JP2017190426A - Resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition comprising a polyarylene sulfide resin and a carbon fiber, the resin composition having all of excellent mechanical strength, excellent rigidity, and excellent thermal conductivity, and also having excellent outgassing property.SOLUTION: A resin composition contains (A) polyarylene sulfide resin (A component) 100 pts.wt, and (B) PAN-based carbon fiber with a tensile elasticity of 350-500 GPa and amount of addition of a size agent of 1.0-2.0 wt.% (B component) 10-150 pts.wt.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition comprising a polyarylene sulfide resin and carbon fiber, which has excellent mechanical strength, rigidity, thermal conductivity, and excellent outgassing properties.

  Polyarylene sulfide resin is an engineering plastic that is excellent in chemical resistance, heat resistance, mechanical properties, and the like. For this reason, polyarylene sulfide resins are widely used in applications such as electrical and electronic, vehicle-related, aircraft, and housing facilities as metal substitutes by taking advantage of their excellent characteristics. In particular, recently, due to the growing demand for weight reduction, application to members that require high mechanical strength, rigidity, and heat dissipation has been studied.

However, since the polyarylene sulfide resin has a thermal conductivity that is significantly smaller than that of a metal material, it is difficult to dissipate heat and easily stores heat. Further, since the polyarylene sulfide resin has a high molding temperature, there is a problem that the amount of outgas increases and the workability decreases.
As an attempt to improve the thermal conductivity of polyarylene sulfide resin, for example, polyarylene sulfide resin, carbon fiber and graphite having specific tensile elastic modulus, metal powder, alumina, magnesia, titania, dolomite, boron nitride, aluminum nitride A resin composition (Patent Document 1) consisting of one or more selected from the above has been proposed. However, the resin composition has insufficient thermal conductivity, and the mechanical strength and rigidity are not described.

  Further, as an attempt to increase both the thermal conductivity and mechanical strength of the polyarylene sulfide resin, for example, polyarylene sulfide resin, carbon fiber having a specific thermal conductivity, a specific low melting point alloy, a specific metal powder, Resin composition comprising coated magnesium oxide powder, carnauba wax and graphite (Patent Document 2), polyarylene sulfide resin, resin composition comprising specific metal powder and fibrous filler (Patent Document 3), specific polyphenylene sulfide Resin, a specific polyphenylene ether resin, a carbon fiber having a specific thermal conductivity and a specific graphite resin composition (Patent Document 4), a thermoplastic resin, and a specific ratio of pitch-based carbon fiber and PAN-based carbon fiber. Resin composition (Patent Document 5), polyarylene sulfide, carbon fiber without sizing agent Resin composition (Patent Document 6) comprising at least one thermally conductive filler selected from metal silicon powder, coated magnesium oxide powder, and high-purity magnesite powder, and a silane compound, polyarylene sulfide resin, specific mixed carbon fiber And the resin composition (patent document 7) which consists of 1 or more types of heat conductive fillers selected from a covering magnesium oxide powder and a high purity magnesite powder is proposed. However, although the resin compositions described in Patent Documents 2 to 7 have sufficient thermal conductivity, the tensile strength and the mechanical strength of bending strength are not sufficient, and the mechanical rigidity is not described.

  Moreover, as an attempt to improve the outgassing property, for example, a resin composition comprising carbon fibers and a thermoplastic resin whose weight loss at 400 ° C. in an inert atmosphere is 0.5% or less (Patent Document 8), 250 to 330. There has been proposed a resin composition (Patent Document 9) comprising a carbon fiber heat-treated at ° C. and a thermoplastic resin. However, although the outgas property and the mechanical strength are sufficient, the thermal conductivity is not described.

JP 2002-129015 A JP 2007-45988 A JP 2007-146105 A JP 2004-137401 A JP 2014-51587 A JP 2007-291300 A JP 2007-291220 A JP-A-5-229869 Japanese Patent Laid-Open No. 10-1877

  An object of the present invention is to provide a resin composition comprising a polyarylene sulfide resin and carbon fiber, which has excellent mechanical strength, rigidity, thermal conductivity, and excellent outgas properties. .

  As a result of intensive studies, the present inventors have found that a resin composition comprising a polyarylene sulfide resin and a specific carbon fiber can achieve both excellent mechanical strength, rigidity, and thermal conductivity, and has excellent outgassing properties. The present invention has been reached.

Specifically, the above problem is that (A) polyarylene sulfide resin (component A) 100 parts by weight, (B) tensile modulus is 350 to 500 GPa, and sizing agent adhesion is 1.0 to 2.0 weight. % PAN-based carbon fiber (component B) is achieved by a resin composition containing 10 to 150 parts by weight.
One of the preferred embodiments of the present invention is characterized in that (2) the B component is a PAN-based carbon fiber having a thermal conductivity of 15 to 120 W / mK in the fiber axis direction measured by a laser flash method. It is the resin composition of the said structure 1.
One of the preferred embodiments of the present invention is (3) a molded body molded from the polyarylene sulfide resin composition having the above constitution 1 or 2.
One of the preferred embodiments of the present invention is as follows: (4) (A) Polyarylene sulfide resin (component A) 100 parts by weight, (B) Tensile modulus is 350 to 500 GPa, and sizing agent adhesion is 1.0. It is a manufacturing method of the resin composition containing 10-150 weight part of PAN-type carbon fiber (B component) which is -2.0 weight%.
One of the preferred embodiments of the present invention is the method for producing a resin composition of the above constitution 4, wherein the component (5) is a PAN-based carbon fiber graphitized at 2000 to 3000 ° C. .
One preferred embodiment of the present invention is that (6) component A is polymerized by directly heating a diiodoaryl compound, solid sulfur, and a polymerization terminator and / or a polymerization reaction catalyst without using a polar solvent. It is a polyarylene sulfide resin obtained by the method to make the resin composition of the said structure 4 or 5 characterized by the above-mentioned.

Details of the present invention will be described below.
(Component A: polyarylene sulfide resin)
As the polyarylene sulfide resin used as the component A of the present invention, any polyarylene sulfide resin may be used as long as it belongs to the category called polyarylene sulfide resin.
The polyarylene sulfide resin has, for example, p-phenylene sulfide unit, m-phenylene sulfide unit, o-phenylene sulfide unit, phenylene sulfide sulfone unit, phenylene sulfide ketone unit, phenylene sulfide ether unit, diphenylene sulfide unit as structural units. , A substituent-containing phenylene sulfide unit, a branched structure-containing phenylene sulfide unit, and the like. Among them, those containing a p-phenylene sulfide unit of 70 mol% or more, particularly 90 mol% or more. Furthermore, poly (p-phenylene sulfide) is more preferable.

The total chlorine content of the polyarylene sulfide resin used as the component A of the present invention is preferably 500 ppm or less, more preferably 300 ppm or less, and even more preferably 50 ppm or less. If the total chlorine content exceeds 500 ppm, the amount of gas generated may increase and the weld strength may be reduced.
The total sodium content of the polyarylene sulfide resin used as the component A of the present invention is preferably 39 ppm or less, more preferably 10 ppm or less, and even more preferably 8 ppm or less. If it exceeds 39 ppm, not only the weld strength is reduced due to an increase in the generated gas, but also the heat and moisture resistance is reduced due to an increase in the water absorption of the resin due to the coordinate bond between sodium metal and water molecules in a high temperature and high humidity environment. There is a case.

  The dispersity (Mw / Mn) represented by the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyarylene sulfide resin used as the component A of the present invention is preferably 2.7 or more, more preferably 2 .8 or more, more preferably 2.9 or more. When the degree of dispersion is less than 2.7, burrs are often generated during molding. The upper limit of the dispersity (Mw / Mn) is not particularly defined, but is preferably 10 or less. Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values calculated in terms of polystyrene by gel permeation chromatography (GPC). Note that 1-chloronaphthalene was used as the solvent, and the column temperature was 210 ° C.

  The method for producing the polyarylene sulfide resin is not particularly limited, and the polymerization is carried out by a known method, but as a particularly suitable polymerization method, there are US Pat. Nos. 4,746,758 and 4,786. No. 713, Special Table 2013-522385, Japanese Patent Application Laid-Open No. 2012-233210, Japanese Patent No. 5167276, and the like. These production methods are methods in which a diiodoaryl compound and solid sulfur are polymerized by direct heating without a polar solvent.

The production method includes an iodination step and a polymerization step. In the iodination step, an aryl compound is reacted with iodo to obtain a diiodoaryl compound. In the subsequent polymerization step, a polyarylene sulfide resin is produced by polymerizing the diiodoaryl compound with solid sulfur using a polymerization terminator. Iodine is generated in a gaseous state in this step, and this is recovered and used again in the iodination step. Essentially iodine is a catalyst.
A typical solid sulfur used in the production method includes a cyclooctasulfur form (S ₈ ) in which ₈ atoms are linked at room temperature. However, the sulfur compound used in the polymerization reaction is not limited, and any form can be used as long as it is solid or liquid at room temperature.

  Representative diiodoaryl compounds used in the production method include at least one selected from the group consisting of diiodobenzene, diiodonaphthalene, diiodobiphenyl, diiodobisphenol and diiodobenzophenone, and alkyl A derivative of an iodoaryl compound in which a group or a sulfone group is bonded or oxygen or nitrogen is introduced is also used. Iodoaryl compounds are classified into different isomers depending on the bonding position of the iodo atom, and preferred examples of these isomers are p-diiodobenzene, 2,6-diiodonaphthalene, and p, p′-diiodo. A compound in which iodine is symmetrically located at both ends of an aryl compound molecule, such as biphenyl. The content of the iodoaryl compound is preferably 500 to 10,000 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined taking into account the formation of disulfide bonds.

  Typical polymerization terminators used in the production method include monoiodoaryl compounds, benzothiazoles, benzothiazole sulfenamides, thiurams, dithiocarbamates, aromatic sulfide compounds and the like. Preferable examples of monoiodoaryl compounds include at least one selected from the group consisting of iodobiphenyl, iodophenol, iodoaniline, and iodobenzophenone. Preferable examples of the benzothiazoles include at least one selected from the group consisting of 2-mercaptobenzothiazole and 2,2′-dithiobisbenzothiazole. Preferred examples of benzothiazole sulfenamides include N-cyclohexylbenzothiazole 2-sulfenamide, N, N-dicyclohexyl-2-benzothiazole sulfenamide, 2-morpholinothiobenzothiazole, benzothiazole sulfenamide , Dibenzothiazole disulfide, and at least one selected from the group consisting of N-dicyclohexylbenzothiazole 2-sulfenamide. Preferable examples of thiurams include at least one selected from the group consisting of tetramethylthiuram monosulfide and tetramethylthiuram disulfide. Preferable examples of the dithiocarbamates include at least one selected from the group consisting of zinc dimethyldithiocarbamate and zinc diethyldithiocarbamate. Preferable examples of the aromatic sulfide compound include at least one selected from the group consisting of diphenyl sulfide, diphenyl disulfide, diphenyl ether, biphenyl, and benzophenone. The content of the polymerization terminator is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined taking into account the formation of disulfide bonds.

  In the production method, a polymerization reaction catalyst can be blended in the polymerization step as necessary, and typical polymerization reaction catalysts include various nitrobenzene derivatives. Among these polymerization reaction catalysts, preferable examples are as follows. 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, iodonitrobenzene, 2,6-diiodo-4-nitroamine Species are mentioned. The content of the polymerization reaction catalyst is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined taking into account the formation of disulfide bonds.

Typical examples of the reaction conditions of the production method include initial reaction conditions of a temperature of 180 to 250 ° C. and a pressure of 50 to 450 Torr (6.7 to 60 kPa), a temperature of 270 to 350 ° C. and a pressure of 0.001 to 20 Torr (0 The reaction is allowed to proceed for 1 to 30 hours while raising the temperature and lowering the pressure to the final reaction conditions of 0.00013-2.7 kPa). Preferably, the initial reaction conditions are a temperature of 180 ° C. or more and a pressure of 450 Torr (60 kPa) or less in consideration of the reaction rate, and the final reaction conditions are a temperature of 350 ° C. or less and a pressure of 20 Torr (2. 7 kPa) or less.
However, the polymerization reaction conditions are not particularly limited because they depend on the structural design and production rate of the reactor and are known to those skilled in the art. Reaction conditions can be appropriately set by those skilled in the art in consideration of process conditions.

In addition, as a polyarylene sulfide resin used as the component A of the present invention, a carboxy group, a carboxy group derivative group, a thiol group, a sulfone group, a hydroxy group, an amino group, an epoxy group for the purpose of obtaining higher mechanical strength. A polyarylene sulfide resin having a reactive functional group such as a mercapto group, a cyano group, or a nitro group at the terminal can also be used. By using the polyarylene sulfide resin having the reactive functional group at the terminal, a resin composition exhibiting excellent compatibility with other polymer materials and carbon fibers and having higher mechanical strength is obtained. Can do. More preferable examples of the polyarylene sulfide resin having a reactive functional group at the terminal include a polyarylene sulfide resin having at least one terminal group structure selected from a carboxyl group and an amino group. The polyarylene sulfide resin having at least one terminal group structure selected from the carboxyl group and the amino group is about 1600 to 1800 cm ⁻¹ derived from a carboxyl group or amino group in the FT-IR spectrum of FT-IR spectroscopy. It shows a peak at about 3300～3500Cm ^-1 derived group, and when the height strength aromatic ring stretching peak appearing in 1400～1600Cm ^-1 was 100%, the about 1600～1800Cm ^-1 or about 3300～3500Cm ^{- 1} is a polyarylene sulfide resin having a relative height intensity of ¹ peak of 0.001 to 10%.

  A particularly preferred example of the polyarylene sulfide resin having at least one terminal group structure selected from the carboxyl group and amino group is a polyarylene sulfide resin having a carboxyl group terminal group structure, which is represented by the following general formula (1 ).

（式中、Ａｒ基はアリーレン基である。）

(In the formula, Ar group is an arylene group.)

Here, as the arylene group, a p-phenylene group, an m-phenylene group, an o-phenylene group, a substituted phenylene group, or the like can be used. Specifically, the substituted phenylene group includes one or more F, Cl, Br, C1-C3 alkyl, trifluoromethyl, C1-C3 alkoxy, trifluoromethoxy, trifluoromethylthio, dimethylamino, cyano, (C1 to C3 _alkyl) SO 2 -, (C1~C3 _alkyl) NHSO 2 -, (C1~C3 _{alkyl) 2NSO 2 -, NH 2 SO} 2 - is optionally substituted by phenylene groups.

  The method for introducing the reactive functional group into the polyarylene sulfide resin is not particularly limited, and the polymerization is performed by a known method, but one or a plurality of general formulas (2) may be formed on the conjugated aromatic ring skeleton. The method of using the polymerization terminator which has group represented is mentioned. Examples of the conjugated aromatic ring skeleton used in the polymerization terminator include diphenyl disulfide, monoiodobenzene, thiophenol, 2,2′-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, and N-cyclohexyl-2-benzo. Examples include thiazolylsulfenamide, 2- (morpholinothio) benzothiazole, N, N′-dicyclohexyl-1,3-benzothiazole-2-sulfenamide.

（式中、Ｒは水素原子またはアルカリ金属原子である）

(Wherein R is a hydrogen atom or an alkali metal atom)

  As a suitable polymerization method of the method for producing a polyarylene sulfide resin having a carboxyl group terminal group structure, a step of polymerizing a reactant containing a diiodo aromatic compound and a sulfur element, while proceeding through the polymerization reaction step, And a production method in which a compound having a group is added and the terminal group of the polyarylene sulfide main chain is substituted with a carboxyl group. A typical example used in the compound having a carboxyl group is at least one selected from the group consisting of 2-iodobenzoic acid, 3-iodobenzoic acid, 4-iodobenzoic acid, and 2,2′-dithiobenzoic acid. Species are mentioned. The compound having a carboxyl group can be added in an amount of about 0.0001 to 5 parts by weight based on 100 parts by weight of the diiodo aromatic compound.

(B component: carbon fiber)
The carbon fiber used as the component B of the present invention is a PAN-based carbon fiber having a tensile modulus of 350 to 500 GPa. The tensile modulus of the B component is preferably 360 to 490 GPa, more preferably 370 to 480 GPa. When the tensile modulus of the B component is less than 350 GPa, the thermal conductivity is inferior, and when it exceeds 500 GPa, the mechanical strength decreases. The tensile modulus was measured according to JIS R 7608. Moreover, B component needs to be a PAN-type carbon fiber, and when it is not a PAN-type carbon fiber, mechanical strength falls remarkably.
The sizing agent adhesion amount of component B is 1.0 to 2.0% by weight, preferably 1.1 to 1.9% by weight, and more preferably 1.2 to 1.8% by weight. When the sizing agent adhesion amount of the component B is less than 1.0% by weight, the production or molding processability decreases, and when it exceeds 2.0% by weight, the outgas amount increases.

The thermal conductivity of the component B is preferably 15 to 120 W / mK, more preferably 20 to 110 W / mK, and still more preferably 25 to 100 W / mK. If the thermal conductivity of the B component is less than 15 W / mK, the mechanical rigidity and thermal conductivity may be inferior, and if it exceeds 120 W / mK, the mechanical strength may be reduced. The thermal conductivity was measured by the following method. That is, carbon fiber strands are cut and bundled to prepare a sample in a cylindrical shape with a diameter of 8 mm and a thickness of 3 mm, and the thermal conductivity in the fiber axis direction of the carbon fiber is measured by a laser flash method using LFA-447 manufactured by NETZSCH. Asked.
The PAN-based carbon fiber that is the component B can be produced, for example, by the following method.

<Precursor fiber>
The precursor fiber is produced by spinning a spinning solution containing a monomer containing acrylonitrile in an amount of 90% by weight or more, preferably 95% by weight or more and 10% by weight or less of any other monomer. An acrylic precursor fiber is preferable. Examples of other monomers include itaconic acid and (meth) acrylic acid esters. Precursor fibers are obtained by subjecting the raw fiber after spinning to water washing, drying, stretching, and oiling treatment. At this time, steam stretching is performed so that the total stretching ratio is 5 to 15 times. The number of filaments of the precursor fiber is preferably 1000 filaments or more, more preferably 12000 filaments or more in terms of production efficiency.

<Flame resistance treatment>
The obtained precursor fiber was preheated before flameproofing treatment at 200 to 260 ° C. and a stretch ratio of 0.90 to 1.00, and subsequently subjected to flameproofing treatment in heated air at 200 to 260 ° C. for 10 to 100 minutes. The The treatment at this time is generally carried out in a draw ratio range of 0.85 to 1.15, but 0.95 or more is more preferable in order to obtain a carbon fiber having high strength and high elastic modulus. In this flameproofing treatment, the precursor fibers are oxidized fibers having a fiber density of 1.34 to 1.38 g / cm ³ , and the tension (stretch distribution) at the time of flameproofing is not particularly limited. .

<First carbonization treatment>
The flame-treated fiber is carbonized by adopting a conventionally known method. For example, the temperature is gradually increased in a first carbonization furnace at 300 to 800 ° C. in a nitrogen atmosphere, and the first carbonization in the first stage is performed under tension by controlling the tension of the flameproof fiber.

<Second carbonization treatment>
In order to promote further carbonization and graphitization (high crystallization of carbon), the temperature is gradually increased in a second carbonization furnace at 800 to 2000 ° C. in an inert gas atmosphere such as nitrogen, and the first carbonization is performed. Firing is performed by controlling the tension of the fiber.
In each carbonization furnace, it is not preferable to introduce fibers rapidly from the vicinity of the furnace entrance, for example, abruptly at the maximum temperature, because many surface defects and internal defects are generated. Further, if the residence time becomes longer than necessary at a high temperature portion in the furnace, graphitization proceeds excessively, and brittle carbon fibers are obtained, which is not preferable. In the first carbonization treatment to the second carbonization treatment step, the tension may be controlled, and the treatment may be performed in a plurality of furnaces so as to have predetermined physical properties as necessary.

<Graphitization treatment>
In order to obtain a higher elastic modulus, graphitization is further performed at a high temperature of 2000 to 3000 ° C. The temperature of carbonization treatment and graphitization treatment may be appropriately adjusted according to the elastic modulus of the target carbon fiber. The higher the treatment temperature and the longer the treatment time, the higher the elastic modulus of the carbon fiber. Tend.

<Surface oxidation treatment>
The carbon fiber strand is subjected to surface oxidation treatment in an electrolytic solution. The amount of electricity applied to the carbon fiber by the surface treatment may be adjusted as appropriate so as to obtain the target surface functional group amount, but it is preferably in a range of 50 to 500 coulombs with respect to 1 g of the carbon fiber. When the amount of electricity applied to 1 g of carbon fiber is adjusted within this range, it is easy to obtain a carbon fiber having excellent mechanical properties as a fiber and improved adhesion to a resin. On the other hand, if the amount of electricity applied to 1 g of carbon fiber is less than 50 coulombs, the adhesiveness with the resin tends to decrease, and if it exceeds 500 coulombs, the fiber strength tends to decrease due to excessive treatment.

As the electrolytic solution, an aqueous solution of an inorganic acid or an inorganic base and an inorganic salt is preferably used. For example, when a strong acid such as sulfuric acid or nitric acid is used as the electrolyte, the surface treatment efficiency is preferable. In addition, it is preferable to use an inorganic salt such as ammonium sulfate or sodium hydrogen carbonate as the electrolyte because the risk of the electrolytic solution is lower than when an inorganic acid is used.
The electrolyte concentration of the electrolytic solution is preferably 0.1 N or more, and more preferably 0.1 to 1 N. If the electrolyte concentration is less than 0.1 N, the electrical conductivity is low, so there is a tendency that it is not suitable for electrolysis. On the other hand, if the electrolyte concentration is too high, the electrolyte is deposited and the concentration stability is low. Tend to be.
The higher the temperature of the electrolytic solution, the higher the electrical conductivity, so that the treatment can be promoted. On the other hand, when the temperature of the electrolytic solution exceeds 40 ° C., it becomes difficult to provide uniform conditions without time fluctuation due to fluctuations in concentration due to evaporation of moisture, etc., so that the temperature is preferably 15 to 40 ° C.

<Sizing process>
The surface-treated carbon fiber strand is passed through a sizing solution and a sizing agent is applied. The concentration of the sizing agent in the sizing liquid is preferably 10 to 25% by weight, and the adhesion amount of the sizing agent is preferably 0.4 to 1.7% by weight. The sizing agent applied to the carbon fiber strand is not particularly limited. For example, epoxy resin, urethane resin, polyester resin, vinyl ester resin, polyamide resin, polyether resin, acrylic resin, polyolefin resin, polyimide resin or a modified product thereof. Is mentioned. Note that a suitable sizing agent can be appropriately selected according to the matrix resin of the composite material. Moreover, this sizing agent can also be used in combination of 2 or more types. In the sizing agent application treatment, an emulsion method is generally used in which carbon fiber strands are immersed in an aqueous emulsion obtained using an emulsifier or the like. In addition, auxiliary components such as a dispersant and a surfactant may be added to the sizing agent in order to improve the handleability, scratch resistance, fluff resistance, and impregnation properties of the carbon fiber.

<Drying process>
The carbon fiber strand after the sizing treatment is subjected to a drying treatment to evaporate water or the like that was a dispersion medium at the time of the sizing treatment, and a carbon fiber strand for producing a composite material is obtained. It is preferable to use an air dryer for drying. The drying temperature is not particularly limited, but is generally set to 100 to 180 ° C. in the case of a general-purpose aqueous emulsion. Moreover, in this invention, it is also possible to pass through the heat processing process (200 degreeC or more) after a drying process.

<Chop process>
The carbon fiber chopped strand is produced by cutting the carbon fiber bundle into a predetermined length. 3-15 mm is preferable and, as for the length of a carbon fiber chopped strand, 5-10 mm is more preferable. Carbon fiber chopped strands having a length of less than 3 mm have a tendency that the handling density of the chopped strands tends to be lowered because the bulk density of the chopped strands is reduced. Carbon fiber chopped strands exceeding 15 mm tend to have low supply stability when the chopped strands are supplied to an injection molding machine, an extruder for producing pellets, or the like. As a cutting method, a rotary cutter such as a roving cutter or a commonly used cutter such as a guillotine cutter can be appropriately used. A higher bulk density of the carbon fiber chopped strand is preferable because it can be stably supplied to a molding machine when producing a composite material, and is preferably 500 g / L or more.

<Heating process>
The heat treatment is performed at 250 to 330 ° C. in the air. When the heat treatment temperature is less than 250 ° C., when the amount of carbon fiber chopped strands attached is large and the remaining resin composition is used, the outgassing property is lowered. When the heat treatment temperature exceeds 330 ° C., the fiber is easily opened and the quantitative supply is deteriorated. Since the heat treatment time affects the heat treatment temperature, it is necessary to adjust each time. When the heat treatment temperature is 250 to 300 ° C, the heat treatment time is 10 to 25 hours, and the heat treatment temperature is 300 to 330 ° C. In this case, the heat treatment time is preferably 5 to 15 hours.
Content of B component is 10-150 weight part with respect to 100 weight part of A component, Preferably it is 15-120 weight part, More preferably, it is 20-100 weight part. When the content of the B component is less than 10 parts by weight, the mechanical strength, rigidity and thermal conductivity are inferior, and when it exceeds 150 parts by weight, production or moldability is deteriorated.

(Other ingredients)
The resin composition in the present invention can contain an elastomer component as long as the effects of the present invention are not impaired. Suitable elastomer components include core-shells such as acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), and silicone-acrylic composite rubber-based graft copolymer. Examples of the graft copolymer resin include thermoplastic elastomers such as silicone-based thermoplastic elastomers, olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers.

  The resin composition in the present invention can contain other thermoplastic resins as long as the effects of the present invention are not impaired. Other thermoplastic resins include, for example, general-purpose plastics represented by polyethylene resin, polypropylene resin, polyalkylmethacrylate resin, polyphenylene ether resin, polyacetal resin, aromatic polyester resin, liquid crystalline polyester resin, polyamide resin, cyclic resin Engineering plastics represented by polyolefin resin, polyarylate resin (amorphous polyarylate, liquid crystalline polyarylate), polytetrafluoroethylene, polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, etc. What is called super engineering plastics can be mentioned.

  The resin composition in the present invention is an antioxidant, a heat stabilizer (hindered phenol, hydroquinone, phosphite, and substituted products thereof), a weather resistance (resorcinol, Salicylates, benzotriazoles, benzophenones, hindered amines, etc.), mold release agents and lubricants (montanic acid and its metal salts, its esters, their half esters, stearyl alcohol, stearamide, various bisamides, bisureas, polyethylene waxes, etc.) , Pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.) ), Antistatic agent (alkyl resin) Fate type anionic antistatic agent, quaternary ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc.), flame retardant (red phosphorus) , Phosphate esters, melamine cyanurate, magnesium hydroxide, aluminum hydroxide and other hydroxides, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resins or their brominated flame retardants And a combination of antimony trioxide and the like and other polymers can be added.

(Manufacture of resin composition)
The resin composition of the present invention can be produced by mixing the above components simultaneously or in any order with a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, or extruder. Preferably, melt kneading by a twin screw extruder is preferable, and if necessary, it is preferable to supply arbitrary components from the second supply port into other melt-mixed components using a side feeder or the like. As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.

The screw used in the twin-screw extruder is configured as a single screw by inserting and complexly combining screw pieces of various shapes between the forward flight pieces for transportation, and integrating them as a single screw. Examples include a combination of screw pieces such as a forward kneading piece, a reverse kneading piece, and a reverse flight piece arranged in an appropriate order and position in consideration of the characteristics of the raw material to be processed.
Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Although the shape of the obtained pellet can take general shapes, such as a cylinder, a prism, and a spherical shape, it is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.5 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 4 mm.

(About molded products)
A molded product using the resin composition of the present invention can be obtained by molding the pellets produced as described above. Preferably, it is obtained by injection molding or extrusion molding. In injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, and heat insulation gold Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, multicolor molding, sandwich molding, and ultrahigh-speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding. In extrusion molding, various shaped extrusion molded products, sheets, films and the like are obtained. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can also be formed into a molded product by rotational molding, blow molding or the like.

  The resin composition of the present invention is a resin composition comprising a polyarylene sulfide resin and a specific PAN-based carbon fiber, and is a resin composition having both excellent mechanical strength, rigidity, and thermal conductivity. (Notebook, ultrabook), tablet, mobile phone housing, inverter housing for hybrid and electric vehicles, display, OA equipment, mobile phone, personal digital assistant, facsimile, compact disc, portable MD, portable radio cassette, Enclosures and trays and chassis for electrical and electronic devices such as PDAs (mobile information terminals such as electronic notebooks), video cameras, digital still cameras, optical equipment, audio equipment, air conditioners, lighting equipment, entertainment equipment, toy goods, and other home appliances Internal members such as cases, their cases, mechanism parts, panel Applications such as building materials, motor parts, alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, suspension parts, various valves such as exhaust gas valves, fuel-related, various exhaust system or intake system pipes, air intake nozzle snorkel, Intake manifold, various arms, various frames, various hinges, various bearings, fuel pump, gasoline tank, CNG tank, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad Wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, air cylinder Thermostat base, heating / air flow control valve, radiator motor brush holder, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner Panel switch board, coil for fuel related electromagnetic valve, connector for fuse, battery tray, AT bracket, head lamp support, pedal housing, handle, door beam, protector, chassis, frame, armrest, horn terminal, step motor rotor, lamp socket, Lamp reflector, lamp housing, brake piston, noise shield, radiator support, Spare tire cover, seat shell, solenoid bobbin, engine oil filter, ignition device case, under cover, scuff plate, pillar trim, propeller shaft, wheel, fender, fascia, bumper, bumper beam, bonnet, aero parts, platform, cowl louver, Automobiles, motorcycle-related parts such as roofs, instrument panels, spoilers and various modules, parts and skins, landing gear pods, winglets, spoilers, edges, ladders, elevators, failings, ribs and other aircraft-related parts, parts and Widely useful in outer panels, windmill blades, etc., especially parts around engines of automobiles and motorcycles, semiconductor elements with high heat generation, sealing parts such as resistors, or high frictional heat Useful in sliding component occurs, the effect on that brings industry is exceptional.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

[Evaluation of resin composition]
(1) Tensile strength at break Measured according to ISO 527 (measurement condition 23 ° C.). The test piece was molded by an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C. The larger this value, the better the mechanical strength of the resin composition.

(2) Bending strength It measured based on ISO178 (measurement conditions 23 degreeC). The test piece was molded by an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C. The larger this value, the better the mechanical strength of the resin composition.

(3) Flexural modulus Measured according to ISO178 (measuring condition 23 ° C.). The test piece was molded by an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C. The larger this value, the better the mechanical rigidity of the resin composition.

(4) Thermal conductivity Samples were cut into 3 mm × 10 mm strips from 4 mm-thick test pieces molded under the same conditions as in (1) above, aligned side by side, and lasered using NETZSCH LFA-447. The thermal conductivity in the flow direction of the sample was determined by the flash method. The larger this value, the better the thermal conductivity of the resin composition and the better the heat dissipation.

(5) Amount of outgas The pellet was heated from room temperature in a nitrogen gas atmosphere by a thermogravimetric analyzer (Thermo plus EVO2 differential type differential thermobalance TG8121 manufactured by Rigaku Corporation) and held at 130 ° C for 1 hour, and then heated. The temperature was raised to 320 ° C. at a rate of 20 ° C./min. The weight loss rate (% by weight) before and after heating at 320 ° C. for 30 minutes was calculated as the amount of outgas. The smaller this value, the better the outgassing property of the resin composition and the lower the outgassing property.

[Examples 1 to 5, Comparative Examples 1 to 7]
The polyarylene sulfide resin and the carbon fiber were melt-kneaded at the respective compounding amounts shown in Table 1 using a vent type twin screw extruder to obtain pellets. The vent type twin screw extruder used was TEX-30XSST (completely meshed, rotating in the same direction) manufactured by Nippon Steel Works. Extrusion conditions were a discharge rate of 16 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 320 ° C. from the first supply port to the die part. The carbon fiber was supplied from the second supply port using the side feeder of the extruder, and the polyarylene sulfide resin was supplied from the first supply port to the extruder. The first supply port here is a supply port farthest from the die, and the second supply port is a supply port located between the die of the extruder and the first supply port. The obtained pellets were dried with a hot air circulation dryer at 130 ° C. for 5 hours, and then the cylinder temperature was 320 ° C. and the mold temperature was 140 ° C. with an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.). Test specimens for evaluation were molded under the conditions. Each component of the symbol notation in Table 1 is as follows.

<A component>
PPS-1: Polyphenylene sulfide resin obtained by the following production method [Production method]
To 300.00 g of paradiiodobenzene and 27.00 g of sulfur, 0.60 g of diphenyl disulfide (content of 0.65% by weight based on the weight of the finally polymerized PPS) was added as a polymerization terminator, and the temperature reached 180 ° C. After heating to completely melt and mix them, the temperature was raised to 220 ° C. and the pressure was reduced to 200 Torr. The resulting mixture was subjected to a polymerization reaction for 8 hours while gradually changing the temperature and pressure so that the final temperature and pressure were 320 ° C. and 1 Torr, respectively, to produce a polyphenylene sulfide resin. The total chlorine content was 20 ppm or less (below the detection limit), and the total sodium content was 7 ppm.

PPS-2: Polyarylene sulfide resin having a carboxyl group end group structure obtained by the following production method [Production method]
A reaction product containing 5130 g of paradiiodobenzene and 450 g of sulfur and 4 g of mercaptobenzothiazole as a reaction initiator is heated to 180 ° C. to completely melt and mix, then the temperature is raised to 220 ° C. and the pressure is set to 350 Torr. The pressure dropped. The resulting mixture was subjected to a polymerization reaction while gradually changing the temperature and pressure so that the final temperature and pressure were 300 ° C. and 1 Torr or less, respectively. When the polymerization reaction has progressed 80% (the degree of progress of the polymerization reaction was confirmed by the method of relative ratio by viscosity ((current viscosity / target viscosity) × 100%)), 25 g of mercaptobenzothiazole was added as a polymerization terminator And reacted. After 1 hour, 51 g of 4-iodobenzoic acid was added and reacted in a nitrogen atmosphere for 10 minutes. After gradually raising the degree of vacuum to 0.5 Torr or less and further reacting for 1 hour, the reaction was terminated. Was produced at the end of the main chain. The total chlorine content was 20 ppm or less (below the detection limit), and the total sodium content was 7 ppm.

<B component>
CF-1: PAN-based carbon fiber obtained by the following production method [Production method]
PAN-based carbon fiber “TENAX” (product name) UMS40 (manufactured by Toho Tenax Co., Ltd., tensile strength: 4,700 MPa, tensile elastic modulus: 390 GPa, sizing agent: polyurethane, sizing agent adhesion amount: 1.3% by weight) The carbon fiber strands were twisted to a twisting number of 3 / m and continuously introduced into a sizing agent bath made of a polyetherketone solution of polyurethane resin (Crisbon 6216SL, manufactured by DIC Corporation) for bundling treatment. And dried at 150 ° C. for 2 minutes. The amount of sizing agent attached to the carbon fiber strand was 2.5% by weight. The carbon fiber strand after the bundling treatment is cut into a length of 6 mm and further subjected to a heat treatment at 270 ° C. for 24 hours to obtain a PAN-based carbon fiber (tensile elastic modulus: 390 GPa, sizing agent adhesion amount: 1.5% by weight) Manufactured.

CF-2: PAN-based carbon fiber “Tenax” (product name) UMS40 is replaced with PAN-based carbon fiber “Tenax” (product name) UMS45 (manufactured by Toho Tenax Co., Ltd., tensile strength: 4,600 MPa, tensile modulus: 425 GPa, A PAN-based carbon fiber (tensile elastic modulus: 425 GPa, sizing agent adhesion amount: 1) obtained by the same production method as CF-1 except that the sizing agent was changed to polyurethane, sizing agent adhesion amount: 1.1 wt%. .5% by weight)
CF-3: PAN-based carbon fiber “TENAX” (product name) UMS40 is converted to PAN-based carbon fiber “TENAX” product name) UMS55 (manufactured by Toho Tenax Co., Ltd., tensile strength: 4,000 MPa, tensile elastic modulus: 550 GPa, sizing PAN-based carbon fiber (tensile elastic modulus: 550 GPa, sizing agent adhesion amount: 1.) obtained by the same production method as CF-1, except that the agent was changed to polyurethane: sizing agent adhesion amount: 0.7% by weight. 5% by weight)
CF-4: PAN-based carbon fiber (“Tenax” manufactured by Toho Tenax Co., Ltd. (product name) HTC432 6 mm, tensile strength: 4,200 MPa, tensile elastic modulus: 240 GPa, cut length: 6 mm, sizing agent: polyurethane, size (Amount of adhering agent: 2.3% by weight)

CF-5: Pitch-based carbon fiber obtained by the following production method [Production method]
Synthetic mesophase pitch was melt-spun as a precursor to obtain a carbon fiber strand composed of 40000 pitch fibers. This carbon fiber strand is infusible in an air atmosphere, further carbonized and graphitized in a nitrogen atmosphere, then subjected to surface treatment and sizing treatment, cut to a length of 6 mm, and pitch-based carbon fiber (tensile strength: 2 , 600 MPa, tensile elastic modulus: 450 GPa, sizing agent: epoxy, sizing agent adhesion amount: 1.8% by weight).
CF-6: PAN-based carbon fiber obtained by the same production method as CF-1 except that no heat treatment was performed (tensile elastic modulus: 425 GPa, sizing agent adhesion amount: 2.5% by weight)
CF-7: PAN-based carbon fiber obtained by the same production method as CF-1 except changing the heating temperature to 350 ° C. (tensile elastic modulus: 425 GPa, sizing agent adhesion amount: 0.8 wt%)
[Thermal conductivity of carbon fiber]
CF-1: 29W / mK
CF-2: 50W / mK
CF-3: 132W / mK
CF-4: 9W / mK
CF-5: 100W / mK
CF-6: 28W / mK
CF-7: 30W / mK

Claims (6)

  (A) PAN-based carbon fiber (B) having a tensile elastic modulus of 350 to 500 GPa and a sizing agent adhesion amount of 1.0 to 2.0% by weight with respect to 100 parts by weight of polyarylene sulfide resin (component A) Component) A resin composition containing 10 to 150 parts by weight.   2. The resin composition according to claim 1, wherein the B component is a PAN-based carbon fiber having a thermal conductivity in the fiber axis direction measured by a laser flash method of 15 to 120 W / mK.   The molded object shape | molded with the polyarylene sulfide resin composition of Claim 1 or 2.   (A) Production of a resin composition containing 10 to 150 parts by weight of a PAN-based carbon fiber (B component) having a tensile modulus of 350 to 500 GPa with respect to 100 parts by weight of a polyarylene sulfide resin (A component) Method.   The method for producing a resin composition according to claim 4, wherein the component B is a PAN-based carbon fiber graphitized at 2000 to 3000 ° C.   The component A is a polyarylene sulfide resin obtained by a method in which a diiodoaryl compound, solid sulfur, and a polymerization terminator and / or a polymerization reaction catalyst are polymerized by direct heating without using a polar solvent. The manufacturing method of the resin composition of Claim 4 or 5.