JP6957859B2 - Fiber-reinforced thermoplastic resin molded products and fiber-reinforced thermoplastic resin molded materials - Google Patents

Description

The present invention relates to thermoplastic resins, carbon fibers, organic fibers, and fiber-reinforced thermoplastic resin molded products and fiber-reinforced thermoplastic resin molded materials containing boron nitride and / or graphite.

Molded articles containing reinforcing fibers and thermoplastic resins are widely used in sports equipment applications, aerospace applications, general industrial applications, etc. because of their light weight and excellent mechanical properties. Reinforcing fibers used in these molded products include metal fibers such as aluminum fibers and stainless fibers, inorganic fibers such as silicon carbide fibers and carbon fibers, and organic fibers such as aramid fibers and polyparaphenylene benzoxazole (PBO) fibers. And so on. Carbon fibers are preferable from the viewpoint of the balance between specific strength, specific rigidity and light weight, and among them, polyacrylonitrile (PAN) -based carbon fibers are preferably used.

Due to the excellent specific strength and rigidity of carbon fibers, carbon fiber reinforced molded products have excellent light weight and mechanical properties. Therefore, it is widely used in various fields such as electronic device housings and automobile parts. However, in electronic device housing applications, the amount of heat generated per component tends to increase due to the performance improvement of the mounted electronic components. Therefore, in molded products such as housings, improvement in thermal conductivity is required in addition to light weight and mechanical properties.

As means for enhancing the mechanical properties of the carbon fiber reinforced thermoplastic resin molded product, for example, carbon fiber, organic fiber and thermoplastic resin are included, and the average fiber length and the average fiber end distance of the carbon fiber and the average fiber of the organic fiber are included. A fiber-reinforced thermoplastic resin molded product (see, for example, Patent Document 1) in which the length and the distance between the average fiber ends are in a specific range has been proposed. However, the molded product described in Patent Document 1 has a problem that the bending strength and the thermal conductivity are insufficient.

On the other hand, as a fiber-reinforced thermoplastic resin molded body or resin composition having excellent thermal conductivity, for example, the Young ratio of carbon fibers and flexible fibers composed of rigid carbon fibers and flexible fibers is specific. A fiber-reinforced resin molded body (see, for example, Patent Document 2) formed by using long fiber pellets impregnated or coated with a resin for pellet forming into a carbon fiber roving having a relationship, a thermoplastic resin, carbon fibers, and average particles. A resin composition containing graphite having a defined diameter has been proposed (for example, Patent Document 3). However, the molded product described in Patent Document 2 still has insufficient bending strength and thermal conductivity, and the molded product obtained from the resin composition described in Patent Document 3 has a problem that the impact strength is insufficient. there were.

As described above, in the prior art, in the fiber-reinforced thermoplastic resin molded product using the thermoplastic resin as a matrix, the fiber-reinforced thermoplastic resin molded product having high mechanical properties, particularly excellent bending strength and impact strength, and high thermal conductivity. Has not been obtained, and the development of such a fiber-reinforced thermoplastic resin molded product has been desired.

International Publication No. 2014/98103 International Publication No. 2008/105225 Japanese Unexamined Patent Publication No. 2013-001818

In view of the above problems of the prior art, the present invention provides a fiber-reinforced thermoplastic resin molded product having excellent bending strength, impact strength and thermal conductivity, and a fiber-reinforced thermoplastic resin molded product capable of obtaining such a molded product. The purpose is to do.

In order to solve the above problems, the present invention mainly has the following configurations.
A fiber-reinforced thermoplastic resin molded product containing a thermoplastic resin (A), carbon fibers (B), organic fibers (C), and boron nitride and / or graphite (D), wherein the thermoplastic resin (A), 20 to 93 parts by weight of the thermoplastic resin (A) and carbon fiber (B) with respect to a total of 100 parts by weight of carbon fiber (B), organic fiber (C), and boron nitride and / or graphite (D). 5 to 40 parts by weight, organic fiber (C) to 1 to 30 parts by weight, and boron nitride and / or graphite (D) to 1 to 30 parts by weight. A fiber-reinforced thermoplastic resin molded product _{having an L Wb} ) of 0.7 to 2 mm and a weight average fiber length (L _{wc) of the organic fiber (C) of 2.5 to 5 mm.}
Thermoplastic resin (A), carbon fiber (B), organic fiber (C), boron nitride and / or graphite (D), and compound (E) having a melt viscosity at 200 ° C. lower than that of the thermoplastic resin (A). Fiber-reinforced thermoplastic resin molding material containing, with respect to a total of 100 parts by weight of the thermoplastic resin (A), carbon fiber (B), organic fiber (C), and boron nitride and / or graphite (D). , 20 to 93 parts by weight of thermoplastic resin (A), 5 to 40 parts by weight of carbon fiber (B), 1 to 30 parts by weight of organic fiber (C) boron nitride and / or graphite (D) 1 to 30 parts. A fiber-reinforced thermoplastic resin molding material containing 1 to 20 parts by weight and 1 to 20 parts by weight of a compound (E) having a melt viscosity at 200 ° C. lower than that of the thermoplastic resin (A).

Since the fiber-reinforced thermoplastic resin molded product of the present invention contains carbon fibers, organic fibers, and boron nitride and / or graphite, it has a high reinforcing effect and is excellent in bending strength, impact strength, and thermal conductivity. The fiber-reinforced thermoplastic resin molded product and the fiber-reinforced thermoplastic resin molded material of the present invention are extremely useful for electrical / electronic equipment, OA equipment, home appliances, housings, automobile parts, and the like.

It is a schematic diagram which shows the cross section of the molding material in the form which the carbon fiber (B) contains the organic fiber (C) in the cross section of a molding material. It is a schematic diagram which shows the cross section of the molding material in the form which the organic fiber (C) contains the carbon fiber (B) in the cross section of a molding material. It is a schematic diagram which shows the cross section of the molding material of the form which exists in the state which the bundle of carbon fiber (B) and the bundle of organic fiber (C) are separated by the boundary part in the cross section of a molding material.

The fiber-reinforced thermoplastic resin molded product (sometimes referred to as “molded product”) and the fiber-reinforced thermoplastic resin molded material (sometimes referred to as “molded material”) of the present invention are at least the thermoplastic resin (A) and carbon fiber. Includes (B), organic fiber (C), and (D) boron nitride and / or graphite (D).

In the present invention, the thermoplastic resin (A) is a matrix resin constituting a molded product and a molding material. The thermoplastic resin (A) preferably has a molding temperature (melting temperature) of 200 to 450 ° C., and is preferably a polyolefin resin, a polystyrene resin, a polyamide resin, a vinyl halide resin, a polyacetal resin, a saturated polyester resin, or a polycarbonate resin. Examples thereof include polyarylsulfone resin, polyarylketone resin, polyarylene ether resin, polyarylene sulfide resin, polyaryl ether ketone resin, polyether sulfone resin, polyarylene sulfide sulfone resin, polyarylene resin, polyamide resin, and the like. Both correspond to electrical insulators. Two or more of these can also be used. As the polyolefin resin, polypropylene resin is preferable.

Among the thermoplastic resins (A), polypropylene resin, polyamide resin, polycarbonate resin, and polyarylene sulfide resin, which are lightweight and have an excellent balance of mechanical properties and moldability, are more preferable, and polypropylene resin is excellent in versatility. Polypropylene resin is more preferred.

The polypropylene resin may be non-denatured or modified. The non-modified polypropylene resin is specifically at least one selected from the group consisting of a homopolymer of propylene, propylene and α-olefin, conjugated diene, non-conjugated diene and other thermoplastic monomers. Examples thereof include a copolymer with a monomer. Examples of the copolymer include a random copolymer and a block copolymer. Examples of the α-olefin include ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-hexene, 4,4-. Α-olefins having 2 to 12 carbon atoms excluding propylene, such as dimethyl-1-hexene, 1-nonene, 1-octene, 1-hexene, 1-hexene, 1-decene, 1-undecene, 1-dodecene, etc. Can be mentioned. Examples of the conjugated diene or non-conjugated diene include butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene and the like. Two or more of these may be used. For example, polypropylene, ethylene / propylene copolymer, propylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer and the like are preferable. A homopolymer of propylene is preferable from the viewpoint of improving the rigidity of the molded product. Random or block copolymers of propylene and at least one monomer selected from the group consisting of α-olefins, conjugated diene and non-conjugated diene are preferred from the viewpoint of further improving the impact strength of the molded product.

Further, as the modified polypropylene resin, an acid-modified polypropylene resin is preferable, and an acid-modified polypropylene resin having a carboxylic acid and / or a carboxylic acid base bonded to a polymer chain is more preferable. The acid-modified polypropylene resin can be obtained by various methods. For example, the unmodified polypropylene resin has a monomer having a neutralized or unneutralized carboxylic acid group and / or a saponified or non-neutralized carboxylic acid ester group. The monomer can be obtained by graft polymerization.

Here, examples of the monomer having a carboxylic acid group that has been neutralized or not neutralized, or the monomer having a carboxylic acid ester group that has been saponified or not saponified, are examples. Examples thereof include ethylene-based unsaturated carboxylic acid, its anhydride, and ethylene-based unsaturated carboxylic acid ester.

Examples of the ethylene-based unsaturated carboxylic acid include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid. Examples of the anhydride include TM nadic acid (endosis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride and the like.

Examples of the ethylene-based unsaturated carboxylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, and tert-butyl ( Meta) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) Acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobolonyl (meth) acrylate, (Meta) acrylic acid esters such as dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, hydroxyethyl acrylate, 2-hydroxyethyl ( Hydroxyl-containing (meth) acrylic acid esters such as meta) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, glycidyl Epoxy group-containing (meth) acrylic acid esters such as (meth) acrylate and methylglycidyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N Aminoalkyls such as -dimethylaminopropyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dihydroxyethylaminoethyl (meth) acrylate Examples include (meth) acrylates.

Two or more of these can also be used. Among these, ethylene-based unsaturated carboxylic acid anhydrides are preferable, and maleic anhydride is more preferable.

In order to further improve the bending strength and tensile strength of the molded product, it is preferable to use both the non-modified polypropylene resin and the modified polypropylene resin. In particular, from the viewpoint of the balance between flame retardancy and bending strength and tensile strength, it is preferable to use the non-modified polypropylene resin and the modified polypropylene resin so that the weight ratio is 95/5 to 75/25. It is more preferably 95/5 to 80/20, and even more preferably 90/10 to 80/20.

The polyamide resin is a resin mainly composed of amino acids, lactams, diamines and dicarboxylic acids. The main raw materials thereof are, for example, amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactam such as ε-caprolactam and ω-laurolactam, tetramethylenediamine and hexa. Fats such as methylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine Aromatic diamines such as group diamines, metaxylylene diamines and paraxylylene diamines, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3 , 5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, Alicyclic diamines such as aminoethylpiperazin, aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, Aromatic dicarboxylic acids such as 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexane Examples thereof include alicyclic dicarboxylic acids such as dicarboxylic acids. Two or more of these may be used.

A polyamide resin having a melting point of 200 ° C. or higher is particularly useful because it is excellent in heat resistance and strength. Specific examples thereof include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66), and polytetramethylene adipamide (polytetramethylene adipamide). Nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyhexamethylene terephthalamide / polycaproamide copolymer (nylon 6T / 6), polyhexamethylene adipamide / poly Hexamethylene terephthalamide copolymer (nylon 66 / 6T), polylaurylamide / polyhexamethylene terephthalamide copolymer (nylon 12T / 6), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), poly Hexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (nylon 66 / 6I / 6), Polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / polydodecaneamide copolymer (nylon 6T / 12), polyhexamethylene terephthalamide / poly (2-methyl) Examples thereof include pentamethylene) terephthalamide copolymer (nylon 6T / M5T), polyxylylene adipamide (nylon XD6), polynonamethylene terephthalamide (nylon 9T) and copolymers thereof. Two or more of these may be used. Among these, nylon 6 and nylon 66 are more preferable.

The degree of polymerization of the polyamide resin is not particularly limited, but since it has excellent fluidity during molding and a thin-walled molded product can be easily obtained, 25 of a solution prepared by dissolving 0.25 g of the polyamide resin in 25 ml of 98% concentrated sulfuric acid. The relative viscosity measured at ° C. is preferably in the range of 1.5 to 5.0, more preferably in the range of 2.0 to 3.5.

The polycarbonate resin is obtained by reacting divalent phenols with a carbonate precursor. It may be a copolymer obtained by using two or more kinds of divalent phenols or two or more kinds of carbonate precursors. Examples of the reaction method include an interfacial polymerization method, a molten transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. Such a polycarbonate resin is known per se, and for example, the polycarbonate resin described in JP-A-2002-129027 can be used.

Examples of the divalent phenol include 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4-hydroxyphenyl) alkane (bisphenol A, etc.), and 2,2-bis {((). Examples thereof include 4-hydroxy-3-methyl) phenyl} propane, α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and the like. .. Two or more of these may be used. Among these, bisphenol A is preferable, and a polycarbonate resin having higher impact strength can be obtained. On the other hand, the copolymer obtained by using bisphenol A and other divalent phenols is excellent in high heat resistance or low water absorption.

Carbonic acid precursors include, for example, carbonyl halides, carbonic acid diesters, haloformates and the like. Specific examples thereof include phosgene, diphenyl carbonate, dihaloformates of divalent phenols and the like.

In producing the polycarbonate resin from the above-mentioned dihydric phenols and carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing the oxidation of the dihydric phenols, or the like may be used, if necessary.

Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher-functional polyfunctional aromatic compound, or may be co-containing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. It may be a polymerized polyester carbonate resin, a copolymerized polycarbonate resin copolymerized with a bifunctional aliphatic alcohol (including an alicyclic group), a bifunctional carboxylic acid and a bifunctional alcohol. May be a polyester carbonate resin obtained by co-polymerizing the above. Moreover, you may use 2 or more types of these polycarbonate resins.

The molecular weight of the polycarbonate resin is not particularly limited, but those having a viscosity average molecular weight of 10,000 to 50,000 are preferable. When the viscosity average molecular weight is 10,000 or more, the strength of the molded product can be further improved. The viscosity average molecular weight is more preferably 15,000 or more, and even more preferably 18,000 or more. On the other hand, when the viscosity average molecular weight is 50,000 or less, the molding processability is improved. The viscosity average molecular weight is more preferably 40,000 or less, further preferably 30,000 or less. When two or more types of polycarbonate resins are used, it is preferable that the viscosity average molecular weight of at least one type is in the above range. In this case, as another polycarbonate resin, it is preferable to use a polycarbonate resin having a viscosity average molecular weight of more than 50,000, preferably more than 80,000. Such a polycarbonate resin has high entropy elasticity, which is advantageous when gas-assisted molding or the like is used in combination, and also improves melting characteristics such as drip prevention property, drawdown property, and jetting improvement. Demonstrate the characteristics of

The viscosity average molecular weight (M) of the polycarbonate resin was obtained by inserting the specific viscosity (ηsp) obtained at 20 ° C. from a solution of 0.7 g of the polycarbonate resin in 100 ml of methylene chloride into the following formula.
ηsp / c = [η] +0.45 × [η] ² (However, [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 M ^0.83
c = 0.7.

The melt viscosity of the polycarbonate resin is not limited, but the melt viscosity at 200 ° C. is preferably 10 to 25,000 Pa · s. When the melt viscosity at 200 ° C. is 10 Pa · s or more, the strength of the molded product can be further improved. The melt viscosity is more preferably 20 Pa · s or more, and further preferably 50 Pa · s or more. On the other hand, when the melt viscosity at 200 ° C. is 25,000 Pa · s or less, the molding processability is improved. The melt viscosity is more preferably 20,000 Pa · s or less, and further preferably 15,000 Pa · s or less.

As polycarbonate resin, "Iupilon" (registered trademark) manufactured by Mitsubishi Engineering Plastics Co., Ltd., "Novalex" (registered trademark), "Panlite" (registered trademark) manufactured by Teijin Chemicals Ltd., and Idemitsu Petrochemical Co., Ltd. Those marketed as "Taflon" (registered trademark) can also be used.

Examples of the polyphenylene sulfide resin include polyphenylene sulfide (PPS) resin, polyphenylene sulfide sulfone resin, polyphenylene sulfide ketone resin, and random or block copolymers thereof. Two or more of these may be used. Of these, polyphenylene sulfide resin is particularly preferably used.

The polyarylene sulfide resin is described in, for example, a method for obtaining a polymer having a relatively small molecular weight described in Japanese Patent Application Laid-Open No. 45-3368, Japanese Patent Application Laid-Open No. 52-12240 and JP-A-61-7332. It can be produced by any method such as a method for obtaining a polymer having a relatively large molecular weight.

The obtained polyarylene disulfide resin is crosslinked / polymerized by heating in air, heat-treated under an atmosphere of an inert gas such as nitrogen or under reduced pressure, washed with an organic solvent, hot water, an acid aqueous solution, etc., acid anhydride, Various treatments such as activation with a functional group-containing compound such as an amine, isocyanate, and a functional group-containing disulfide compound may be performed.

As a method for cross-linking / increasing the molecular weight of the polyarylene sulfide resin by heating, for example, in an atmosphere of an oxidizing gas such as air or oxygen or in an atmosphere of a mixed gas of the oxidizing gas and an inert gas such as nitrogen or argon. , A method of heating in a heating container at a predetermined temperature until a desired melt viscosity is obtained can be exemplified. The heat treatment temperature is preferably in the range of 200 to 270 ° C., and the heat treatment time is preferably in the range of 2 to 50 hours. By adjusting the treatment temperature and the treatment time, the viscosity of the obtained polymer can be adjusted to a desired range. Examples of the heat treatment device include a normal hot air dryer, a rotary type, and a heating device with a stirring blade. From the viewpoint of efficient and more uniform heat treatment, it is preferable to use a heating device with a rotary type or a stirring blade.

When the polyarylene sulfide resin is treated under reduced pressure, the pressure is ^{preferably 7,000 Nm-2} or less. Examples of the heat treatment device include a normal hot air dryer, a rotary type, and a heating device with a stirring blade. From the viewpoint of efficient and more uniform heat treatment, it is preferable to use a heating device with a rotary type or a stirring blade.

When the polyarylene sulfide resin is washed with an organic solvent, the organic solvent includes, for example, a nitrogen-containing polar solvent such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide; a sulfoxide-sulfone solvent such as dimethylsulfoxide and dimethylsulfone; , Methyl ethyl ketone, diethyl ketone, acetophenone and other ketone solvents; dimethyl ether, dipropyl ether, tetrahydrofuran and other ether solvents; chloroform, methylene chloride, trichloroethylene, dichloride ethylene, dichloroethane, tetrachloroethane, chlorbenzene and other halogen solvents. Alcohol or phenolic solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol; aromatic hydrocarbon solvents such as benzene, toluene, xylene and the like. Two or more of these may be used. Among these organic solvents, N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like are preferably used. Examples of the cleaning method with an organic solvent include a method of immersing a polyarylene sulfide resin in an organic solvent. If necessary, it is also possible to stir or heat as appropriate. The cleaning temperature for cleaning the polyarylene sulfide resin in an organic solvent is preferably room temperature to 150 ° C. The polyarylene sulfide resin that has been washed with an organic solvent is preferably washed with water or warm water several times in order to remove the residual organic solvent.

When the polyarylene sulfide resin is washed with hot water, the water used is preferably distilled water or deionized water in order to exhibit the effect of preferable chemical modification of the polyarylene sulfide resin by hot water washing. Hot water washing is usually carried out by adding a predetermined amount of polyarylene sulfide resin to a predetermined amount of water, heating and stirring at normal pressure or in a pressure vessel. As for the ratio of the polyarylene sulfide resin to water, a bath ratio of 200 g or less of the polyarylene sulfide resin is preferably selected with respect to 1 liter of water.

Examples of the method for acid-treating the polyarylene sulfide resin include a method of immersing the polyarylene sulfide resin in an acid or an aqueous solution of an acid. If necessary, it is also possible to stir or heat as appropriate. Examples of the acid include aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid; halo-substituted aliphatic saturated carboxylic acids such as chloroacetic acid and dichloroacetic acid, and aliphatic unsaturated monocarboxylic acids such as acrylic acid and crotonic acid. Carous acids; aromatic carboxylic acids such as benzoic acid and salicylic acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid; and inorganic acidic compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid and silicic acid. Can be mentioned. Among these acids, acetic acid or hydrochloric acid is preferably used. The acid-treated polyarylene sulfide resin is preferably washed with water or warm water several times in order to remove residual acid or salt. The water used for washing is preferably distilled water or deionized water.

The melt viscosity of the polyarylene sulfide resin is preferably 80 Pa · s or less, and more preferably 20 Pa · s or less under the conditions of 310 ° C. and a shear rate of 1000 / sec. The lower limit of the melt viscosity is not particularly limited, but is preferably 5 Pa · s or more. Two or more kinds of polyarylene sulfide resins having different melt viscosities may be used in combination. The melt viscosity can be measured using a capillograph (manufactured by Toyo Seiki Co., Ltd.) under the conditions of a die length of 10 mm and a die hole diameter of 0.5 to 1.0 mm.

As polyphenylene sulfide resin, "Trelina" (registered trademark) manufactured by Toray Industries, Inc., "DIC.PPS" (registered trademark) manufactured by DIC Corporation, "Durafide" (registered trademark) manufactured by Polyplastics Co., Ltd., etc. It is also possible to use the one marketed as.

The content of the thermoplastic resin (A) in the molded product and the molding material of the present invention is the thermoplastic resin (A), carbon fiber (B), organic fiber (C), and boron nitride and / or graphite (D). 20 to 93 parts by weight with respect to 100 parts by weight in total. When the content of the thermoplastic resin (A) is less than 20 parts by weight, the fiber dispersibility of the carbon fibers (B) and the organic fibers (C) in the molded product is lowered, and the impact strength is lowered. The content of the thermoplastic resin (A) is preferably 30 parts by weight or more. On the other hand, when the content of the thermoplastic resin (A) exceeds 93 parts by weight, the contents of the carbon fibers (B) and the organic fibers (C) are relatively small, so that the reinforcing effect of the fibers is low and the impact is impacted. The strength decreases. The content of the thermoplastic resin (A) is preferably 85 parts by weight or less, more preferably 75 parts by weight or less.

The carbon fiber (B) in the present invention is a continuous reinforcing fiber bundle, and as a reinforcing material, imparts high mechanical properties to a molded product. Since the carbon fiber (B) has excellent specific strength, it contributes to the bending strength of the molded product. In addition, it has a higher thermal conductivity than the thermoplastic resin (A), and when used in combination with boron nitride and / or graphite (D), which will be described later, a heat conduction path is likely to be formed. The thermal conductivity can be significantly improved.

The carbon fiber (B) is not particularly limited, and examples thereof include PAN-based carbon fiber, pitch-based carbon fiber, cellulose-based carbon fiber, vapor-phase growth-based carbon fiber, and graphitized fibers thereof. The PAN-based carbon fiber is a carbon fiber made from polyacrylonitrile fiber. Pitch-based carbon fibers are carbon fibers made from petroleum tar or petroleum pitch. Cellulose-based carbon fibers are carbon fibers made from viscose rayon, cellulose acetate, or the like. The vapor phase growth type carbon fiber is a carbon fiber made from a hydrocarbon or the like. Of these, PAN-based carbon fibers are preferable because they have an excellent balance between strength and elastic modulus. Further, in order to further improve the conductivity, carbon fibers coated with a metal such as nickel, copper or ytterbium can also be used.

Further, as the carbon fiber (B), the surface oxygen concentration ratio [O / C], which is the ratio of the number of atoms of oxygen (O) and carbon (C) on the fiber surface measured by X-ray photoelectron spectroscopy, is 0. It is preferably .05 to 0.5. When the surface oxygen concentration ratio is 0.05 or more, a sufficient amount of functional groups can be secured on the surface of the carbon fiber, and stronger adhesion to the thermoplastic resin (A) can be obtained. Therefore, bending of the molded product can be obtained. Strength and tensile strength are further improved. The surface oxygen concentration ratio is more preferably 0.08 or more, further preferably 0.1 or more. The upper limit of the surface oxygen concentration ratio is not particularly limited, but is generally preferably 0.5 or less from the viewpoint of the balance between the handleability and productivity of carbon fibers. The surface oxygen concentration ratio is more preferably 0.4 or less, and further preferably 0.3 or less.

The surface oxygen concentration ratio of the carbon fiber (B) is determined by X-ray photoelectron spectroscopy according to the following procedure. First, when a sizing agent or the like adheres to the carbon fiber surface with a solvent, the sizing agent or the like adhering to the carbon fiber surface is removed with a solvent. After cutting the carbon fiber bundle to 20 mm, spreading it on a copper sample support and arranging it, AlKα1 and 2 are used as an X-ray source, and the inside of the sample chamber is kept ^{at 1 × 10-8 Torr.} The kinetic energy value (KE) of the main peak of _{C 1s} is adjusted to 1202 eV as a correction value of the peak due to charging at the time of measurement. The C 1s peak area was _{defined as K.I.} E. It is obtained by drawing a straight baseline in the range of 1191 to 1205 eV. The O 1s peak area was _{defined as K.I.} E. It is obtained by drawing a straight baseline in the range of 947 to 959 eV.

Here, the surface oxygen concentration ratio [O / C] is _{calculated as an atomic number ratio from the ratio of the O 1s} peak area and the C _1s peak area using a sensitivity correction value peculiar to the apparatus. As the X-ray photoelectron spectrometer, a model ES-200 manufactured by Kokusai Electric Inc. is used, and the sensitivity correction value is 1.74.

The means for adjusting the surface oxygen concentration ratio [O / C] to 0.05 to 0.5 is not particularly limited, but for example, methods such as electrolytic oxidation treatment, chemical solution oxidation treatment, and gas phase oxidation treatment. Can be mentioned. Of these, electrolytic oxidation treatment is preferable.

The average fiber diameter of the carbon fiber (B) is not particularly limited, but is preferably 1 to 20 μm, more preferably 3 to 15 μm, from the viewpoint of mechanical properties and surface appearance of the molded product. The number of single fibers in the case of a carbon fiber bundle is not particularly limited, but is preferably 100 to 350,000, and more preferably 20,000 to 100,000 from the viewpoint of productivity.

The carbon fiber (B) may be surface-treated for the purpose of improving the adhesiveness between the carbon fiber (B) and the thermoplastic resin (A). Examples of the surface treatment method include electrolytic treatment, ozone treatment, ultraviolet treatment, and the like.

Even if the carbon fiber is provided with a sizing agent for the purpose of preventing fluffing of the carbon fiber (B) and improving the adhesiveness between the carbon fiber (A) and the thermoplastic resin (A). It doesn't matter. By adding the sizing agent, the surface properties such as functional groups on the surface of the carbon fiber can be improved, and the adhesiveness and the overall composite properties can be improved.

Examples of the sizing agent include epoxy resins, phenol resins, polyethylene glycols, polyurethanes, polyesters, emulsifiers and surfactants. Two or more of these may be used. The sizing agent is preferably water-soluble or water-dispersible. An epoxy resin having excellent wettability with the carbon fiber (B) is preferable, and a polyfunctional epoxy resin is more preferable.

Examples of the polyfunctional epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, and phenol novolac type epoxy resin. Of these, an aliphatic epoxy resin that easily exhibits adhesiveness to the thermoplastic resin (A) is preferable. Since the aliphatic epoxy resin has a flexible skeleton, it tends to have a structure with high toughness even if the crosslink density is high. Further, when the aliphatic epoxy resin is present between the carbon fiber / the thermoplastic resin, it is flexible and difficult to peel off, so that the strength of the molded product can be further improved.

Examples of the polyfunctional aliphatic epoxy resin include diglycidyl ether compounds and polyglycidyl ether compounds. Examples of the diglycidyl ether compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ethers, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and the like. Examples thereof include polytetramethylene glycol diglycidyl ethers and polyalkylene glycol diglycidyl ethers. Examples of the polyglycidyl ether compound include glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ethers, sorbitol polyglycidyl ethers, arabitol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers, and trimethylol. Examples thereof include propaneglycidyl ethers, pentaerythritol polyglycidyl ethers, and polyglycidyl ethers of aliphatic polyhydric alcohols.

Among the above aliphatic epoxy resins, trifunctional or higher functional aliphatic epoxy resins are preferable, and aliphatic polyglycidyl ether compounds having three or more highly reactive glycidyl groups are more preferable. The aliphatic polyglycidyl ether compound has a good balance of flexibility, crosslink density, and compatibility with the thermoplastic resin (A), and can further improve the adhesiveness. Among these, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ethers, polyethylene glycol glycidyl ethers, and polypropylene glycol glycidyl ethers are more preferable.

The amount of the sizing agent adhered is preferably 0.01 to 10% by weight based on 100% by weight of the total of the carbon fiber bundle containing the sizing agent and the carbon fiber (B). When the amount of the sizing agent adhered is 0.01% by weight or more, the adhesiveness with the thermoplastic resin (A) can be further improved. The amount of the sizing agent adhered is more preferably 0.05% by weight or more, further preferably 0.1% by weight or more. On the other hand, when the amount of the sizing agent adhered is 10% by weight or less, the physical properties of the thermoplastic resin (A) can be maintained at a higher level. The amount of the sizing agent adhered is more preferably 5% by weight or less, further preferably 2% by weight or less.

The means for applying the sizing agent is not particularly limited, but for example, a sizing treatment liquid in which the sizing agent is dissolved (including dispersion) in a solvent (including a dispersion medium for dispersion) is prepared, and the sizing treatment solution is prepared. Examples thereof include a method in which the solvent is dried and vaporized to remove the treatment liquid after the treatment liquid is applied to the carbon fibers. Examples of the method of applying the sizing treatment liquid to the carbon fibers include a method of immersing the carbon fibers in the sizing treatment liquid via a roller, a method of contacting the carbon fibers with the roller to which the sizing treatment liquid is attached, and a method of atomizing the sizing treatment liquid. Then, a method of spraying on carbon fiber can be mentioned. Further, the means for applying the sizing agent may be either a batch type or a continuous type, but a continuous type that has good productivity and can reduce the variation is preferable. At this time, it is preferable to adjust the concentration of the sizing treatment liquid, the temperature, the thread tension, and the like so that the amount of the sizing agent adhered to the carbon fiber (B) becomes uniform within an appropriate range. Further, it is more preferable to ultrasonically vibrate the carbon fibers when the sizing treatment agent is applied.

The drying temperature and drying time should be adjusted according to the amount of the compound adhered, but the solvent used for the sizing treatment liquid is completely removed, the time required for drying is shortened, and the thermal deterioration of the sizing agent is prevented. From the viewpoint of preventing the sizing-treated carbon fiber (B) from becoming hard and deteriorating the spreadability, the drying temperature is preferably 150 ° C. or higher and 350 ° C. or lower, and more preferably 180 ° C. or higher and 250 ° C. or lower.

Examples of the solvent used in the sizing treatment liquid include water, methanol, ethanol, dimethylformamide, dimethylacetamide, acetone and the like. Water is preferable from the viewpoint of easy handling and disaster prevention. Therefore, when a compound that is insoluble or sparingly soluble in water is used as a sizing agent, it is preferable to add an emulsifier and a surfactant and disperse the compound in water. Specific emulsifiers or surfactants include styrene-maleic anhydride copolymers, olefin-maleic anhydride copolymers, formalin condensates of naphthalene sulfonate, anionic emulsifiers such as sodium polyacrylic acid, and polyethyleneimine. , Cationic emulsifiers such as polyvinyl imidazoline, nonylphenol ethylene oxide adducts, polyvinyl alcohol, polyoxyethylene ether ester copolymers, nonionic emulsifiers such as sorbitan ester ethyl oxide adducts and the like can be used. A nonionic emulsifier with a small interaction is preferable because it does not hinder the adhesive effect of the functional group contained in the sizing agent.

The content of carbon fiber (B) in the molded product and molding material of the present invention is that of the thermoplastic resin (A), carbon fiber (B), organic fiber (C), and boron nitride and / or graphite (D). It is 5 to 40 parts by weight with respect to 100 parts by weight in total. When the content of the carbon fiber (B) is less than 5 parts by weight, the bending strength and the impact strength of the molded product are lowered. The content of the carbon fiber (B) is preferably 10 parts by weight or more. On the other hand, when the content of the carbon fibers (B) exceeds 40 parts by weight, the dispersibility of the fibers decreases, so that the entanglement between the fibers increases. As a result, fiber breakage occurs, so that the fiber length is shortened and the impact strength is reduced. The content of the carbon fiber (B) is preferably 30 parts by weight or less.

The molded product and molding material of the present invention contain organic fibers (C) in addition to the carbon fibers (B) described above. Inorganic fibers such as carbon fiber (B) are rigid and brittle, so they are hard to get entangled and easily broken. Therefore, there is a problem that the fiber bundle made of only inorganic fibers is easily cut during the production of the molded product or easily falls off from the molded product. Therefore, by including the organic fiber (C) that is flexible and hard to break, the impact strength of the molded product can be significantly improved.

The tensile elongation at break of the organic fiber (C) is preferably 10 to 50%. When the tensile elongation at break of the organic fiber is 10% or more, the impact strength of the molded product can be further improved. On the other hand, when the tensile elongation at break of the organic fiber is 50% or less, the fiber strength and the rigidity of the molded product can be further improved. 40% or less is more preferable.

The tensile elongation at break (%) of the organic fiber (C) can be determined by the following method. In a room under standard conditions (20 ° C, 65% RH), a tensile test was conducted under the conditions of a grip interval of 250 mm and a tensile speed of 300 mm / min, and the length at the time of fiber cutting was measured (however, when cutting near the chuck). (Excluded from the data as chuck out), calculate up to two decimal places by the following formula, and round off the second decimal place. The average value of the data n3 is obtained and used as the tensile elongation at break in the present invention.
Tensile elongation at break (%) = [(length at cutting (mm) -250) / 250] × 100.

The single fiber fineness of the organic fiber (C) is preferably 0.1 to 10 dtex.

The organic fiber (C) can be appropriately selected within a range that does not significantly reduce the mechanical properties of the molded product. For example, polyolefin resins such as polyethylene and polypropylene, polyamide resins such as nylon 6, nylon 66 and aromatic polyamides, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polytetrafluoroethylene and perfluoroethylene propene copolymers, Fibers obtained by spinning fluororesins such as ethylene / tetrafluoroethylene copolymer, liquid crystal polyesters, liquid crystal polymers such as liquid crystal polyesteramide, polyarylene sulfides such as polyether ketone, polyether sulfone, and polyphenylene sulfide, and resins such as polyacrylonitrile. Can be mentioned. Two or more of these may be used. From these organic fibers (C), it is preferable to appropriately select and use them depending on the tensile elongation at break and the combination with the thermoplastic resin (A). In particular, the melting temperature of the organic fiber (C) is preferably 30 ° C. to 150 ° C. higher, more preferably 50 to 100 ° C. higher than the molding temperature (melting temperature) of the thermoplastic resin (A). Alternatively, the organic fiber (C) made of a resin that is incompatible with the thermoplastic resin (A) exists in the molded product while maintaining the fiber state, so that the impact strength of the molded product can be further improved. preferable. Examples of the organic fiber (C) having a high melting temperature include polyethylene terephthalate fiber, polyamide fiber, polyphenylene sulfide fiber, and fluororesin fiber. As the organic fiber (C) in the present invention, it is preferable to use at least one fiber selected from the group consisting of these.

In the present invention, the content of the organic fiber (C) in the molded product and the molding material is determined by the thermoplastic resin (A), the carbon fiber (B), the organic fiber (C), and the boron nitride and / or graphite (D). ) Is 1 to 30 parts by weight with respect to 100 parts by weight in total. When the content of the organic fiber (C) is less than 1 part by weight, the impact strength of the molded product is lowered. The content of the organic fiber (C) is preferably 5 parts by weight or more. On the other hand, when the content of the organic fiber (C) exceeds 30 parts by weight, the entanglement between the fibers increases, the dispersibility of the organic fiber (C) in the molded product decreases, and the impact strength of the molded product decreases. Often causes. The content of the organic fiber (C) is preferably 20 parts by weight or less, more preferably 10 parts by weight or less.

The molded article and molded material of the present invention further contain boron nitride and / or graphite (D). In the present invention, boron nitride and / or graphite (D) has the effect of improving the thermal conductivity of the molded product. Further, interestingly, by containing boron nitride and / or graphite (D), the weight average fiber length in the above-mentioned carbon fiber (B) and organic fiber (C) molded products can be increased, and bending can be performed. The strength can be greatly improved. In addition, the thermal conductivity in the thickness direction of the molded product can be increased. The reason for this cannot be determined, but probably due to the presence of boron nitride and / or graphite (D) around the carbon fibers (B) and organic fibers (C), boron nitride and / or graphite (D) during molding. ) Is subjected to the shearing force to disperse the shearing force, so that the breakage of the carbon fibers (B) and the organic fibers (C) is suppressed, and the weight average fiber lengths of the carbon fibers (B) and the organic fibers (C) are lengthened. It is presumed that it can be done. Such an effect is exhibited by either boron nitride or graphite, but graphite is contained from the viewpoint of the effect of increasing the weight average fiber length of the carbon fibers (B) and the organic fibers (C) and the balance of thermal conductivity. It is preferable to do so.

The graphite is not particularly limited, and examples thereof include natural graphite and various artificial graphites. Examples of natural graphite include earthy graphite, lump graphite, and scaly graphite. Artificial graphite is obtained by artificially orienting irregularly arranged micrographite crystals by heat-treating amorphous carbon. In addition to artificial graphite used as a general carbon material, kish graphite, decomposed graphite, etc. Examples include pyrolyzed graphite. Artificial graphite used as a general carbon material can be produced by graphitization treatment using petroleum coke or coal-based pitch coke as a main raw material. Among these, scaly graphite is preferable from the viewpoint of further improving bending strength, impact strength and thermal conductivity.

Scale graphite shows a thin and flat shape like fish scales. Since scaly graphite has a large specific surface area, it is easy to form a good conductive path. The scaly graphite having an aspect ratio of 2.5 or more is preferable. The aspect ratio of scaly graphite is A for the length in the major axis direction of scaly graphite (the longest diameter of scaly graphite), and the length in the minor axis direction of scaly graphite (length in the thickness direction of scaly graphite). ) Is B, and is represented by the ratio of A to B (A / B). The aspect ratio can be measured by magnifying the particles (for example, at a magnification of 1000 times) using a scanning electron microscope, for example.

Further, the maximum particle size of boron nitride and / or graphite (D) in the molded product of the present invention is preferably 10 to 100 μm. By setting the maximum particle size of boron nitride and / or graphite (D) contained in the molded product to 10 μm or more, it is possible to efficiently promote the formation of a heat conduction path and further improve the heat conductivity. can. On the other hand, the appearance of the molded product can be improved by setting the maximum particle size of boron nitride and / or graphite (D) contained in the molded product to 100 μm or less.

Here, the maximum particle size of boron nitride and / or graphite (D) graphite in the present invention is the boron nitride and / or boron nitride observed on the photograph when the cross section of the molded product is photographed at a magnification of 200 to 2000 times. Alternatively, it refers to the average value obtained by selecting 50 graphites having a large particle size and measuring the particle size of 50 graphites. The average value here is an arithmetic mean, and is a value obtained by dividing the total particle size by 50, which is the number of particle sizes. If the boron nitride and / or graphite observed on the photograph is not circular, the maximum diameter is measured as the particle size.

As a method for setting the particle size of boron nitride and / or graphite in the molded product in the above range, for example, a fiber-reinforced thermoplastic resin molding material in which the particle size of boron nitride and / or graphite is in a preferable range described later. Examples include a method of molding.

The content of boron nitride and / or graphite (D) in the molded product of the present invention is determined by the thermoplastic resin (A), carbon fiber (B), organic fiber (C), and boron nitride and / or graphite ( It is 1 to 30 parts by weight with respect to 100 parts by weight in total of D). Here, the content of boron nitride and / or graphite (D) refers to the content when only one of boron nitride and graphite is contained, and the total content when both are contained. .. If the content of boron nitride and / or graphite (D) is less than 1 part by weight, the thermal conductivity of the obtained molded product will decrease. Further, it is possible to reduce the effect of increasing the weight average fiber length in the molded products of the carbon fiber (B) and the organic fiber (C) described above, and the bending strength is lowered. The content of boron nitride and / or graphite (D) is preferably 5 parts by weight or more. On the other hand, if the graphite content exceeds 30 parts by weight, the impact strength decreases. The content of boron nitride and / or graphite (D) is preferably 25 parts by weight or less.

The molded product and molding material of the present invention have a melt viscosity at 200 ° C. in addition to the thermoplastic resin (A), carbon fiber (B), organic fiber (C), and boron nitride and / or graphite (D). It is preferable to contain a compound (E) lower than the thermoplastic resin (A) (hereinafter, may be referred to as "compound (E)"). Since the melt viscosity of the compound (E) at 200 ° C. is lower than that of the thermoplastic resin (A), the fluidity of the compound (E) at the time of molding is high, and the thermoplasticity of the carbon fibers (B) and the organic fibers (C) is high. The effect of dispersing in the resin (A) can be enhanced. Examples of the compound (E) include an epoxy resin, a phenol resin, a terpene resin, and a cyclic polyarylene sulfide resin. Two or more of these may be contained. As the compound (E), a compound having a high affinity with the thermoplastic resin (A) is preferable. By selecting the compound (E) having a high affinity with the thermoplastic resin (A), the carbon fiber (B) is efficiently compatible with the thermoplastic resin (A) during the production or molding of the molding material. And the dispersibility of the organic fiber (C) can be further improved.

The compound (E) is appropriately selected depending on the combination with the thermoplastic resin (A). For example, if the molding temperature is in the range of 150 ° C. to 270 ° C., the terpene resin is preferably used. When the molding temperature is in the range of 270 ° C. to 320 ° C., an epoxy resin, a phenol resin, and a cyclic polyarylene sulfide resin are preferably used. Specifically, when the thermoplastic resin (A) is a polypropylene resin, the compound (E) is preferably a terpene resin. When the thermoplastic resin (A) is a polycarbonate resin or a polyarylene sulfide resin, the compound (E) is preferably an epoxy resin, a phenol resin, or a cyclic polyarylene sulfide resin. When the thermoplastic resin (A) is a polyamide resin, the compound (E) is preferably a terpene phenol resin.

The melt viscosity of compound (E) at 200 ° C. is preferably 0.01 to 10 Pa · s. When the melt viscosity at 200 ° C. is 0.01 Pa · s or more, the fracture starting from the compound (E) can be further suppressed, and the impact strength of the molded product can be further improved. The melt viscosity is more preferably 0.05 Pa · s or more, and further preferably 0.1 Pa · s or more. On the other hand, when the melt viscosity at 200 ° C. is 10 Pa · s or less, the compound (E) can be easily impregnated into the carbon fibers (B) and the organic fibers (C). Therefore, when molding the molding material of the present invention, the dispersibility of the carbon fibers (B) and the organic fibers (C) can be further improved. The melt viscosity is preferably 5 Pa · s or less, and more preferably 2 Pa · s or less. Here, the melt viscosities of the thermoplastic resin (A) and the compound (E) at 200 ° C. can be measured by a viscoelasticity measuring instrument at 0.5 Hz using a 40 mm parallel plate.

As will be described later, when the compound (E) is attached to the carbon fibers (B) and the organic fibers (C) to obtain the (F) composite fiber bundle, the melting temperature (melting bath) when the compound (E) is supplied. The temperature inside) is preferably 100 to 300 ° C. Therefore, as an index of the impregnation property of the compound (E) into the carbon fibers (B) and the organic fibers (C), attention was paid to the melt viscosity of the compound (E) at 200 ° C. When the melt viscosity at 200 ° C. is in the above-mentioned preferable range, the carbon fiber (B) and the organic fiber (C) are excellently impregnated in such a preferable melt temperature range, so that the carbon fiber (B) and the organic fiber (C) are excellent. ) Can be further improved, and the bending strength and tensile strength of the molded product can be further improved.

The number average molecular weight of compound (E) is preferably 200 to 50,000. When the number average molecular weight is 200 or more, the bending strength and the tensile strength of the molded product can be further improved. The number average molecular weight is more preferably 1,000 or more. Further, when the number average molecular weight is 50,000 or less, the viscosity of the compound (E) is appropriately low, so that the carbon fibers (B) and the organic fibers (C) contained in the molded product are excellently impregnated. , The dispersibility of the carbon fibers (B) and the organic fibers (C) in the molded product can be further improved. The number average molecular weight is more preferably 3,000 or less. The number average molecular weight of such a compound can be measured by gel permeation chromatography (GPC).

The weight loss of compound (E) at 10 ° C./min temperature rise (in air) at the molding temperature is preferably 5% by weight or less. More preferably, it is 3% by weight or less. When the heating weight loss is 5% by weight or less, the generation of decomposition gas can be suppressed when the carbon fibers (B) and the organic fibers (C) are impregnated, and the generation of voids can be suppressed during molding. can. In addition, the generated gas can be suppressed especially in molding at a high temperature.

The weight loss by heating in the present invention represents the weight loss rate of the compound (E) before and after heating under the heating conditions, where the weight of the compound (E) before heating is 100%, and can be calculated by the following formula. .. The weight before and after heating can be determined by measuring the weight at the molding temperature by thermogravimetric analysis (TGA) using a platinum sample pan under the condition of a heating rate of 10 ° C./min in an air atmosphere. can.
(Weight loss by heating) [Weight%] = {(Weight before heating-Weight after heating) / Weight before heating} x 100.

The rate of change in melt viscosity of compound (E) after heating at 200 ° C. for 2 hours is preferably 2% or less. By setting the rate of change in melt viscosity to 2% or less, even when the composite fiber bundle (F) is manufactured for a long period of time, uneven adhesion and the like can be suppressed and the composite fiber bundle (F) can be stably manufactured. can. The rate of change in melt viscosity is more preferably 1.5% or less, and even more preferably 1.3% or less.

Here, the rate of change in melt viscosity of compound (E) can be determined by the following method. First, using a 40 mm parallel plate, the melt viscosity at 200 ° C. is measured with a viscoelasticity measuring device at 0.5 Hz. Further, after the compound (E) is allowed to stand in a hot air dryer at 200 ° C. for 2 hours, the melt viscosity at 200 ° C. is measured in the same manner, and the viscosity change rate is calculated by the following formula.
(Melting viscosity change rate [%]) = {| (Melting viscosity at 200 ° C. before heating at 200 ° C. for 2 hours-Melting viscosity at 200 ° C. after heating at 200 ° C. for 2 hours) | / (At 200 ° C.) Melt viscosity at 200 ° C. before heating for 2 hours)} × 100.

In the present invention, the epoxy resin preferably used as the compound (E) is a compound having two or more epoxy groups, which does not substantially contain a curing agent and is so-called three-dimensional even when heated. A compound that does not cure by cross-linking. Since the epoxy resin has an epoxy group, it easily interacts with the carbon fibers (B) and the organic fibers (C), and at the time of impregnation, it easily blends with the composite fiber bundle (F) and is easily impregnated. In addition, the dispersibility of the carbon fibers (B) and the organic fibers (C) during the molding process is further improved.

Here, examples of the epoxy resin include a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, and an alicyclic epoxy resin. Two or more of these may be used.

Examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, halogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, resorcinol type epoxy resin, and hydrogenated bisphenol. A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin having ether bond, naphthalene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, etc. Can be mentioned.

Examples of the glycidyl ester type epoxy resin include hexahydrophthalic acid glycidyl ester and dimer acid diglycidyl ester.

Examples of the glycidylamine type epoxy resin include triglycidyl isocyanurate, tetraglycidyldiaminodiphenylmethane, tetraglycidylmethylenediamine, and aminophenol type epoxy resin.

Examples of the alicyclic epoxy resin include 3,4-epoxy-6-methylcyclohexylmethylcarboxylate and 3,4-epoxycyclohexylmethylcarboxylate.

Among them, glycidyl ether type epoxy resin is preferable, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are more preferable because the balance between viscosity and heat resistance is excellent.

The number average molecular weight of the epoxy resin used as the compound (E) is preferably 200 to 5000. When the number average molecular weight of the epoxy resin is 200 or more, the mechanical properties of the molded product can be further improved. 800 or more is more preferable, and 1000 or more is further preferable. On the other hand, when the number average molecular weight of the epoxy resin is 5000 or less, the composite fiber bundle (F) is excellently impregnated, and the dispersibility of the carbon fibers (B) and the organic fibers (C) can be further improved. 4000 or less is more preferable, and 3000 or less is further preferable. The number average molecular weight of the epoxy resin can be measured by using gel permeation chromatography (GPC).

The terpene resin includes, for example, a polymer or a copolymer obtained by polymerizing a terpene monomer with an aromatic monomer or the like in the presence of a Friedel-Crafts type catalyst in an organic solvent, if necessary. Can be mentioned.

Examples of the terpine monomer include α-pinene, β-pinene, dipentene, d-limonene, myrcene, aloosimene, osimene, α-ferrandrene, α-terpinene, γ-terpinene, terpineol, 1,8-cineole, and the like. Examples thereof include 1,4-cineol, α-terpineol, β-terpineol, γ-terpineol, sabinene, paramentadiens and curenes. Examples of the aromatic monomer include styrene and α-methylstyrene. Among them, α-pinene, β-pinene, dipentene, and d-limonene are preferable because they have excellent compatibility with the thermoplastic resin (A), and further, homopolymers of these terpene monomers are more preferable.

Further, a hydrogenated terpene resin obtained by hydrogenating these terpene resins or a terpene phenol resin obtained by reacting a terpene monomer with phenols in the presence of a catalyst can also be used. Here, as the phenols, those having 1 to 3 substituents of at least one selected from the group consisting of an alkyl group, a halogen atom and a hydroxyl group on the benzene ring of phenol are preferably used. Specific examples thereof include cresol, xylenol, ethylphenol, butylphenol, t-butylphenol, nonylphenol, 3,4,5-trimethylphenol, chlorophenol, bromophenol, chlorocresol, hydroquinone, resorcinol, orsinol and the like. Two or more of these may be used. Of these, phenol and cresol are preferred. Among these, the hydrogenated terpene resin is preferable because it has excellent compatibility with the thermoplastic resin (A), particularly the polypropylene resin.

The glass transition temperature of the terpene resin is not particularly limited, but is preferably 30 to 100 ° C. When the glass transition temperature is 30 ° C. or higher, the handleability of the compound (E) at the time of molding is excellent. Further, when the glass transition temperature is 100 ° C. or lower, the fluidity of the compound (E) during the molding process can be appropriately suppressed and the moldability can be improved.

The number average molecular weight of the terpene resin is preferably 200 to 5000. When the number average molecular weight is 200 or more, the bending strength and the tensile strength of the molded product can be further improved. Further, when the number average molecular weight is 5000 or less, the viscosity of the terpene resin is appropriately low, so that the impregnation property is excellent, and the dispersibility of the carbon fibers (B) and the organic fibers (C) in the molded product is further improved. Can be done. The number average molecular weight of the terpene resin can be measured by gel permeation chromatography (GPC).

The content of compound (E) in the molded product and molding material of the present invention is the sum of the thermoplastic resin (A), carbon fiber (B), organic fiber (C), and boron nitride and / or graphite (D). 1 to 20 parts by weight is preferable with respect to 100 parts by weight. When the content of the compound (E) is 1 part by weight or more, the fluidity of the carbon fibers (B) and the organic fibers (C) in the molded product is further improved, and the dispersibility is further improved. The content of compound (E) is preferably 2 parts by weight or more, and preferably 4 parts by weight or more. On the other hand, when the content of the compound (E) is 20 parts by weight or less, the bending strength, tensile strength and impact strength of the molded product can be further improved. 15 parts by weight or less is preferable, 12 parts by weight or less is more preferable, and 10 parts by weight or less is further preferable.

The molded article and the molded material of the present invention may contain other components in addition to the above (A) to (E) as long as the object of the present invention is not impaired. Examples of other components include thermosetting resins, inorganic fillers other than carbon fiber, flame retardants, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, and coloring. Examples thereof include inhibitors, heat stabilizers, mold release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, and coupling agents.

In the molded product of the present invention, the weight average fiber length (L _wb ) of the carbon fiber (B) in the molded product is 0.7 to 2 mm. _{When the average fiber length (L wb} ) of the carbon fibers (B) is less than 0.7 mm, the effect of improving the bending strength and impact strength of the molded product is difficult to achieve. L _wb is preferably 1.0 mm or more. On the other hand, when the weight average fiber length (L _wb ) exceeds 2.0 mm, the entanglement of the carbon fibers (B) between the single yarns is less likely to be suppressed and the dispersibility is less likely to be improved, so that the bending strength of the molded product is difficult. It is difficult to achieve the improvement effect. L _wb is more preferably 1.7 mm or less.

Further, in the molded product of the present invention, the weight average fiber length (L _wc ) of the organic fiber (C) in the molded product is 2.5 to 5 mm. When the weight average fiber length (L _wc ) of the organic fiber (C) is less than 2.5 mm, the reinforcing effect of the organic fiber (C) in the molded product is difficult to exert, and the impact strength is inferior. The L _wc is preferably 2.7 mm or more. On the other hand, when the average fiber length (L _wb ) exceeds 5 mm, the entanglement of the organic fibers (C) between the single yarns is difficult to be suppressed and the dispersibility is difficult to improve, so that the impact strength of the molded product is inferior. The L _wc is more preferably 4 mm or less.

Here, the "weight average fiber length" in the present invention is the following formula in which the method for calculating the weight average molecular weight is applied to the calculation of the fiber length, and the contribution of the fiber length is taken into consideration instead of simply taking the number average. Refers to the average fiber length calculated from. However, the following formula is applied when the fiber diameter and density of the carbon fiber (B) and the organic fiber (C) are constant.
Weight average fiber length = Σ (Mi ² x Ni) / Σ (Mi x Ni)
Mi: Fiber length (mm)
Ni: Number of reinforcing fibers with fiber length Mi.

The weight average fiber length can be measured by the following method. The molded product is heated while being sandwiched between glass plates on a hot stage set at 200 to 300 ° C. to form a film and uniformly dispersed. The film in which the fibers are uniformly dispersed is observed with an optical microscope (50 to 200 times). The fiber lengths of 1000 randomly selected carbon fibers (B) and organic fibers (C) were measured, and the weight average fiber length (L _wb ) and organic fibers (C) of the carbon fibers (B) were measured from the above formula. The weight average fiber length (L _wc ) of is calculated.

The weight average fiber lengths of the carbon fibers (B) and the organic fibers (C) in the molded product can be adjusted by, for example, molding conditions. Examples of molding conditions include pressure conditions such as back pressure and holding pressure, time conditions such as injection time and holding pressure time, and temperature conditions such as cylinder temperature and mold temperature in the case of injection molding. Specifically, by increasing the pressure condition such as back pressure, the shearing force in the cylinder can be increased, so that the average fiber length of the carbon fibers (A) can be shortened. Further, by shortening the injection time, the shearing force at the time of injection can be increased, and the average fiber length of the carbon fiber (A) can be shortened. Further, by lowering the temperature such as the cylinder temperature and the mold temperature, the viscosity of the flowing resin can be increased and the shearing force can be increased, so that the average fiber length of the carbon fibers (A) can be shortened. In the present invention, the average fiber length of the carbon fibers (A) in the molded product can be set within a desired range by appropriately changing the conditions as described above.

Further, it can be easily adjusted to the above-mentioned preferable range by molding a molding material having a preferable form described later.

The molded product of the present invention preferably has a thermal conductivity of 0.5 to 4 W / m · K measured by a steady-state method in the thickness direction of the molded product. When the thermal conductivity is 0.5 W / m · K or more, the heat generated in the molded product can be efficiently dissipated. The thermal conductivity is more preferably 0.6 W / m · K or more. On the other hand, when the thermal conductivity is 4 W / m · K or less, it is possible to suppress malfunction of the electronic device due to heat transfer to other parts before heat is dissipated. The thermal conductivity is more preferably 3.5 W / m · K or less, further preferably 3 W / m · K or less. Here, the thermal conductivity of the molded product in the present invention refers to the thermal conductivity at 80 ° C., and can be measured using GH-1S manufactured by ULVAC Riko.

The thickness direction of the molded product is perpendicular to the flow direction during injection molding. By increasing the thermal conductivity in the thickness direction, heat can be dissipated more effectively when used in a housing of a component that generates heat. Examples of the method of setting the thermal conductivity in the thickness direction of the molded product within the above-mentioned range include a method of setting the weight average fiber length of the carbon fibers (B) in the molded product within the above-mentioned preferable range.

The molded product of the present invention preferably has a bending strength of 150 to 300 MPa. When the bending strength is 150 MPa or more, the durability of the molded product can be improved. 180 MPa or more is more preferable, and 200 MPa or more is further preferable. Here, the bending strength of the molded product can be measured according to ISO 178. Examples of the method for setting the bending strength of the molded product within the above-mentioned range include a method for setting the weight average fiber length of the carbon fibers (B) existing inside the molded product within the above-mentioned preferable range.

Next, the form of the molding material of the present invention will be described. In the present invention, the "molding material" means a raw material used when molding a molded product by injection molding or the like.

In the present invention, the thermoplastic resin (A), carbon fiber (B), organic fiber (C), boron nitride and / or graphite (D), and the melt viscosity at 200 ° C. are lower than those of the thermoplastic resin (A). A fiber-reinforced thermoplastic resin molding material containing the compound (E), which is a total of 100 of the thermoplastic resin (A), carbon fibers (B), organic fibers (C), and boron nitride and / or graphite (D). With respect to parts by weight, 20 to 93 parts by weight of the thermoplastic resin (A), 5 to 40 parts by weight of the carbon fiber (B), 1 to 30 parts by weight of the organic fiber (C), and boron nitride and / or graphite ( The molding of the present invention comprises a fiber-reinforced thermoplastic resin molding material containing 1 to 30 parts by weight of D) and 1 to 20 parts by weight of a compound (E) having a melt viscosity at 200 ° C. lower than that of the thermoplastic resin (A). It can be suitably used as a molding material for obtaining a product.

As the thermoplastic resin (A), carbon fiber (B), organic fiber (C), boron nitride and / or graphite (D), and compound (E) in the molding material, the molded product of the present invention has been described above. (A) to (E) can be used, and those exemplified as other components for the molded product of the present invention can also be contained. Moreover, those effects are also as described above.

The molding material of the present invention preferably has a fiber bundle containing carbon fibers (B) and organic fibers (C), which are continuous fiber bundles, in the thermoplastic resin (A). A composite fiber bundle (F) in which the compound (E) is filled between each single fiber of the fiber bundle may be provided. The composite fiber bundle (F) is a state in which the fiber bundle is impregnated with the compound (E), and the carbon fibers (B) and the organic fibers (C) are dispersed like islands in the sea of the compound (E). Is.

In the molding material of the present invention, boron nitride and / or graphite (D) may be contained in any of the raw materials. It may be contained in the fiber bundle or the composite fiber bundle (F), may be contained in the thermoplastic resin (A), or may be contained in both of them. As an embodiment contained in the fiber bundle or the composite fiber bundle (F), for example, the thermoplastic resin (A) and boron nitride and / or graphite (D) are impregnated in the fiber bundle (F) together with the compound (E). Examples thereof include a mode in which the carbon fiber (B) and the organic fiber (C) are attached to the surface of the carbon fiber (B) or contained in the single fiber. Boron nitride and / or graphite (D) is preferably contained in the thermoplastic resin (A).

The molding material of the present invention has a structure in which the fiber bundle or composite fiber bundle (F) is coated with a composition containing the thermoplastic resin (A) and boron nitride and / or graphite (D). Is preferable. The composition may further contain other components if necessary. Here, the "coated structure" means that the composition containing the thermoplastic resin (A) and boron nitride and / or graphite (D) is applied to the surface of the fiber bundle or the composite fiber bundle (F). Refers to a structure that is arranged and adhered.

Although the molding material compound (E) of the present invention is contained, the compound (E) often has a low molecular weight, and is usually a relatively brittle and easily crushable solid or a liquid at room temperature. By including the thermoplastic resin (A) on the outside of the composite fiber bundle (F), the high molecular weight thermoplastic resin (A) protects the composite fiber bundle (F) and transports and handles the molding material. The shape of the molding material can be maintained by suppressing crushing and scattering of the compound (E) due to impact and scratching at the time. From the viewpoint of handleability, the molding material of the present invention preferably retains the above-mentioned shape until it is subjected to molding.

The composition containing the composite fiber bundle (F), the thermoplastic resin (A), and boron nitride and / or graphite (D) is a part of the composite fiber bundle (F) in the vicinity of the boundary. It may be in a state where it has penetrated and is compatible with each other, or it may be in a state where the composite fiber bundle (F) is impregnated with the composition.

In the molding material of the present invention, it is preferable that carbon fibers (B) and organic fibers (C) are unevenly distributed in the cross section of the fiber bundle. Here, the fiber bundle cross section refers to a cross section perpendicular to the fiber longitudinal direction of the fiber bundle. By unevenly distributing the carbon fibers (B) and the organic fibers (C) in the fiber bundle cross section, the entanglement of the carbon fibers (B) and the organic fibers (C) during molding is suppressed, and the carbon fibers (B) and the organic fibers are suppressed. A molded product in which (C) is uniformly dispersed can be obtained. Therefore, the impact strength of the molded product can be further improved. Here, in the present invention, "uneven distribution" means that the carbon fibers (B) and the organic fibers (C) are not evenly present in all regions but partially unevenly present in the fiber bundle cross section. Say. For example, in the fiber bundle cross section as shown in FIG. 1, the carbon fiber (B) 1 contains the organic fiber (C) 2, or the organic fiber (C) 2 is carbon as shown in FIG. In a so-called core-sheath structure such as a form containing fiber (B) 1 or in a fiber bundle cross section as shown in FIG. 3, a bundle of carbon fiber (B) 1 and a bundle of organic fiber (C) 2 are present. A structure or the like that exists in a state of being separated by a certain boundary portion is mentioned as an aspect of "uneven distribution" in the present invention. In the present invention, the term "inclusion" refers to a mode in which the carbon fiber (B) is arranged in the core portion and the organic fiber (C) is arranged in the sheath portion, or the organic fiber (C) is arranged in the core portion and the carbon fiber (B) is provided in the sheath portion. Refers to the mode of arranging in the part. In the case of the embodiment shown in FIG. 3, at least a part of each of the carbon fiber (B) and the organic fiber (C) in the cross section of the fiber bundle (F) is an outer layer thermoplastic resin (A), boron nitride and / or graphite. It is in contact with the composition 3 containing (D). At this time, in the embodiment in which the carbon fiber (B) or the organic fiber (C) is in contact with the composition, the carbon fiber (B) or the organic fiber (C) is in contact with the composition via the compound (E). Aspects are also included.

In the present invention, as a method of confirming that the carbon fibers (B) and the organic fibers (C) are unevenly distributed in the fiber bundle, for example, a cross section perpendicular to the fiber longitudinal direction of the molding material is magnified. Examples thereof include a method of observing with an optical microscope set to 300 times and performing image processing of the obtained microscope image for analysis.

As a method of unevenly distributing the carbon fibers (B) and the organic fibers (C) in the cross section of the fiber bundle, a method of aligning the bundle of the carbon fibers (B) and the bundle of the organic fibers (C) to produce the above-mentioned molding material. Can be mentioned. By aligning the bundles with each other to produce a molding material, the carbon fibers (B) and the organic fibers (C) exist as independent fiber bundles and can be unevenly distributed. Increasing the number of single fibers in the bundle of carbon fibers (B) and organic fibers (C) to be used can make the bundle larger, and decreasing the number of single fibers can make the bundle smaller. Is possible.

In the molding material of the present invention, it is preferable that the length of the fiber bundle and the length of the molding material are substantially the same. Since the length of the fiber bundle is substantially the same as the length of the molding material, the fiber lengths of the carbon fibers (B) and the organic fibers (C) in the molded product can be lengthened, resulting in better mechanical properties. Can be obtained. The length of the molding material is the length in the fiber bundle orientation direction in the molding material. Further, "substantially the same length" means that the fiber bundle is not intentionally cut inside the molding material, and the fiber bundle that is significantly shorter than the total length of the molding material is not substantially included. In particular, the amount of the fiber bundle shorter than the total length of the molding material is not limited, but the content of the fiber bundle having a length of 50% or less of the total length of the molding material is 30% by mass or less in the total fiber bundle. It is preferably 20% by mass or less, and more preferably 20% by mass or less. It is preferable that the molding material is continuous while maintaining substantially the same cross-sectional shape in the longitudinal direction.

The length of the molding material is usually in the range of 3 mm to 15 mm. The length of the molding material is obtained by taking a photograph of the molding material at a magnification of 10 to 100 times and measuring the length of the molding material in the fiber bundle orientation direction among the molding materials observed on the photograph. The method for measuring the molding material can be calculated by randomly selecting 100 pieces, measuring the lengths of 100 pieces, and obtaining the average value thereof.

The maximum particle size of boron nitride and / or graphite (D) in the molding material of the present invention is preferably 50 to 500 μm. When the maximum particle size of boron nitride and / or graphite (D) in the molding material is 50 μm or more, breakage of the carbon fibers (B) and the organic fibers (C) can be further suppressed. The particle size of boron nitride and / or graphite (D) is more preferably 60 μm or more, further preferably 70 μm or more. On the other hand, when the maximum particle size of boron nitride and / or graphite (D) in the molding material is 500 μm or less, the dispersibility in the molded product can be improved and the appearance can be improved. The maximum particle size of boron nitride and / or graphite (D) is more preferably 400 μm or less, further preferably 300 μm or less. Further, by setting the maximum particle size of boron nitride and / or graphite (D) in the molding material to the above-mentioned preferable range, the maximum particle size of boron nitride and / or graphite (D) in the molded product is set to the above-mentioned preferable range. Can be easily adjusted.

Here, the maximum particle size of boron nitride and / or graphite in the molding material can be measured in the same manner as the maximum particle size of boron nitride and / or graphite in the molded product.

By molding the molding material, it is possible to obtain a molded product having excellent dispersibility of carbon fibers (B) and organic fibers (C) and excellent bending strength, impact strength and thermal conductivity.

Subsequently, a method for producing the molding material of the present invention will be described. The molding material of the present invention can be obtained, for example, by the following method.

First, the roving of the carbon fiber (B) and the roving of the organic fiber (C) are combined in parallel with respect to the fiber longitudinal direction to prepare a fiber bundle having the carbon fiber (B) and the organic fiber (C). Next, the fiber bundle is impregnated with the melted compound (E) to prepare a composite fiber bundle (F). Further, a fiber bundle or a composite fiber bundle (F) is guided to an impregnated die filled with a composition containing the molten thermoplastic resin (A) and boron nitride and / or graphite (D), and the thermoplastic resin (A) and nitride are nitrided. A composition containing boron and / or graphite (D) is coated on the outside of the fiber bundle or composite fiber bundle (F) and pulled out through a nozzle. Examples thereof include a method of obtaining a molding material by pelletizing to a predetermined length after cooling and solidifying. The thermoplastic resin (A) and boron nitride and / or graphite (D) may be impregnated in the fiber bundle as long as it is contained outside the composite fiber bundle (F).

Further, a molding material in which the composite fiber bundle (F) produced by the above method is coated with a composition containing a thermoplastic resin (A) and boron nitride and / or graphite (D), and a thermoplastic resin (A) are pellet-blended. Then, a mixture of molding materials may be obtained. In this case, the content of carbon fiber (B), organic fiber (C), boron nitride and / or graphite (D) in the molded product can be easily adjusted. Further, a molding material in which carbon fibers (B) are coated with a thermoplastic resin (A) and, if necessary, a composition melt-kneaded with boron nitride and / or graphite (D), and organic fibers (C) are coated with a thermoplastic resin (A). ) And, if necessary, a molding material coated with a composition obtained by melt-kneading boron nitride and / or graphite (D) may be pellet-blended to obtain a molding material mixture. The compound (E) is preferably impregnated into the carbon fibers (B) and / or the organic fibers (C). Further, it is more preferable that the compound (E) is impregnated with the carbon fiber (B) and the organic fiber (C) with the compound (I) described later. At this time, boron nitride and / or graphite (D) may be contained in any of the molding materials, or may be contained in only one of the molding materials. Here, the pellet blend refers to stirring and mixing a plurality of materials (pellets) at a temperature at which the resin components do not melt to obtain a substantially uniform state, which is different from melt kneading, and is mainly used for injection molding or injection molding. It is preferably used when a pellet-shaped molding material such as extrusion molding is used.

The molding material mixture will be described in more detail. The molding material mixture includes at least a thermoplastic resin (A), carbon fibers (B), boron nitride and / or graphite (D), and a carbon fiber reinforced thermoplastic resin molding material (X) containing compound (E). "Carbon fiber reinforced molding material (X)") and at least thermoplastic resin (H), organic fiber (C), boron nitride and / or graphite (D), and melt viscosity at 200 ° C. are hot. Organic fiber reinforced thermoplastic resin molding material (Y) containing compound (I) lower than plastic resin (H) (sometimes referred to as "compound (I)") (sometimes referred to as "organic fiber reinforced molding material (Y)" Yes) is preferred. The carbon fiber reinforced molding material (X) contains a composite fiber bundle (G) formed by impregnating the carbon fiber (B) with the compound (E), and the thermoplastic resin (A) is formed on the outside of the composite fiber bundle (G). It is preferable to have a structure containing boron nitride and / or graphite (D), and it is preferable that the length of the carbon fiber (B) and the length of the carbon fiber reinforced molding material are substantially the same. Further, the organic fiber reinforced molding material (Y) contains a composite fiber bundle (J) formed by impregnating the organic fiber (C) with the compound (I), and a thermoplastic resin (H) is provided on the outside of the composite fiber bundle (J). ) Is preferably included. As the compound (I), the compound exemplified in the compound (E) described above can be used, and the compound (E) and the compound (I) may be the same compound or different compounds. good. As the thermoplastic resin (H), the resin exemplified in the thermoplastic resin (A) described above can be used, and even if the thermoplastic resin (A) and the thermoplastic resin (H) are the same compound, they may be used. It may be a different compound.

The carbon fiber reinforced molding material (X) is thermoplastic with respect to a total of 100 parts by weight of the thermoplastic resin (A), carbon fiber (B), boron nitride and / or graphite (D), and compound (E). Contains 20 to 93 parts by weight of resin (A), 5 to 40 parts by weight of carbon fiber (B), 1 to 30 parts by weight of boron nitride and / or graphite (D), and 1 to 20 parts by weight of compound (E). Is preferable. The organic fiber reinforced molding material (Y) is the organic fiber (C) with respect to a total of 100 parts by weight of the organic fiber (C), boron nitride and / or graphite (D), the thermoplastic resin (H) and the compound (I). Is preferably contained in an amount of 1 to 30 parts by weight, boron nitride and / or graphite (D) in an amount of 1 to 30 parts by weight, a thermoplastic resin (H) in an amount of 20 to 93 parts by weight, and compound (I) in an amount of 1 to 20 parts by weight. ..

For a total of 100 parts by weight of the carbon fiber reinforced molding material (X) and the organic fiber reinforced molding material (Y), 50 to 80 parts by weight of the carbon fiber reinforced molding material (X) and the organic fiber reinforced molding material (Y) are used. It is preferable to blend 20 to 50 parts by weight.

Next, a method for producing the molded product of the present invention will be described. By molding the above-mentioned molding material of the present invention, it is possible to obtain a molded product having excellent dispersibility of carbon fibers (B) and organic fibers (C) and excellent bending strength, impact strength and thermal conductivity. As the molding method, a molding method using a mold is preferable, and various molding methods such as injection molding, extrusion molding, and press molding can be used. In particular, a continuously stable molded product can be obtained by a molding method using an injection molding machine. The conditions for injection molding are not particularly specified, but for example, injection time: 0.5 seconds to 10 seconds, more preferably 2 seconds to 10 seconds, back pressure: 0.1 MPa to 10 MPa, more preferably 2 MPa to 8 MPa. , Holding pressure: 1 MPa to 50 MPa, more preferably 1 MPa to 30 MPa, Holding time: 1 second to 20 seconds, more preferably 5 seconds to 20 seconds, Cylinder temperature: 200 ° C. to 320 ° C., Mold temperature: 20 ° C. to The condition of 100 ° C. is preferable. Here, the cylinder temperature indicates the temperature of a portion where the molding material of the injection molding machine is heated and melted, and the mold temperature indicates the temperature of the mold for injecting the resin for forming a predetermined shape. By appropriately selecting these conditions, particularly the injection time, back pressure, and mold temperature, the fiber lengths of the carbon fibers and organic fibers in the molded product can be easily adjusted.

The molded product of the present invention is excellent in mechanical properties, particularly bending strength, impact strength and thermal conductivity. The molded products and molding materials of the present invention are used for automobile parts such as instrument panels, door beams, undercovers, spare tire covers, front ends, structural members, internal parts, telephones, facsimiles, VTRs, copiers, etc. TVs, microwave ovens, audio equipment, toiletries, laser discs (registered trademarks), refrigerators, air conditioners and other household and office electrical equipment parts, personal computers, keyboards inside personal computers, etc. Examples include members for electrical and electronic devices represented by a keyboard support that supports the above.

Examples will be shown below and the present invention will be described in more detail, but the present invention is not limited to the description of these examples. First, a method for evaluating various characteristics used in this embodiment will be described.

(1) Measurement of melt viscosity For the thermoplastic resins (A) and compound (E) used in each Example and Comparative Example, a 40 mm parallel plate was used at 0.5 Hz, and a viscoelasticity measuring instrument was used at 200 ° C. The melt viscosity was measured. Further, after the compound (E) was allowed to stand in a hot air dryer at 200 ° C. for 2 hours, the melt viscosity at 200 ° C. was measured in the same manner, and the rate of change in melt viscosity before and after drying was measured.

(2) Measurement of Weight Average Fiber Length The molded product was heated while being sandwiched between glass plates on a hot stage set at 200 to 300 ° C. to form a film and uniformly dispersed. A film in which carbon fibers (B) and organic fibers (C) were uniformly dispersed was observed with an optical microscope (50 to 200 times). The fiber lengths of 1000 randomly selected carbon fibers (B) and 1000 randomly selected organic fibers (C) were measured, and the weight average fiber length was calculated from the following formula. ..
Average fiber length = Σ (Mi ² x Ni) / Σ (Mi x Ni)
Mi: Fiber length (mm)
Ni: Number of fibers with fiber length Mi

(3) Measurement of bending strength of molded products For the ISO type dumbbell test pieces obtained in each example and comparative example, the fulcrum distance was set to 64 mm using a 3-point bending test tool (indenter radius 5 mm) in accordance with ISO 178. The bending strength was measured under the test conditions of a test speed of 2 mm / min. As a testing machine, an "Instron (registered trademark)" universal testing machine type 5566 (manufactured by Instron) was used.

(4) Charpy impact strength measurement of molded products The parallel parts of the ISO type dumbbell test pieces obtained in each example and comparative example were cut out, and the C1-4-01 type testing machine manufactured by Tokyo Testing Machine Co., Ltd. was used to comply with ISO179. Then, a Charpy impact test with a V notch was carried out, and the impact strength (kJ / cm ² ) was calculated.

(5) Measurement of Thermal Conductivity of Molded Product A test piece having a thickness of 20 mm × 20 mm × 4 mm was cut out from the ISO type dumbbell test piece obtained in each Example and Comparative Example, and 80 by using GH-1S manufactured by ULVAC Riko. The thermal conductivity in the thickness direction at ° C was measured. Further, five test pieces having a thickness of 20 mm × 4 mm × 4 mm were cut out from the ISO type dumbbell test piece, the five test pieces were arranged side by side with the flow direction vertical, and 80 using GH-1S manufactured by ULVAC Riko. The thermal conductivity in the flow direction at ° C was measured.

(6) Evaluation of Fiber Dispersity of Molded Product The number of undispersed CF bundles present on the front and back surfaces of a test piece having a thickness of 80 mm × 80 mm × 3 mm obtained in each Example and Comparative Example was visually counted. The evaluation was performed on 50 molded products, and the fiber dispersibility was judged for the total number of molded products according to the following criteria, and A was regarded as acceptable.
A: Less than one undispersed CF bundle B: One or more undispersed CF bundles.

(7) Measurement of Grain Size of (D) Graphite of Molded Product and Molding Material The central part of the 80 mm × 10 mm × 4 mm thick test piece obtained by each Example and Comparative Example, or the cross section of the molding material, with a magnification of 200. A photograph was taken at a magnification of ~ 2000, and 50 of the (D) graphites observed on the photograph were selected from those having a large particle size, and the particle size of 50 pieces was measured to obtain the average value. When the graphite was not circular as observed on the photograph, the maximum diameter was measured as the particle size.

(8) Length of Molding Material The molding material was photographed at a magnification of 10 to 100 times, and among the molding materials observed on the photograph, the length of the molding material in the fiber bundle orientation direction was measured. It was calculated by randomly selecting 100 molding materials, measuring the lengths of 100 molding materials, and calculating the average value thereof.

Reference example 1. Preparation of carbon fiber (B) Spinning, firing treatment, and surface oxidation treatment were performed from a polymer containing polyacrylonitrile as the main component, and the total number of single yarns was 24,000, the diameter of single fibers was 7 μm, and the mass per unit length was 1. Continuous carbon fibers having a specific gravity of 6 g / m, a specific gravity of 1.8 g / cm ³ , and a surface oxygen concentration ratio of [O / C] of 0.2 were obtained. The strand tensile strength of this continuous carbon fiber was 4,880 MPa, and the strand tensile elastic modulus was 225 GPa. Subsequently, a sizing agent mother liquor in which glycerol polyglycidyl ether was dissolved in water so as to be 2% by weight was prepared as a polyfunctional compound, the sizing agent was added to the carbon fibers by an immersion method, and the carbon fibers were dried at 230 ° C. rice field. The amount of adhering sizing agent to the carbon fibers thus obtained was 1.0% by weight.

Thermoplastic resin (A)
(A-1)
Pellet blend of polypropylene resin ("Prime Polypro" (registered trademark) J137 manufactured by Prime Polymer Co., Ltd.) and maleic acid-modified polypropylene resin ("Admer" (registered trademark) QE840 manufactured by Mitsui Chemicals, Inc.) at a weight ratio of 85/15. Was used. As a result of measuring the melt viscosity at 200 ° C. by the method described in (1) above, it was 50 Pa · s.

(A-2)
A polycarbonate resin (manufactured by Teijin Chemicals Ltd., "Panlite" (registered trademark) L-1225L) was used. As a result of measuring the melt viscosity at 200 ° C. by the method described in (1) above, it was 14000 Pa · s.

(A-3)
A polyphenylene sulfide resin (“Trelina (registered trademark)” M2888 manufactured by Toray Industries, Inc.) was used. As a result of measuring the melt viscosity by the method described in (1) above, it was 50 Pa · s except that the measurement temperature was set to 310 ° C.

Organic fiber (C)
(C-1)
Polyester fibers (manufactured by Toray Industries, Inc., "Tetron (registered trademark)" 2200T-480-705M, single fiber fineness: 4.6 dtex, melting point: 260 ° C.) were used. The thermal conductivity was 0.15 W / m · K.

(C-2)
Polyphenylene sulfide fibers (“torque converter” (registered trademark) 400T-100-190 manufactured by Toray Industries, Inc., single fiber fineness 4.0 dtex, melting point 285 ° C.) were used. The thermal conductivity was 0.29 W / m · K.

(C-3)
Polytetrafluoroethylene fibers (“Toyoflon” (registered trademark) 440T-60F-S290-M190 manufactured by Toray Industries, Inc., single fiber fineness 7.3 dtex, melting point 327 ° C.) were used. The thermal conductivity was 0.25 W / m / K.

(C-4)
Liquid crystal polyester fibers (“Zexion” (registered trademark) 220T-48f manufactured by KB Seiren Co., Ltd., single fiber fineness 4.0 dtex, melting point 330 ° C.) were used. The thermal conductivity was 0.60 W / m · K.

Graphite (D)
(D-1)
Graphite: Scaly graphite CFW-50A (manufactured by Chuetsu Graphite Industry Co., Ltd.) was used.

(D-2)
Boron Nitride: Scaled Boron Nitride SGP (manufactured by Denka Corporation) was used.

Compound (E)
(E-1)
A solid hydrogenated terpene resin (“Clearon” (registered trademark) P125 manufactured by Yasuhara Chemical Co., Ltd., softening point 125 ° C.) was used. This was put into a tank in the impregnation aid coating device, the temperature in the tank was set to 200 ° C., and the mixture was heated for 1 hour to be in a molten state. At this time, the melt viscosity at 200 ° C. was measured by the method described in (1) above and found to be 1 Pa · s, and the rate of change in melt viscosity was calculated to be 1.2% (E-). 2)
A solid bisphenol A type epoxy resin (jER1004AF (E-2) manufactured by Mitsubishi Chemical Corporation, softening point 97 ° C.) was used as the compound (E) when the polycarbonate resin was used as the thermoplastic resin (A). As a result of measuring the melt viscosity by the method described in (1) above in the same manner as P125 described above, it was 1 Pa · s, and as a result of calculating the rate of change in melt viscosity, it was 1.1%. rice field.

(Example 1)
A long fiber reinforced resin pellet manufacturing device equipped with a coating die for the wire coating method installed at the tip of a TEX-30α twin-screw extruder (screw diameter 30 mm, L / D = 32) manufactured by Japan Steel Works, Ltd. In use, the extruder cylinder temperature was set to 220 ° C., the thermoplastic resin (A-1) and graphite (D-1) shown above were supplied from the main hopper, and melt-kneaded at a screw rotation speed of 200 rpm. The amount of graphite (D-1) was 20 parts by weight with respect to 100 parts by weight in total of (A) to (D). The discharge amount of the compound (E) melted by heating at 200 ° C. was adjusted to 8.7 parts by weight with respect to 100 parts by weight in total of (A) to (D), and the carbon fiber (B) and the carbon fiber (B) and A die that is applied to a fiber bundle made of organic fibers (C-1) to form a composite fiber bundle (F), and then a composition containing a molten thermoplastic resin (A-1) and graphite (D-1) is discharged. It was fed to the mouth (3 mm in diameter) and placed continuously so as to cover the periphery of the carbon fibers (B) and the organic fibers (C-1). At this time, carbon fibers (B) and organic fibers (C-1) were unevenly distributed in the internal cross section of the composite fiber bundle (F). In the uneven distribution state, at least a part of each of the carbon fibers (B) and the organic fibers (C-1) was in contact with the composition containing the thermoplastic resin (A-1) and graphite (D-1). After cooling the obtained strand, it was cut into pellet lengths of 7 mm with a cutter to obtain long fiber pellets. At this time, the take-up speed was adjusted so that the carbon fiber (B) was 20 parts by weight and the organic fiber (C-1) was 10 parts by weight with respect to a total of 100 parts by weight of (A) to (D). The lengths of the carbon fibers (B) and the organic fibers (C) of the obtained long fiber pellets were substantially the same as the pellet lengths. The uneven distribution state was observed with an optical microscope having a cross section perpendicular to the fiber longitudinal direction of the obtained long fiber pellets set to a magnification of 300 times, and the obtained microscopic image was image-processed and analyzed.

Using an injection molding machine (J110AD manufactured by Japan Steel Works, Ltd.), the long fiber pellets thus obtained have an injection time of 5 seconds, a back pressure of 5 MPa, a holding pressure of 20 MPa, a holding pressure time of 10 seconds, and a cylinder temperature. An ISO mold dumbbell test piece as a molded product was produced by injection molding under the conditions of: 230 ° C. and mold temperature: 60 ° C. Here, the cylinder temperature indicates the temperature of a portion where the molding material of the injection molding machine is heated and melted, and the mold temperature indicates the temperature of the mold for injecting the resin for forming a predetermined shape. The obtained test piece (molded product) was allowed to stand in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours, and then subjected to characteristic evaluation. The evaluation results evaluated by the above method are summarized in Table 1.

(Example 2)
Example 1 except that graphite (D-1) is 10 parts by weight and thermoplastic resin (A-1) is 60 parts by weight with respect to a total of 100 parts by weight of (A) to (D). A molded product was prepared in the same manner and evaluated. The evaluation results are summarized in Table 1.

(Example 3)
A molded product was prepared and evaluated in the same manner as in Example 1 except that the organic fiber (C) was changed to (C-2). The evaluation results are summarized in Table 1.

(Example 4)
The thermoplastic resin (A) was changed to (A-2), the organic fiber (C) was changed to (C-3), the compound (E) was changed to (E-2), and the cylinder temperature was changed to 300 ° C. and gold. A molded product was produced and evaluated in the same manner as in Example 1 except that the mold temperature was changed to 80 ° C. The evaluation results are summarized in Table 1.

(Example 5)
The thermoplastic resin (A) was changed to (A-2), the organic fiber (C) was changed to (C-4), the compound (E) was changed to (E-2), and the cylinder temperature was changed to 300 ° C. and gold. A molded product was produced and evaluated in the same manner as in Example 1 except that the mold temperature was changed to 80 ° C. The evaluation results are summarized in Table 1.

(Example 6)
Example 5 except that the total of 100 parts by weight of (A) to (D) was changed so that the organic fiber (C-4) was 20 parts by weight and the graphite (D-1) was 10 parts by weight. A molded product was prepared in the same manner and evaluated. The evaluation results are summarized in Table 1.

(Example 7)
The thermoplastic resin (A) was changed to (A-3), the organic fiber (C) was changed to (C-3), the compound (E) was changed to (E-2), and the cylinder temperature was changed to 330 ° C. and gold. A molded product was produced and evaluated in the same manner as in Example 1 except that the mold temperature was changed to 130 ° C. The evaluation results are summarized in Table 1.

( Comparative Example 5 )
A molded product was prepared and evaluated in the same manner as in Example 1 except that graphite (D) was changed to boron nitride (D-2). The evaluation results are summarized in Table 1.

(Comparative Example 1)
The thermoplastic resin (A-1) is 60 parts by weight, the organic fiber (C) is 0 parts by weight, and the compound (E) is 6.4 parts by weight, based on a total of 100 parts by weight of (A) to (D). A molded product was prepared and evaluated in the same manner as in Example 1 except for the above. The evaluation results are summarized in Table 2.

(Comparative Example 2)
For a total of 100 parts by weight of (A) to (D), 35 parts by weight of the thermoplastic resin (A-1), 45 parts by weight of the carbon fiber (B), and 0 part by weight of the organic fiber (C-1). A molded product was prepared and evaluated in the same manner as in Example 1 except that the amount of compound (E) was 12.4 parts by weight. The evaluation results are summarized in Table 2.

(Comparative Example 3)
The thermoplastic resin (A-1) is 70 parts by weight, the carbon fiber (B) is 0 parts by weight, and the compound (E) is 4.3 parts by weight, based on a total of 100 parts by weight of (A) to (D). A molded product was produced and evaluated in the same manner as in Example 1 except for the above. The evaluation results are summarized in Table 2.

(Comparative Example 4)
The same as in Example 1 except that the thermoplastic resin (A) is 70 parts by weight and the graphite (D-1) is 0 parts by weight with respect to a total of 100 parts by weight of (A) to (D). A molded product was prepared and evaluated. The evaluation results are summarized in Table 2.

In both the materials of Examples 1 to 4 and Example 8, carbon fibers (B), organic fibers (C) and graphite or boron nitride (D) are present in the molded product, and high bending strength and impact strength are obtained. In addition, it showed high thermal conductivity. In addition, Examples 5 and 6 in which LCP fibers were used as the organic fibers (C) showed higher thermal conductivity. Further, in Example 6, since the amount of graphite can be reduced as compared with Example 5, the impact strength is high.

On the other hand, in Comparative Example 1, since the organic fiber (C) was not contained, the fiber reinforcing effect was weak and the impact strength was low. In Comparative Example 2 in which the organic fiber (C) was not contained and the content of the carbon fiber (B) was increased, the thermal conductivity was exhibited, but the fiber reinforcing effect was weak as in Comparative Example 1, and the carbon fiber ( B) The impact strength was low because the fibers were entangled with each other and the fibers were broken in the molded product. In Comparative Example 3, since the carbon fiber (B) was not contained, the impact strength and the bending strength were low. In Comparative Example 4, since graphite (D) was not contained, the result was that the thermal conductivity was low.

Since the fiber-reinforced thermoplastic resin molded product of the present invention has excellent bending strength, impact strength and thermal conductivity, it is suitably used for electrical / electronic equipment, OA equipment, home appliances, housings, automobile parts, and the like. ..

1 Carbon fiber (B)
2 Organic fiber (C)
3 Composition containing thermoplastic resin (A) and boron nitride and / or graphite (D)

Claims (13)

A fiber-reinforced thermoplastic resin molded product containing thermoplastic resin (A), carbon fiber (B), organic fiber (C), and graphite (D).
20 to 93 parts by weight of the thermoplastic resin (A) and carbon fiber ( B) is 5 to 40 parts by weight, organic fiber (C) is 1 to 30 parts by weight, graphite (D) is 1 to 30 parts by weight, and a compound having a melt viscosity at 200 ° C. lower than that of the thermoplastic resin (A) ( E) is contained in an amount of 1 to 20 parts by weight, the carbon fiber (B) has a weight average fiber length (L _Wb ) of 0.7 to 2 mm, and the organic fiber (C) has a weight average fiber length (L _wc). ) Is 2.5 to 5 mm, a fiber-reinforced thermoplastic resin molded product. The fiber-reinforced thermoplastic resin molded product according to claim 1, wherein the thermal conductivity in the thickness direction is 0.5 to 4 W / m · K. The fiber-reinforced thermoplastic resin molded product according to claim 1 or 2, which has a bending strength of 150 to 300 MPa. The fiber-reinforced thermoplastic resin molded product according to any one of claims 1 to 3, wherein the graphite (D) contains scaly graphite. The fiber-reinforced thermoplastic resin molded product according to any one of claims 1 to 4, wherein the maximum particle size of graphite (D) is 10 to 100 μm. The fiber-reinforced thermoplastic resin according to any one of claims 1 to 5, wherein the organic fiber (C) is at least one selected from the group consisting of polyethylene terephthalate fiber, polyamide fiber, polyphenylene sulfide fiber and fluororesin fiber. Molding. The fiber-reinforced thermoplastic resin molding according to any one of claims 1 to 6, wherein the thermoplastic resin (A) is at least one selected from the group consisting of polypropylene resin, polyamide resin, polycarbonate resin and polyphenylene sulfide resin. Goods. Fiber-reinforced thermoplastic containing thermoplastic resin (A), carbon fiber (B), organic fiber (C), graphite (D), and compound (E) having a melt viscosity at 200 ° C. lower than that of the thermoplastic resin (A). 20 to 20 to 100 parts by weight of the thermoplastic resin (A), carbon fiber (B), organic fiber (C), and graphite (D), which are resin molding materials. 93 parts by weight, carbon fiber (B) 5 to 40 parts by weight, organic fiber (C) 1 to 30 parts by weight, graphite (D) 1 to 30 parts by weight, and thermoplastic resin with melt viscosity at 200 ° C. A fiber-reinforced thermoplastic resin molding material containing 1 to 20 parts by weight of a compound (E) lower than that of (A). The composite fiber bundle (F) formed by impregnating the carbon fibers (B) and the organic fibers (C) with the compound (E) is coated with the composition containing the thermoplastic resin (A) and the graphite (D). The fiber-reinforced thermoplastic resin molding material according to claim 8 , wherein the lengths of the carbon fibers (B) and the organic fibers (C) and the length of the fiber-reinforced thermoplastic resin molding material are substantially the same. The fiber-reinforced thermoplastic resin molding material according to claim 8 or 9 , wherein the graphite (D) contains scaly graphite. The fiber-reinforced thermoplastic resin molding material according to any one of claims 8 to 10 , wherein the maximum particle size of the graphite (D) is 50 to 500 μm. The fiber-reinforced thermoplastic resin molding material according to any one of claims 8 to 11 , wherein the organic fiber (C) is at least one selected from the group consisting of polyethylene terephthalate fiber, polyamide fiber and polyphenylene sulfide fiber. The fiber-reinforced thermoplastic resin molding according to any one of claims 8 to 12 , wherein the thermoplastic resin (A) is at least one selected from the group consisting of polypropylene resin, polyamide resin, polycarbonate resin and polyphenylene sulfide resin. material.

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