellent melt fluidity during processing, and a molded product comprising the same Obtainable.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin (A) that can be used in the present invention is not particularly limited, but ethylene-α-olefin copolymers such as polyethylene, polypropylene, and ethylene-propylene copolymers, polymethylpentene, Polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetal, fluororesin (polyvinylidene fluoride, polytetrafluoroethylene, etc.), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate , Polylactic acid, polystyrene, polyacrylonitrile, styrene-acrylonitrile copolymer, ABS resin, polyphenylene ether (PPE), modified PPE, polyamide, polyimide, polyamideimide, polyether Ruimido, polymethacrylic acid esters of polymethyl methacrylate, polyacrylic acids, polycarbonate, polyarylate, polyphenylene sulfide, polysulfone, polyether sulfone, polyether nitrile, polyether ketone, polyketone, liquid crystal polymers, and the like. Of these, polyamide is preferable in terms of moldability, chemical resistance, and economy, and liquid crystal polymer is also preferable in terms of moldability, heat resistance, and mechanical strength.

Examples of the polyamide resin that can be used in the present invention include homopolyamide and copolyamide obtained by polymerization of lactam or aminocarboxylic acid, or polycondensation of diamine and carboxylic acid, and mixtures thereof.

Preferred examples of the polyamide resin include polycapramide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polycoupleramide / polyhexamethylene adipamide copolymer (nylon 6/66) , Polyundecamide (nylon 11), polycapramide / polyundecamide copolymer (nylon 6/11), polydodecamide (nylon 12), polycoupler / polydodecamide copolymer (nylon 6/12), polyhexamethylene sebamide (nylon 610) , Polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (nylon 116), polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalamide (Niro) 6T), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polycapramide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polycoupleramide / polyhexamethylene isophthalamide copolymer (nylon 6 / 6I) ), Polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polytrimethylhexamethylene terephthalamide (nylon) TMDT), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl-4-aminocyclohexyl) Tandodekamido (nylon dimethyl PACM12), poly-m-xylylene adipamide (nylon MXD6), polyundecamethylene terephthalamide (nylon 11T), and mixtures thereof or copolymers thereof. Of these, nylon 6 and nylon 66 are preferable in terms of moldability and economy.

The liquid crystal polymer that can be used in the present invention refers to a melt-processable polymer having a property capable of forming an optically anisotropic melt phase. Such a liquid crystal polymer has a property that polymer molecular chains take a regular parallel arrangement by receiving a shear stress in a molten state. Such polymer molecules are generally elongated, flat, fairly rigid along the long axis of the molecule, and have a plurality of chain extension bonds that are usually either coaxial or parallel. Examples include wholly aromatic or semi-aromatic polyesters, polyester imides, polyester amides, and mixtures thereof.

Preferred examples of the liquid crystal polymer include liquid crystal polyester, liquid crystal polyester amide, liquid crystal polyester carbonate, and liquid crystal polyester elastomer. Among these, liquid crystalline polyester is preferable in terms of moldability.

Examples of the liquid crystal polyester include a polyester that forms an anisotropic melt phase composed of a structural unit selected from an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic dicarbonyl unit, an ethylenedioxy unit, and the like.

The resin composition of the present invention contains a filler (B). Although it does not specifically limit as a filler (B) used by this invention, The thing used for the purpose of improving a mechanical property, a thermal property, etc., electroconductivity, thermal conductivity, magnetism, piezoelectricity, electromagnetic wave absorption As typical examples, those used for the purpose of imparting functions such as flame retardancy and ultraviolet absorption can be given. Examples of the form of the filler (B) include a spherical shape, a powder shape, a fiber shape, a needle shape, a scale shape, a scale shape, a whisker shape, a microcoil shape, and a nanotube shape.

Specific examples of the filler (B) include acetylene black, ketjen black, carbon nanotube, carbon nanofiber, metal powder (silver, copper, aluminum, titanium, nickel, tin, iron, stainless steel, etc.), conductive zinc oxide , Tin oxide, indium oxide, various ferrites, magnetic iron oxide, aluminum oxide, magnesium oxide, zinc oxide, magnesium carbonate, silicon carbide, aluminum nitride, boron nitride, silicon nitride, carbon, graphite, barium titanate, zirconate titanate Lead, potassium titanate, zonotlite, mica, talc, montmorillonite, hydrotalcite, calcium carbonate, zinc carbonate, wollastonite, barium sulfate, molybdenum disulfide, ethylene fluoride (for example, Teflon (registered trademark) powder, silica, Glass beads, Las balloon, titanium oxide, aluminum hydroxide, magnesium hydroxide, antimony trioxide, boric acid, zinc borate, cerium oxide, calcium oxide, silica gel, sepiolite, activated carbon, zeolite, tungsten, zirconium oxide, cellulose fine particles, wood flour, Okara, fir shell, glass fiber, carbon fiber, graphitized carbon fiber, aramid fiber, metal fiber, stainless steel fiber, silica fiber, silica / alumina fiber, zirconia fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, kenaf And natural fibers such as hemp.

In the resin composition of the present invention, the volume ratio (A / B) between the thermoplastic resin (A) and the filler (B) [including a heat conductive filler (B1) described later] is 20/80 to 95. / 5 is preferable, 30/70 to 90/10 is more preferable, and 30/70 to 60/40 is particularly preferable. When the blending amount of the filler (B) is less than 5% by volume, the effect of blending the filler may not be sufficiently obtained. When the blending amount exceeds 80% by volume, the fluidity is remarkably lowered during molding. In some cases, the load of the engine becomes too high and the operability is lowered.

In the present invention, in order to impart thermal conductivity to the resin composition, a thermally conductive filler (B1) having a thermal conductivity of 10 W / (m · K) or more is used as the filler (B). Can do. As the heat conductive filler (B1), either a conductive filler or an insulating filler can be used. The thermal conductivity of the heat conductive filler (B1) can be measured using the sintered product. Specific examples of the thermally conductive filler (B1) (representing a representative value of thermal conductivity [unit: W / (m · K)] in parentheses), aluminum oxide (36), magnesium oxide (60 ), Zinc oxide (25), magnesium carbonate (15), silicon carbide (160), aluminum nitride (170), boron nitride (210), silicon nitride (40), carbon (10 to several hundreds), graphite (10 to Hundreds of inorganic fillers, silver (427), copper (398), aluminum (237), titanium (22), nickel (90), tin (68), iron (84), stainless steel (15), etc. Metal-based fillers. These can be used alone or in combination of two or more.

The average particle diameter of the heat conductive filler (B1) is preferably 0.5 to 300 μm, more preferably 1 to 150 μm, excluding specific particles described later. If the average particle size is less than 0.5 μm, an agglomerate is likely to occur due to poor dispersion, and a uniform molded product cannot be obtained, resulting in a decrease in mechanical properties and a variation in thermal conductivity. If the average particle size exceeds 300 μm, it may be difficult to fill the resin in a high concentration or the surface of the molded product may become rough.

Among the fillers exemplified above, in the present invention, graphite and boron nitride are used as the thermally conductive filler (B1) because of its high thermal conductivity efficiency when blended into the thermoplastic resin (A). It is preferable. In view of economy, it is preferable to use aluminum oxide, magnesium oxide, magnesium carbonate, or zinc oxide.

Examples of the form of the graphite filler that can be used in the present invention include a spherical shape, a powder shape, a fiber shape, a needle shape, a scale shape, a whisker shape, a microcoil shape, and a nanotube shape. Among these, scaly graphite and graphitized carbon fiber are particularly preferable because they can increase the heat conduction efficiency when blended with the thermoplastic resin (A).

The average particle size of the flake graphite is preferably 1 to 300 μm, and more preferably 5 to 150 μm. If the average particle size is less than 1 μm, agglomerates are likely to occur due to poor dispersion, and thus a uniform molded product cannot be obtained, and the mechanical properties may be lowered or the thermal conductivity may be varied. When the average particle size exceeds 300 μm, it becomes difficult to fill the resin composition at a high concentration, and the surface of the molded product may become rough.

The graphitized carbon fiber is preferably pitch-based carbon fiber, which is described in, for example, JP2003-49327A. Among them, graphite is obtained by firing at a high temperature of 1000 to 3000 ° C. using mesophase pitch as a raw material. Pitch-based carbon fibers with improved chemical conversion are preferred. The degree of graphitization is not particularly limited, but the thermal conductivity in the length direction increases as the graphite fiber is approached. In the present invention, the thermal conductivity in the length direction of the graphitized carbon fiber is usually 100 W / (m · K) or more, preferably 500 W / (m · K) or more.

The average fiber diameter of the graphitized carbon fiber is preferably 1 to 30 μm, more preferably 5 to 20 μm. When the average fiber diameter is less than 1 μm, sufficient thermal conductivity cannot be obtained, and when the average fiber diameter exceeds 30 μm, moldability and the like may be deteriorated.

The average fiber length of the graphitized carbon fiber is preferably 1 to 20 mm, and more preferably 3 to 15 mm. If the average fiber length is less than 1 mm, sufficient thermal conductivity cannot be obtained. The longer the average fiber length, the higher the thermal conductivity, the higher the bending strength and the bending elastic modulus. However, when the average fiber length exceeds 20 mm, the fluidity is greatly lowered, which is not preferable in terms of moldability.

Examples of commercially available products of graphitized carbon fiber include the product name “GRANOC” manufactured by Nippon Graphite Fiber Co., Ltd., and the product name “Dialead” manufactured by Mitsubishi Chemical Corporation.

Examples of the form of boron nitride that can be used in the present invention include a spherical shape, a powdery shape, a fibrous shape, a needle shape, a scale shape, a whisker shape, a microcoil shape, and a nanotube shape. Since it becomes easy to orient in a surface direction when it is set as a molded body, and as a result, heat conductivity can be raised, it is preferable that it is scaly. By containing boron nitride, thermal conductivity can be improved without reducing the insulating properties of the resin composition.

The average particle size of boron nitride is preferably 1 to 200 μm, and more preferably 5 to 100 μm. When the average particle size is less than 1 μm, agglomerates are likely to occur due to poor dispersion, and therefore, a uniform molded product cannot be obtained, and mechanical properties may be deteriorated or thermal conductivity may be varied. When the average particle diameter exceeds 200 μm, it becomes difficult to fill the resin composition at a high concentration, and the surface of the molded product may become rough.

The crystal system of boron nitride is not particularly limited. Boron nitride having any crystal structure such as hexagonal system, cubic system, and the like is applicable. Of these, boron nitride having a hexagonal crystal structure is preferable because of its high thermal conductivity.

Examples of the form of aluminum oxide, magnesium oxide, magnesium carbonate, and zinc oxide that can be used in the present invention include a spherical shape, a fiber shape, a spindle shape, a rod shape, a needle shape, a cylindrical shape, and a columnar shape. Since it can suppress the fall of the fluidity | liquidity of resin when it mix | blends with a thermoplastic resin (A), it is preferable that it is spherical. By containing aluminum oxide, magnesium oxide, and magnesium carbonate, thermal conductivity can be improved without reducing the insulating properties of the resin composition.

The average particle diameter of aluminum oxide, magnesium oxide, magnesium carbonate, and zinc oxide is preferably 0.5 to 150 μm, and more preferably 1 to 100 μm. If the average particle size is less than 0.5 μm, agglomerates are likely to occur due to poor dispersion, and therefore, a uniform molded product cannot be obtained, and mechanical properties may deteriorate or thermal conductivity may vary. When the average particle diameter exceeds 150 μm, it becomes difficult to fill the resin composition at a high concentration, and the surface of the molded product may become rough.

The filler (B) used in the present invention may be subjected to a surface treatment with a coupling agent in order to improve adhesion to the thermoplastic resin (A). Examples of coupling agents include silane coupling agents and titanium coupling agents such as γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N- Aminosilane coupling agents such as β- (aminoethyl) -γ-aminopropyldimethoxymethylsilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylethoxysilane, β- (3,4-epoxy Mention may be made of epoxy silane coupling agents such as (cyclohexyl) ethyltrimethoxysilane, and titanium coupling agents such as isopropyl tristearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate, etc. You can. These may be used alone or in combination.

The resin composition of the present invention contains a predetermined amount of fluidity improver (C). The fluidity improver (C) used in the present invention is either a polyfunctional allyl compound (C1) or a dimer acid-based thermoplastic resin (C2).

The polyfunctional allyl compound (C1) is not particularly limited, but is required to be liquid at the melt processing temperature of the resin composition. Moreover, since the polyfunctional allyl compound (C1) can reduce the melt viscosity of the added resin, it will effectively act as a plasticizer.

Specific examples of the polyfunctional allyl compound (C1) include triallyl isocyanurate, monoglycidyl diallyl isocyanurate, diglycidyl monoallyl isocyanurate, trimethallyl isocyanurate, monoglycidyl dimethallyl isocyanurate, diglycidyl monometa. Allyl isocyanurate, triallyl cyanurate, monoglycidyl diallyl cyanurate, diglycidyl monoallyl cyanurate, trimethallyl cyanurate, monoglycidyl dimethallyl cyanurate, diglycidyl monomethallyl cyanurate, allyl glycidyl amine, diallyl mono Glycidylamine, monoallyldiglycidylamine, monoglycidyldimethallylamine, diglycidylmonomethallylamine, glycidylacrylic chlorate, Allyl glycidyl adipate, allyl glycidyl carbonate, allyl glycidyl dimethyl ammonium chloride, allyl glycidyl fumarate, allyl glycidyl isophthalate, allyl glycidyl malonate, allyl glycidyl oxalate, allyl glycidyl phthalate, allyl glycidyl propyl isocyanurate, allyl glycidyl sebacate, allyl Examples thereof include glycidyl succinate, allyl glycidyl terephthalate, allyl glycidyl tartrate, and glycidyl methyl allyl phthalate. Of these compounds, compounds having an isocyanurate in the skeleton are preferable, and triallyl isocyanurate and monoglycidyl diallyl isocyanurate are particularly preferable from the viewpoints of handleability and economy.

Moreover, as a polyfunctional allyl compound (C1), in addition to the above compound, a primary amine compound (D) represented by the following formula (i), a polyfunctional compound (E) having an allyl group and a glycidyl group, An allyl compound obtained by the above reaction can be used.

R- (NH ₂ ) _n (i)
Here, n = 1 to 4 and R represents an aromatic or aliphatic 1 to 4 substituted residue.

The primary amine compound (D) represented by the formula (i) is preferably a diamine having n = 2. Specific examples of diamines with n = 2 include ethylenediamine, hexamethylenediamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 1,3-bis (aminomethyl) Cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 4,4'-diaminodicyclohexylpropane, bis (4-aminocyclohexyl) sulfone, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl -4,4'-diaminodicyclohexane, 2,2'-bis (trifluoromethyl) -4,4'-diaminodicyclohexane, 2,2'-bis (trichloromethyl) -4,4'-diaminodicyclohexane 2,2′-bis (tribromomethyl) -4,4′-diaminodicyclohexane, 2,2′-difluoro-4,4′-diaminodicyclohexane, 2,2′-dichloro-4,4′-diaminodicyclohexane, 2,2′-dibromo-4,4′-diaminodicyclohexane, 4, 4'-diaminodicyclohexane, 2,2-bis (4-aminocyclohexyl) -1,1,1,3,3,3-hexafluoropropane, 2,3-diaminobicyclo [2.2.1] Heptane, 2,5-diaminobicyclo [2.2.1] heptane, 2,6-diaminobicyclo [2.2.1] heptane, 2,7-diaminobicyclo [2.2.1] heptane, 2,5 -Bis (aminomethyl) -bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) -bicyclo [2.2.1] heptane, 2,3-bis (aminomethyl) -bicyclo [2 2.1] Hepta , Diethylenetriamine, dipropylenetriamine, triethylenetetramine, 1,2-bis (aminomethyl) benzene, 1,3-bis (aminomethyl) benzene, 1,4-bis (aminomethyl) benzene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-bis (trichloromethyl) -4,4'-diaminobiphenyl, 2, 2'-bis (tribromomethyl) -4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 2, 2′-dibromo-4,4′-diaminobiphenyl, 4,4′-diaminobiphenyl, 4,4′-diamino-benzophenone, 9,9-bis (4-amino Phenyl) fluorene, 9,9-bis (4-amino-2-fluorophenyl) fluorene, 9,9-bis (4-amino-2-bromophenyl) fluorene, 9,9-bis (4-amino-2-) Chlorophenyl) fluorene, 9,9-bis (4-amino-3-fluorophenyl) fluorene, 9,9-bis (4-amino-3-bromophenyl) fluorene, 9,9-bis (4-amino-3- Chlorophenyl) fluorene, 9,9-bis (4-amino-2-trifluoromethylphenyl) fluorene, 9,9-bis (4-amino-3-trifluoromethylphenyl) fluorene, bis (4-aminophenyl) sulfone 1,4-diaminobenzene, 1,3-diaminobenzene, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl Examples include methane, 4,4′-diaminodiphenylpropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 3,4′-diaminodiphenyl ether, and the like. .

Among the primary amine compounds (D) represented by the formula (i), specific examples of monoamines where n = 1 are methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, di-n-propyl. Amine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, di-n-butylamine, monoamylamine, diamylamine, ethylbutylamine, n-hexylamine, di-n-hexylamine, cyclohexylamine, Dodecylamine, hexadecylamine, octadecylamine, aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, o- Chloroaniline, m-chloroa Phosphorus, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, o-aminophenol, m-aminophenol, p-amino Phenol, o-anisidine, m-anisidine, p-anisidine, o-phenidine, m-phenidine, p-phenidine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether, 4-aminophenylphenyl ether, 2- Aminobenzofe 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenyl phenyl sulfide, 3-aminophenyl phenyl sulfide, 4-aminophenyl phenyl sulfide, 2-aminophenyl phenyl sulfone, 3-aminophenyl phenyl sulfone, 4-amino Phenylphenylsulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 5-amino-2- Examples include naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, and 9-aminoanthracene.

Among the primary amine compounds (D) represented by the formula (i), specific examples of n = 3 include 1,3,5-triaminobenzene, tris (3-aminophenyl) amine, tris (4-amino). Phenyl) amine, tris (3-aminophenyl) benzene, tris (4-aminophenyl) benzene, 1,3,5-tris (3-aminophenoxy) benzene, 1,3,5-tris (4-aminophenoxy) Examples thereof include benzene and 1,3,5-tris (4-aminophenoxy) triazine.

Among the primary amine compounds (D) represented by the formula (i), specific examples of tetraamines with n = 4 include 1,2,4,5-tetraaminobenzene, 3,3 ′, 4,4. '-Tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenylsulfone, 3,3 ', 4,4'-tetraaminodiphenyl sulfide, 2,3,6,7-tetraaminonaphthalene, 1, Examples include 2,5,6-tetraaminonaphthalene.

A plurality of these amines can be used in combination for the purpose of adjusting various properties.

The polyfunctional compound (E) having an allyl group and a glycidyl group to be reacted with the primary amine compound (D) is not particularly limited as long as it is a monomeric compound having both an allyl group and a glycidyl group. Examples of the polyfunctional compound (E) include monoglycidyl diallyl isocyanurate, diglycidyl monoallyl isocyanurate, monoglycidyl dimethallyl isocyanurate, diglycidyl monomethallyl isocyanurate, monoglycidyl diallyl cyanurate, diglycidyl monoary Lucyanurate, monoglycidyl dimethallyl cyanurate, diglycidyl monomethallyl cyanurate, allyl glycidyl amine, diallyl monoglycidyl amine, monoallyl diglycidyl amine, monoglycidyl dimethallyl amine, diglycidyl monomethallyl amine, glycidyl acrylic chlorene Tate, allyl glycidyl adipate, allyl glycidyl carbonate, allyl glycidyl dimethyl ammonium chloride, allyl glycidyl fumarate Allyl glycidyl isophthalate, allyl glycidyl malonate, allyl glycidyl oxalate, allyl glycidyl phthalate, allyl glycidyl propyl isocyanurate, allyl glycidyl sebacate, allyl glycidyl succinate, allyl glycidyl terephthalate, allyl glycidyl tartrate, glycidyl methyl allyl phthalate Etc.

Among these compounds, the polyfunctional compound (E) is preferably a compound having an isocyanurate in the skeleton, and particularly preferably monoglycidyl diallyl isocyanurate.

By mixing and heating the primary amine compound (D) and the polyfunctional compound (E) having an allyl group and a glycidyl group, a large number of amines and glycidyl are added in one molecule by heat. A compound having an allyl group is obtained. The mixing ratio of the primary amine compound (D) and the polyfunctional compound (E) in the reaction may be such that the glycidyl group is 1 to 2 equivalents relative to 1 equivalent of the primary amine compound (D). In the case where the primary amine compound (D) is aliphatic, since the nucleophilicity of the amine is strong, two glycidyl groups can be added to one amine. That is, for example, it is considered that a glycidyl group reacts in a 4 mol amount with respect to 1 mol of an aliphatic diamine. In the case where the primary amine compound (D) is aromatic, the nucleophilicity of the amine is relatively weak, and the two glycidyl groups may not be added. That is, for example, it is considered that the glycidyl group reacts in an amount of approximately 2 moles per mole of the aromatic diamine.

The method of reacting the primary amine compound (D) and the polyfunctional compound (E) is not particularly limited. For example, as described above, the primary amine compound (D) and the polyfunctional compound are reacted. By mixing a predetermined amount of (E) and melting by heating, the above reaction can be easily performed. At that time, an appropriate reaction solvent may be used as necessary. What is necessary is just to set the heating temperature for making it react normally in the range of 80-200 degreeC. The atmosphere at the time of making it react is not specifically limited, What is necessary is just to react in air | atmosphere. However, when oxidation by oxygen becomes a problem, the atmosphere may be replaced with an inert gas such as nitrogen gas.

Since the reaction product thus obtained has a high boiling point, it is difficult to volatilize during melt processing, and can be used effectively as a crosslinking aid, end-capping agent and the like. Moreover, since it has many allyl groups in 1 molecule, an allyl group and resin can be bridge | crosslinked by a well-known method, and resin can be strengthened efficiently.

In the resin composition of the present invention, the addition amount of the polyfunctional allyl compound (C1) is 3 to 20 parts by mass with respect to 100 parts by mass in total of the thermoplastic resin (A) and the filler (B). The amount is preferably 4 to 15 parts by mass. When the addition amount is less than 3 parts by mass, sufficient melt fluidity may not be obtained. On the other hand, when the amount exceeds 20 parts by mass, the melt viscosity may be too low and pelletization may not be possible at the time of melt-kneading, or the physical properties of the resulting molded product may be significantly reduced.

Since the polyfunctional allyl compound (C1) has a large number of allyl groups in one molecule, according to a known method, it can be used in combination with a crosslinking agent, or in combination with irradiation treatment such as electron beam or γ-ray. The thermoplastic resin (A) can be crosslinked. Among them, it is preferable to crosslink with an electron beam or a γ ray from the viewpoint that it can be processed in a short time after being formed into a desired shape. Since gamma rays are more permeable than electron rays and therefore irradiation is uniform, crosslinking using gamma rays is more preferred. A known electron accelerator or the like can be used for electron beam irradiation, and an irradiation apparatus such as a known cobalt 60 radiation source can be used for γ-ray irradiation. The irradiation dose of the electron beam is preferably 1 to 300 kGy, more preferably 50 to 100 kGy. In the case of γ-ray irradiation, the irradiation dose is preferably 10 to 100 kGy, more preferably 20 to 40 kGy. If the radiation dose exceeds the upper limit, the strength is reduced due to the decomposition of the resin, which is not preferable. Moreover, if less than the said lower limit, since the effect by bridge | crosslinking is not exhibited, it is unpreferable. Irradiation atmosphere can be usually in the presence of air, but irradiation can be performed in a nitrogen atmosphere or in vacuum as desired.

The dimer acid-based thermoplastic resin (C2) will be described. In the present invention, the dimer acid-based thermoplastic resin (C2) is a dimer acid that is a dimer of fatty acids such as soybean oil, tung oil, or toll oil, or a derivative that can produce an amide thereof, or an ester thereof. It is a thermoplastic resin obtained by polycondensation of a dicarboxylic acid containing a derivative that can be produced as a main acid component with components such as diamine and glycol. The main component of the dimer acid is a dimer, but may further contain a monomer or a trimer. Moreover, the dicarboxylic acid containing the dimer acid which is a dimer of a fatty acid, a derivative capable of generating an amide thereof, or a derivative capable of generating an ester thereof may be hydrogenated.

The dimer acid-based thermoplastic resin (C2) has a lower melt viscosity than the thermoplastic resin (A), and the addition of the dimer acid-based thermoplastic resin effectively reduces the melt viscosity of the resin. . In addition, the dimer acid-based thermoplastic resin (C2) is a resin, has a high decomposition temperature, and does not volatilize during melt processing, so that it can be used effectively as a plasticizer. Furthermore, even if this is added, it is effective in that the mechanical strength is hardly lowered and bleeding does not occur.

The dimer acid-based thermoplastic resin (C2) is not particularly limited, and examples thereof include polyamide and polyester. Of these, polyamide is preferable from the viewpoint of handleability and economy.

The dimer acid-based polyamide is not particularly limited, and examples thereof include a polyamide resin composed of a dicarboxylic acid component containing a dimer acid or a derivative capable of forming an amide thereof and a diamine. Examples include reaction products of dimer acid, which is a dimer of fatty acids such as soybean oil, tung oil, and toll oil, and alkylpolyamines such as ethylenediamine and diethylenetriamine.

The dimer acid-based polyester is not particularly limited, and examples thereof include a polyester resin composed of a dicarboxylic acid component containing a dimer acid or a derivative capable of forming an ester thereof and glycol. For example, dimer acid, which is a dimer of fatty acids such as soybean oil, tung oil, and toll oil, and a reaction product of a glycol component such as ethylene glycol or 1,4-butanediol with terephthalic acid or isophthalic acid. You can list things.

The dimer acid-based polyamide and the dimer acid-based polyester can be used individually or in combination.

In the resin composition of the present invention, the amount of the dimer acid-based thermoplastic resin (C2) added is 10 to 45 parts by volume with respect to 100 parts by volume in total of the thermoplastic resin (A) and the filler (B). It is necessary that it is 10 to 25 parts by volume. If the blending amount of the dimer acid-based thermoplastic resin (C2) is less than 10 parts by volume, the effect of blending the dimer acid-based thermoplastic resin (C2) may not be sufficiently obtained. On the other hand, if the blending amount exceeds 45 parts by volume, mechanical properties may be remarkably lowered, or pelletization may not be possible during melt kneading.

The resin composition of the present invention has a pigment, a heat stabilizer, an antioxidant, a weathering agent, a flame retardant, a lubricant, a release agent, an antistatic agent, a crystal nucleus material, and a compatibilization as long as the characteristics are not significantly impaired An agent or the like can be added. Examples of heat stabilizers and antioxidants include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and the like. Examples of the flame retardant include hydrated metal compounds (such as aluminum hydroxide and magnesium hydroxide), nitrogen-containing compounds (melamine-based and guanidine-based), phosphorus-based flame retardants, halogen-based flame retardants, and inorganic flame retardants. Examples of the crystal nucleus material include a sorbitol compound, benzoic acid and a metal salt of the compound, a phosphate metal salt, a rosin compound, and the like. Examples of the compatibilizer include ionomer compatibilizers, oxazoline compatibilizers, elastomer compatibilizers, reactive compatibilizers, and copolymer-based compatibilizers. These additives may be used alone or in combination of two or more. The method for mixing these with the resin composition of the present invention is not particularly limited.

The resin composition of the present invention comprises a thermoplastic resin (A), a filler (B), a polyfunctional allyl compound (C1) or a dimer acid-based thermoplastic resin (C2), and if necessary. Various additives can be produced by melt-kneading using a general extruder such as a single screw extruder, a twin screw extruder, a roll kneader, or a Brabender. At this time, it is also effective to use a static mixer or a dynamic mixer together. In order to improve the kneading state, it is preferable to use a twin screw extruder. The filler (B) and the polyfunctional allyl compound (C1) or the dimer acid-based thermoplastic resin (C2) are not particularly limited, but in the extruder, from a hopper or using a side feeder. Can be added.

The resin composition of the present invention can be formed into a molded body by molding it into a desired shape using a known melt molding technique such as injection molding, compression molding, extrusion molding, transfer molding, or sheet molding. After the resin composition is molded into a desired shape, the resin can be crosslinked by irradiation with radiation as described above.

In the present invention, specific examples of a molded body obtained by molding a resin composition containing a thermally conductive filler (B1) having a thermal conductivity of 10 W / (m · K) or more include semiconductor elements and resistors. Electrical and electronic parts such as sealing materials for connectors, connectors, sockets, relay parts, coil bobbins, optical pickups, oscillators, computer-related parts; VTRs, TVs, irons, air conditioners, stereos, vacuum cleaners, refrigerators, rice cookers Household electrical product parts such as lighting fixtures; Heat dissipation members for releasing heat from electronic components such as heat dissipation sheets, heat sinks and fans; Lighting fixture components such as lamp sockets, lamp reflectors and lamp housings; Compact discs, laser discs Audio product parts such as speakers; optical cable ferrules, mobile phones, fixed phones, fax machines Communication equipment parts such as modems and modems; Copying machines such as separation claws and heater holders, printer-related parts; machine parts such as impellers, fan gears, gears, bearings, motor parts and cases; mechanism parts for automobiles, engine parts, Automotive parts such as engine compartment parts, electrical parts, interior parts, etc .; cooking utensils such as microwave cooking pans and heat-resistant dishes; aircraft, spacecraft, space equipment parts; sensor parts and the like.

Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to only these examples.

In the following examples and comparative examples, the test methods for various physical property values are as follows.

[1] MFR (melt flow rate):
The pellets of the thermoplastic resin composition were measured for MFR values at a predetermined load and a predetermined temperature using a descending flow tester (manufactured by Toyo Seiki Seisakusho). At this time, an orifice having a diameter of 1 mm and a length of 10 mm was used.

[2] Flexural strength, flexural modulus:
The measurement was performed according to the method described in ASTM standard D-790.

[3] Impact strength:
According to the method described in ASTM standard D-256, Izod impact strength was measured using a notched specimen.

[4] Thermal conductivity:
Thermal conductivity (lambda) calculated | required thermal diffusivity (alpha), density (rho), and specific heat Cp by the following method, and computed it with the following Formula as the product.

λ = αρCp
λ: thermal conductivity (W / (m · K))
α: Thermal diffusivity (m ² / sec)
ρ: Density (g / m ³ )
Cp: Specific heat (J / g · K)
The thermal diffusivity α was measured by a laser flash method using a laser flash method thermal constant measuring device TC-7000 (manufactured by ULVAC-RIKO, Inc.) in the resin flow direction of the bending test piece prepared in [2]. The density ρ was measured using an electronic hydrometer ED-120T (manufactured by Mirage Trading Co.). The specific heat Cp was measured using a differential scanning calorimeter DSC-7 (manufactured by Perkin Elmer) under the condition of a heating rate of 10 ° C./min.

[5] Moldability After sufficiently drying the test resin composition, a strip-shaped sample having a width of 13 mm, a length of 130 mm, and a thickness of 0.8 mm using an injection molding machine (Toshiba Machine Co., Ltd .: EC-100 type). Was injection molded. The state of the obtained molded piece was evaluated in three stages according to the following criteria.

Good: There was no problem in appearance and it could be molded to the specified size. Slightly inferior: Molded to the specified size, but the smoothness of the surface of the molded piece was bad. The raw materials used in Examples and Comparative Examples that could not be performed are shown below.

(1) Thermoplastic resin (A)
PA6A: polyamide 6 obtained by polymerization of lactam (relative viscosity 2.6, density 1.13 g / cm ³ )
PA6B: Polyamide 6 obtained by polymerization of lactam (relative viscosity 1.9, density 1.13 cm ³ )
PA66: polyamide 66 obtained by polymerization of hexamethylenediamine and adipic acid (relative viscosity 2.8, density 1.14 cm ³ )
LCP: Liquid crystalline polyester (Rodlan LC-5000 manufactured by Unitika Ltd., density 1.41 g / cm ³ )
PA12: Polyamide 12 (Rilsan AMN manufactured by Arkema, relative viscosity 2.3, density 1.01 g / cm ³ )
-PP: Polypropylene (Nippon Polypro Corporation MA1B, density 0.9 g / cm3)
PLA: Polylactic acid (manufactured by NatureWorks, weight average molecular weight (MW) = 190,000, density 1.25 g / cm ³ )
(2) Filler (B)
GrA: scaly graphite (manufactured by Nippon Graphite Industries Co., Ltd., average particle size 40 μm, thermal conductivity 100 W / (m · K), density 2.25 g / cm ³ )
GrB: scaly graphite (manufactured by Nippon Graphite Industry Co., Ltd., average particle size 130 μm, thermal conductivity 100 W / (m · K), density 2.25 g / cm ³ )
GrCF: graphitized carbon fiber (manufactured by Nippon Graphite Fiber, average fiber diameter 9 μm, average fiber length 3 mm, density 2.2 g / cm ³ )
BN: hexagonal scaly boron nitride (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 15 μm, density 2.26 g / cm ³ )
ALOA: aluminum oxide (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 10 μm, thermal conductivity 38 W / m · K, density 3.97 g / cm ³ )
ALOB: aluminum oxide (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 50 μm, thermal conductivity 38 W / (m · K), density 3.97 g / cm ³ )
TC: Talc (K-1 manufactured by Nippon Talc Co., Ltd., average particle diameter 8 μm, density 2.7 g / cm ³ )
MgO: Magnesium oxide (manufactured by Kamishima Chemical Co., Ltd., average particle size 5 μm, thermal conductivity 50 W / (m · K), density 3.58 g / cm ³ )
MgCO: Magnesium carbonate (manufactured by Kamishima Chemical Co., Ltd., average particle size 10 μm, thermal conductivity 15 W / (m · K), density 3.05 g / cm ³ )
ZnO: Zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd., average particle size 10 μm, thermal conductivity 25 W / (m · K), density 5.78 g / cm ³ )
AF: Copolyparaphenylene-3,4'-oxydiphenylene terephthalamide fiber (manufactured by Teijin Techno Products, average fiber diameter 12 μm, average fiber length 3 mm, density 1.39 g / cm ³ )
GF: Glass fiber (Owens Corning, average fiber diameter 10 μm, average fiber length 3 mm, density 2.50 g / cm ³ )
(3) Polyfunctional allyl compound (C1)
・ TAIC: triallyl isocyanurate (TAIC, Nippon Kasei Co., Ltd., liquid, boiling point 150 ° C.)
DAMGIC: monoglycidyl diallyl isocyanurate (DA-MGIC, solid, melting point 40 ° C., 5% weight loss temperature 178 ° C. measured by TGA measurement)
・ C11
1,3-bis (aminomethyl) benzene (MXDA) is used as the primary amine compound (D), monoglycidyl isocyanurate (DAMGIC) is used as the multifunctional compound (E), and 2 DAMGICs per 1 equivalent of MXDA. They were weighed to an equivalent weight, added to a round bottom flask, and heated at 80 ° C. for 30 minutes with stirring. Furthermore, it heated at 180 degreeC for 30 minute (s), and the colorless and transparent liquid material was obtained. The obtained liquid was gradually cooled to room temperature, and the solid produced at that time was pulverized to obtain a white powder of a polyfunctional allyl compound (C11).

Using a TGA device (Perkin-Elmer TGA-7), a 5 mg sample was heated from room temperature to 600 ° C. at a temperature increase rate of 20 ° C./min in a nitrogen-substituted atmosphere, and the sample mass change was measured. did. The 5% mass reduction | decrease temperature by the TGA measurement of the obtained powder was 375 degreeC. The 5% mass reduction temperature measured by MXDA TGA was 52 ° C. The melting point of the obtained powder was in the range of 55-70 ° C.

・ C12:
DAMGIC was adjusted to 1 equivalent with respect to 1 equivalent of MXDA. Otherwise, synthesis was carried out in the same manner as in C11 to obtain a colorless and transparent liquid. The obtained liquid was gradually cooled to room temperature, and the solidified solid was pulverized to obtain a white powder of a polyfunctional allyl compound (C12).

The 5% mass reduction temperature of the obtained powder by TGA measurement was 335 ° C. The melting point of the obtained powder was in the range of 50-60 ° C.

・ C13:
Hexamethylenediamine (HMDA) was used as the primary amine compound (D). Otherwise, synthesis was carried out in the same manner as in C11 to obtain a colorless and transparent liquid. The obtained liquid was gradually cooled to room temperature, and the solid produced at that time was pulverized to obtain a white powder of a polyfunctional allyl compound (C13).

The 5% mass reduction temperature of the obtained powder by TGA measurement was 356 ° C. The 5% mass reduction temperature by TGA measurement of HMDA was 76 ° C. The melting point of the obtained powder was in the range of 35 to 45 ° C.

(4) Dimer acid based thermoplastic resin (C2)
・ Production Example 1 (C21)
Dimer acid (manufactured by Tsukino Food Industry Co., Ltd., without hydrogenation) / 1,3-bis (aminomethyl) benzene = 46.5 / 53.5 (molar ratio) was charged into the reaction vessel at 240 ° C. The reaction was performed for 2 hours. After completion of the reaction, it was discharged and cut to obtain dimer acid-based polyamide resin pellets. The resulting pellet had a melt flow rate (MFR) at 230 ° C. and 21.18 N of 1800 g / min.

・ Production Example 2 (C22)
Dimer acid (manufactured by Tsukino Food Industry Co., Ltd., without hydrogenation) /65.3% hexamethylenediamine aqueous solution / caprolactam = 10.3 / 7.3 / 82.4 (molar ratio) were charged into the reaction vessel. And reacted at 250 ° C. for 2 hours. After completion of the reaction, it was discharged and cut to obtain dimer acid-based polyamide resin pellets. The resulting pellet had a melt flow rate (MFR) at 230 ° C. and 21.18 N of 1300 g / min.

・ Production Example 3 (C23)
Dimer acid (manufactured by Tsukino Food Industry Co., Ltd., without hydrogenation) / terephthalic acid / 1,4 butanediol = 13.2 / 26.8 / 60 (molar ratio) was charged into the reaction vessel and brought to 240 ° C. Then, an esterification reaction was carried out, and then a titanium catalyst was added by a conventional method, and a polycondensation reaction was carried out at 240 ° C. for 3 hours. After completion of the reaction, it was discharged and cut to obtain a dimer acid-based polyester resin. The resulting pellet had a melt flow rate (MFR) at 200 ° C. and 21.18 N of 800 g / min.

(5) Plasticizer-HB: p-hydroxybenzoic acid alkyl ester (Exepar HD-PB, liquid, Kao company, 5% mass reduction temperature 285 ° C. measured by TGA measurement)
Example 1
30 parts by mass of polyamide 6 resin (PA6A) and 5 parts by mass of polyfunctional allyl compound (C12) are supplied to a main hopper of a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM26SS, screw diameter 26 mm) at 260 ° C. And melted. In the middle, 70 parts by mass of glass fiber (GF) was supplied from the side feeder and sufficiently melt-kneaded. And after extruding in the shape of a strand and cooling and solidifying, it cut | disconnected to the shape of a pellet, and obtained the resin composition.

After sufficiently drying this resin composition, using an injection molding machine (manufactured by Toshiba Machine Co., Ltd .: EC-100 type), conditions of cylinder temperature 270 ° C., mold temperature 100 ° C., injection time 20 seconds, cooling time 10 seconds Then, the above-described strip-shaped sample was injection molded.

The evaluation results are shown in Table 1. No volatile gas evolution was observed during the kneading and injection molding operations.

(Comparative Example 1)
Compared with Example 1, it changed so that polyfunctional allyl compound (C1) might not be added. Other than that obtained the resin composition like Example 1, this was injection-molded, and the moldability was evaluated. The evaluation results are shown in Table 1. During the kneading and injection molding operations, no generation of volatile gases was observed.

(Examples 2 to 8, Comparative Examples 2 to 7)
Compared with Example 1, the thermoplastic resin (A), the filler (B), and the polyfunctional allyl compound (C1) were changed to the types and amounts shown in Table 1, respectively. Other than that was carried out similarly to Example 1, and obtained the resin composition. And this was injection-molded and the moldability was evaluated. The fibrous filler is supplied from the middle by the side feeder, the other fillers are supplied from the main hopper, and triallyl cyanurate (TAIC), which is a liquid, is injected from the middle of the kneader using a pump, and melt-kneaded. Carried out.

The evaluation results are summarized in Table 1. In Examples 4 and 6, a large amount of volatile gas was generated during the kneading and injection molding operations, and triallyl cyanurate bleeded out on the surface of the obtained molded body.

As is clear from Table 1, in Examples 1-8, the polyfunctional allyl compound (C1) functions as a plasticizer and thus has good moldability, whereas in Comparative Examples 1-7, Since the plasticizer was not blended or the blending amount was too small, a clean molded piece could not be obtained at the same molding temperature.

Example 9
In the main hopper of the same twin-screw extruder used in Example 1, 41 parts by mass of polyamide 6 resin (PA6B), 59 parts by mass of flaky graphite (GrA) as a thermally conductive filler (B1), 4 parts by mass of monoglycidyl isocyanurate (DAMGIC) was supplied and melt-kneaded at 250 ° C. And after extruding in the shape of a strand and cooling and solidifying, it cut | disconnected to the pellet form and obtained the resin composition.

After sufficiently drying the obtained resin composition, the MFR was measured under the conditions of 250 ° C. and a load of 100 kg, and it was 100 g / 10 min.

Next, this resin composition was injection-molded by the same injection molding machine used in Example 1 at a cylinder temperature of 260 ° C., a mold temperature of 100 ° C., an injection time of 20 seconds, and a cooling time of 10 seconds. A molded body of was obtained. Note that generation of volatile gas was not observed in the kneading and injection molding operations.

The evaluation results are shown in Table 2.

(Examples 10 to 27, Comparative Examples 8 to 18)
Compared to Example 9, the thermoplastic resin (A), the thermally conductive filler (B1), the polyfunctional allyl compound (C1), other fillers, and other plasticizers are shown in Table 2, respectively. I changed the amount. Other than that was carried out similarly to Example 1, and obtained the resin composition. The resin composition was injection molded and various physical properties were measured. At that time, the fibrous filler was supplied from the middle by the side feeder, and the other fillers were supplied from the main hopper. Triallyl cyanurate (TAIC), which is a liquid, was injected from the middle of the kneader using a pump to carry out melt kneading.

In Examples 16 and 21, a large amount of volatile gas was generated during kneading and injection molding. In Example 16, triallyl cyanurate bleeded out on the surface of the obtained molded body.

The molded bodies obtained in Examples 10, 12, 14, 16, 17, 19 and Comparative Examples 8, 11, and 14 were irradiated with gamma rays using cobalt 60 as a radiation source at 30 kGy, intensity measurements were then performed, and gamma irradiation was performed. The physical properties before and after were compared.

Table 2 summarizes the evaluation results of Examples 9 to 27 and Comparative Examples 8 to 18.

Examples 9 to 27 had a large MFR value and excellent moldability because the polyfunctional allyl compound (C1) functions as a plasticizer. In contrast, in Comparative Examples 8 to 13 and Comparative Examples 15 to 17, the polyfunctional allyl compound (C1) as a plasticizer was not blended or was too little. The MFR value was small and inferior in moldability as compared with the examples in which the amount was appropriate and the other conditions were the same.

In particular, Examples 21 to 26 and Comparative Examples 15 to 17 were blended with a large amount of the filler (B), but Examples 21 to 26 had a predetermined amount of the polyfunctional allyl compound (C1). It was possible to lower the molding temperature as compared with Comparative Examples 15 to 17. In Comparative Example 14, when a commercially available plasticizer was blended, the MFR value was high and the moldability was excellent, but the mechanical performance of the molded body was inferior to that of the Example. In Comparative Example 18, since the blending amount of the polyfunctional allyl compound (C1) was too large, the melt viscosity was too low, and it was not possible to extrude into a strand shape during melt kneading and solidify by cooling. Could not be produced.

In Examples 10, 12, 14, 16, 17, and 19, since the polyfunctional allyl compound (C1) was blended, the polyamide resin was cross-linked by gamma irradiation, and the bending strength was improved. On the other hand, in Comparative Examples 8, 11, and 14, no polyfunctional allyl compound was blended, and thus no improvement in strength due to gamma irradiation was observed.

(Example 28)
The main hopper of the same twin-screw extruder used in Example 1 was supplied with 35% by volume of polyamide 6 resin (PA6A) and 15% by volume of dimer acid-based thermoplastic resin (C21) and melted at 260 ° C. . In the middle, 50% by volume of glass fiber (GF) was supplied from the side feeder, and after sufficiently melt-kneaded, the melt-kneaded product was extruded into a strand shape and cooled and solidified. Then, it cut | disconnected to the pellet form and obtained the resin composition.

After sufficiently drying this resin composition, the above strip-shaped sample was injection molded under the same conditions as in Example 1 using the same injection molding machine as used in Example 1.

The evaluation results are shown in Table 3. No volatile gas evolution was observed during the kneading and injection molding operations.

(Comparative Example 19)
Compared to Example 28, no dimer acid based thermoplastic resin (C2) was added. Otherwise in the same manner as in Example 28, a resin composition was obtained. The obtained resin composition was injection-molded to evaluate moldability. The evaluation results are shown in Table 3. During the kneading and injection molding operations, no generation of volatile gases was observed.

(Examples 29 to 37, Comparative Examples 20 to 26)
Compared with Example 28, the thermoplastic resin (A), the filler (B), and the dimer acid-based thermoplastic resin (C2) were changed to the types and amounts shown in Table 3, respectively. Otherwise in the same manner as in Example 28, a resin composition was obtained. At that time, the fibrous filler was supplied from the middle by the side feeder, and the other fillers were supplied from the main hopper to carry out melt kneading. The obtained resin composition was injection-molded to evaluate moldability. The evaluation results are summarized in Table 3.

As is clear from Table 3, Examples 28 to 37 had good moldability because the dimer acid-based thermoplastic resin (C2) was blended. On the other hand, in Comparative Examples 19 to 26, the dimer acid-based thermoplastic resin (C2) was not blended or the blending amount was too small. Therefore, under the same molding conditions as in Examples 28 to 37, the surface of the molded piece was smooth. It was inferior in property, or a molded piece having a predetermined size could not be obtained.

(Example 38)
In the main hopper of the same twin-screw extruder used in Example 1, polyamide 6 resin (PA6A) 50% by volume, scaly graphite (GrA) 40% by volume as the heat conductive filler (B1), 10% by volume of dimer acid-based polyamide (C21) was supplied, and melt kneading was performed at 260 ° C. Then, the melt-kneaded product was extruded into a strand shape, cooled and solidified, and cut into a pellet shape to obtain a resin composition.

After sufficiently drying the obtained resin composition, MFR was measured under the conditions of 270 ° C. and a load of 100 kg, and it was 158 g / 10 min.

Using the same injection molding machine as used in Example 1, this resin composition was injection molded at a cylinder temperature of 270 ° C., a mold temperature of 80 ° C., an injection time of 20 seconds, and a cooling time of 10 seconds. A shaped sample was injection molded.

The evaluation results are shown in Table 4. No generation of volatile gases was observed during the kneading and injection molding operations.

(Examples 39 to 56, Comparative Examples 27 to 40)
Compared with Example 38, the thermoplastic resin (A), the thermally conductive filler (B1), the dimer acid-based thermoplastic resin (C2), other fillers, and other plasticizers are shown in Table 4, respectively. And changed the amount. Otherwise in the same manner as in Example 38, a resin composition was obtained. The resin composition was injection molded and various physical properties were measured. At that time, the fibrous filler was supplied from the middle by the side feeder, and the other fillers were supplied from the main hopper to carry out melt kneading.

Table 4 shows the evaluation results of Examples 38 to 46 and Comparative Examples 27 to 34, and Table 5 shows the evaluation results of Examples 47 to 56 and Comparative Examples 35 to 40.

In Examples 38 to 56, since the dimer acid-based thermoplastic resin (C2) functioned as a plasticizer, the MFR value was large and the moldability was excellent. On the other hand, in Comparative Examples 27 to 30 and Comparative Examples 32 to 40, since the dimer acid-based thermoplastic resin (C2) was not blended or was too little, the blending amount of the dimer acid-based thermoplastic resin (C2) was changed. The MFR value was small and inferior in moldability as compared with the examples that were appropriate and other conditions were the same. In particular, Examples 44 to 46 and Comparative Examples 32 to 34 were blended with a large amount of the filler (B), but Examples 44 to 46 had a predetermined amount of dimer acid-based thermoplastic resin (C2 ), The molding temperature could be lowered as compared with Comparative Examples 32-34. In Comparative Example 31, a commercially available plasticizer was blended. In this case, although the MFR value was high and the moldability was excellent, the plasticizer was volatilized at the time of melt kneading, and the mechanical performance of the molded product was inferior to that of the example.

Claims (12)

1. The thermoplastic resin (A), the filler (B), and a predetermined amount of the melt viscosity reducing agent (C), the predetermined amount of the melt viscosity reducing agent (C) are the following (a) and (b) And a resin composition characterized by that.
   (A) The melt viscosity reducing agent (C) is a polyfunctional allyl compound (C1), and the polyfunctional allyl compound (C1) with respect to 100 parts by mass in total of the thermoplastic resin (A) and the filler (B). The content is 3 to 20 parts by mass.
   (B) The melt viscosity reducing agent (C) is a dimer acid-based thermoplastic resin (C2), and the dimer acid-based thermoplastic resin (C2) for a total of 100 parts by volume of the thermoplastic resin (A) and the filler (B). ) Content is 10 to 45 parts by volume.
2. The resin composition according to claim 1, wherein the polyfunctional allyl compound (C1) is a compound having isocyanurate in the skeleton.
3. The polyfunctional allyl compound (C1) is an allyl compound obtained by reacting a primary amine compound (D) represented by the following formula (i) with a polyfunctional compound (E) having an allyl group and a glycidyl group. The resin composition according to claim 1, wherein the resin composition is present.
   R- (NH ₂ ) _n (i)
   Here, n = 1 to 4 and R represents an aromatic or aliphatic 1 to 4 substituted residue.
4. The resin composition according to claim 3, wherein the polyfunctional compound (E) having an allyl group and a glycidyl group is a compound having an isocyanurate in a skeleton.
5. 5. The resin composition according to claim 2, wherein the compound having isocyanurate in the skeleton is monoglycidyl diallyl isocyanurate.
6. The resin composition according to claim 1, wherein the dimer acid-based thermoplastic resin (C2) is a polyamide resin and / or a polyester resin.
7. The resin composition according to claim 1, wherein the filler (B) is a thermally conductive filler (B1) having a thermal conductivity of 10 W / (m · K) or more.
8. The resin composition according to claim 7, wherein the volume ratio (A / B1) of the thermoplastic resin (A) and the thermally conductive filler (B1) is 20/80 to 95/5.
9. The heat conductive filler (B1) has a flake graphite having an average particle diameter of 1 to 300 μm, a graphitized carbon fiber having an average fiber diameter of 1 to 30 μm and an average fiber length of 1 to 20 mm, and an average having a hexagonal crystal structure. Scaly boron nitride having a particle size of 1 to 200 μm, aluminum oxide having an average particle size of 0.5 to 150 μm, magnesium oxide having an average particle size of 0.5 to 150 μm, and magnesium carbonate having an average particle size of 0.5 to 150 μm, 8. The resin composition according to claim 7, wherein the resin composition is at least one selected from zinc oxide having an average particle size of 0.5 to 150 μm.
10. 2. The resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyamide resin.
11. A molded article obtained by molding the resin composition according to any one of claims 1 to 10.
12. A molded body, which is formed by molding the resin composition according to any one of claims 1 to 10 and irradiating with radiation.