JP2011162767A - Carbon fiber reinforced polyphenylene sulfide resin composition, and molding material and molding using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a carbon fiber reinforced polyphenylene sulfide resin composition which excels in impregnating ability into carbon fiber and dispersibility into a molding of carbon fiber, and is for obtaining a molding excellent in a dynamical characteristic, and to provide a molding material and molding using the same. <P>SOLUTION: The carbon fiber reinforced polyphenylene sulfide resin composition comprises the following component (A)-(C): (A) 1-75 mass% of carbon fiber, (B) 17-98.99 mass% of a polyphenylene sulfide resin, and (C) 0.01-8 mass% of polyalkylene terephthalate. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a carbon fiber reinforced polyphenylene sulfide resin composition. More specifically, by using a polyphenylene sulfide resin with improved processability when heated, the impregnation property of the polyphenylene sulfide resin into the carbon fiber and the dispersibility of the carbon fiber in the molded product are good, and the mechanical properties The present invention relates to a carbon fiber reinforced polyphenylene sulfide resin composition capable of producing a molded article excellent in the above, and a molding material and a molded article using the same.

  Resin compositions comprising reinforcing fibers and thermoplastic resins are widely used in sports equipment applications, aerospace applications and general industrial applications because they are lightweight and have excellent mechanical properties. Reinforcing fibers used in these resin compositions reinforce molded products in various forms depending on the intended use. These reinforcing fibers include metal fibers such as aluminum fibers and stainless fibers, organic fibers such as aramid fibers and PBO fibers, inorganic fibers such as silicon carbide fibers, and carbon fibers. Carbon fibers are preferred from the viewpoint of the balance between rigidity and lightness, and among them, polyacrylonitrile-based carbon fibers are suitably used. In addition, polypropylene resins, polyamide resins, polyester resins, polyphenylene sulfide resins, etc. are used as thermoplastic resins used as matrix resins, but polyphenylene sulfide resins are excellent in heat resistance, chemical resistance, and flame retardancy. (Hereinafter abbreviated as PPS resin) are attracting attention as electrical / electronic equipment members and automobile equipment members. In addition, it can be molded into various molded parts, films, sheets, fibers, etc. by injection molding, extrusion molding, etc., and is widely used in fields requiring heat resistance, chemical resistance, and flame resistance.

  Furthermore, various forms such as injection molding materials, prepregs, yarns and mats using continuous carbon fibers are known as molding materials using carbon fibers and thermoplastic resins as a matrix. Such a molding material makes use of the properties of the thermoplastic resin to facilitate molding, does not require a storage load like a thermosetting resin, and the resulting molded product has high toughness and excellent recyclability. It has characteristics and is useful as an industrial material. By using these molding materials, various molded products can be obtained by various molding methods such as injection molding, extrusion molding, stamping molding, and autoclave molding.

  However, when carbon fiber is added, the viscosity of the thermoplastic resin containing the carbon fiber increases, and the moldability deteriorates. Therefore, in order to mold, it is necessary to increase the molding temperature and molding pressure. However, by increasing the molding temperature and molding pressure, resin decomposition and resin burns occur, and many fiber breaks occur during molding. Sometimes. On the other hand, when the molding pressure cannot be increased, an unfilled portion of the thermoplastic resin is generated, which may cause a decrease in strength.

  Further, in the process of producing a molding material, there is a problem in terms of economy and productivity in impregnating a continuous carbon fiber with a thermoplastic resin, and it is not widely used at present. For example, it is well known that the higher the melt viscosity of the resin, the more difficult the impregnation of the reinforcing fiber bundle is. Thermoplastic resins with excellent mechanical properties such as toughness and elongation are high molecular weight polymers, have higher viscosity than thermosetting resins, and require higher processing temperatures, making molding materials easier. In addition, it is unsuitable for manufacturing with good productivity. On the other hand, when a low molecular weight, that is, a low-viscosity thermoplastic resin is used for the matrix resin due to the ease of impregnation, there is a problem that the mechanical properties of the obtained molded product are significantly lowered.

  Patent Document 1 discloses a resin composition composed of a PPS resin and an oligomeric ester, which improves the fluidity of the PPS resin, but the oligomeric ester has poor heat resistance, so that an evaporation gas or Decomposed gas may be generated, or the decomposed gas may become a void in the molded product, thereby reducing physical properties. Further, since the additive has a low molecular weight, it may move to the surface of the molded product, and the additive may contaminate the mold surface or the molded product surface.

  Patent Document 2 discloses a method in which a silane compound is added to a resin composition comprising a PPS resin, an alkoxysilane compound, and reinforcing fibers to improve low burr properties. There is no mention of improvement.

  Patent Document 3 discloses a resin composition composed of a PPS resin, a thermoplastic polyester, an epoxy resin, and reinforcing fibers, but does not mention any improvement in workability by reducing the viscosity of the PPS resin. In addition, the amount of thermoplastic polyester added is large, resulting in insufficient heat resistance and strength deterioration due to hydrolysis.

  Thus, in the prior art, the improvement of the molding processability of the resin composition composed of the PPS resin and the carbon fiber, and the heat resistance and hydrolysis resistance at the time of molding could not be expressed. Therefore, the development of a polyphenylene sulfide resin composition excellent in molding processability and fiber dispersibility during injection molding, and excellent in mechanical properties and hydrolysis resistance when formed into a molded product, and a molding material and molded product using the same are desired. It was rare.

JP 62-45654 A Japanese Patent No. 3079923 JP 59-58052 A

  In view of the background of the prior art, the present invention greatly improves the molding processability of a resin composition composed of carbon fiber and PPS resin, and can produce a molded article excellent in mechanical properties, a carbon fiber reinforced polyphenylene sulfide resin composition, An object of the present invention is to provide a molding material using the same, and a molded article using the same.

  As a result of intensive studies to achieve the above object, the present inventors have found the following carbon fiber reinforced polyphenylene sulfide resin composition, and a molding material and a molded product using the same, which can achieve the above-mentioned problems. .

The carbon fiber reinforced polyphenylene sulfide resin composition of the present invention has the following configuration in order to solve the above problems. That is, it is a carbon fiber reinforced polyphenylene sulfide resin composition comprising the following components (A) to (C).
(A) Carbon fiber 1-75 mass%
(B) Polyphenylene sulfide resin 17 to 99.99% by mass
(C) Polyalkylene terephthalate 0.01-8 mass%.

  Moreover, in order to solve the said subject, the molding material of this invention has the following structure. That is, a molding material using the fiber-reinforced polyphenylene sulfide resin composition, which is obtained by melt-kneading (A) to (C) at 280 to 350 ° C., the fiber-reinforced polyphenylene sulfide A molding material using a resin composition, comprising (E) a carbon fiber reinforced polyphenylene sulfide resin composition obtained by melt-kneading (A) and (B) at 280 to 350 ° C. and (C) (D) a polymer alloy obtained by melt-kneading (B) and (C) at a temperature of 280 to 350 ° C., or a molding material using the carbon fiber reinforced polyphenylene sulfide resin composition A molding material impregnated in (A).

  Furthermore, in order to solve the said subject, the molded article of this invention has the following structure. That is, it is a molded product molded using the molding material.

  When the carbon fiber reinforced polyphenylene sulfide resin composition of the present invention is used as a molding material, the impregnation property of the PPS resin into the carbon fiber is good, and when the molding material is used as a molding product, A molded article having good dispersibility of the fibers in the molded article and excellent mechanical properties can be produced. A molded product molded using the molding material of the present invention is extremely useful for various parts and members such as electrical / electronic equipment, OA equipment, home appliances, automobile parts, internal members, and housings.

It is a DSC curve of PPS resin / PET and PPS resin.

  The present invention is a carbon fiber reinforced polyphenylene sulfide resin composition comprising (A) carbon fiber, (B) polyphenylene sulfide resin, and (C) polyalkylene terephthalate resin. First, these components will be described.

  Examples of the (A) carbon fiber used in the present invention include PAN, pitch and rayon. These may be used alone or in combination of two or more. These carbon fibers are preferable from the viewpoint of improving mechanical properties and reducing the weight of the molded product, and PAN-based carbon fibers are more preferable from the viewpoint of the balance between strength and elastic modulus of the molded product obtained. For the purpose of imparting conductivity, carbon fibers coated with a metal such as nickel, copper or ytterbium can also be used.

  The carbon fiber used in the present invention is composed of 1 to 75% by mass. If it is less than 1% by mass, the mechanical properties of the obtained molded product may be insufficient, and if it exceeds 75% by mass, the fluidity may be lowered during molding such as injection molding. Preferably it is 5-65 mass%, More preferably, it is 10-50 mass%.

  Further, as the carbon fiber, 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 0.05-0. 5 is preferable, more preferably 0.08 to 0.4, and still more preferably 0.1 to 0.3. When the surface oxygen concentration ratio is 0.05 or more, the functional group amount on the surface of the carbon fiber can be secured, and a stronger adhesion to the thermoplastic resin can be obtained. Moreover, although there is no restriction | limiting in particular in the upper limit of surface oxygen concentration ratio, Generally it is preferable to set it as 0.5 or less from the balance of the handleability of carbon fiber, and productivity.

The surface oxygen concentration ratio of the carbon fiber is determined by X-ray photoelectron spectroscopy according to the following procedure. First, after cutting the carbon fiber bundle from which the sizing agent and the like adhering to the carbon fiber surface with a solvent was cut to 20 mm and spreading and arranging on a copper sample support base, using A1Kα1,2 as the X-ray source, The sample chamber is maintained at 1 × 10 ⁸ Torr. The kinetic energy value (KE) of the main peak of C _1s is adjusted to 1202 eV as a peak correction value associated with charging during measurement. C _1s peak area E. Is obtained by drawing a straight base line in the range of 1191 to 1205 eV. O _1s peak area E. Is obtained by drawing a straight base line in the range of 947 to 959 eV.

Here, the surface oxygen concentration ratio is calculated as an atomic number ratio from the ratio of the O _1s peak area to the C _1s peak area using a sensitivity correction value unique to the apparatus. As an X-ray photoelectron spectroscopy apparatus, model ES-200 manufactured by Kokusai Electric Inc. is used, and the sensitivity correction value is set to 1.74.

  The means for controlling the surface oxygen concentration ratio [O / C] to 0.05 to 0.5 is not particularly limited. For example, techniques such as electrolytic oxidation, chemical oxidation, and vapor phase oxidation are used. Among these, electrolytic oxidation treatment is preferable.

  The average fiber diameter of the carbon fibers is not particularly limited, but is preferably in the range of 1 to 20 μm and preferably in the range of 3 to 15 μm from the viewpoint of the mechanical properties and surface appearance of the obtained molded product. More preferred. There is no restriction | limiting in particular in the number of single yarns at the time of setting it as a carbon fiber bundle, It can use within the range of 100-350,000, It can be used especially within the range of 1,000-250,000. preferable. Further, from the viewpoint of productivity of carbon fibers, those having a large number of single yarns are preferable, and it is preferable to use them within a range of 20,000 to 100,000.

  In addition, by applying a sizing agent to the carbon fiber, it is possible to improve the adhesion and composite overall characteristics by adapting to the surface characteristics such as functional groups on the surface of the carbon fiber. In addition, it improves bundling, bending resistance, and abrasion resistance, and suppresses the occurrence of fluff and yarn breakage in the high-order processing step. It can also improve the high-order workability as a so-called paste and bundling agent. it can.

  The sizing agent adhesion amount is not particularly limited, but is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, based on the mass of the carbon fiber alone, 0.1% More preferably, it is applied in an amount of from 2% by weight to 2% by weight. If it is 0.01% by mass or less, the effect of improving adhesiveness is hardly exhibited, and if it is 10% by mass or more, the physical properties of the matrix resin may be lowered.

  Examples of the sizing agent include a bisphenol type epoxy compound, a linear low molecular weight epoxy compound, polyethylene glycol, polyurethane, polyester, an emulsifier, or a surfactant. Moreover, these may use together 1 type, or 2 or more types.

  The means for applying the sizing agent is not particularly limited. For example, there are a method of immersing in a sizing liquid through a roller, a method of contacting a roller to which the sizing liquid is adhered, and a method of spraying the sizing liquid in a mist form. . Moreover, although either a batch type or a continuous type may be sufficient, the continuous type which has good productivity and small variations is preferable. At this time, it is preferable to control the sizing solution concentration, temperature, yarn tension, and the like so that the amount of the sizing agent active ingredient attached to the carbon fiber is uniformly attached within an appropriate range. Moreover, it is more preferable to vibrate the carbon fiber with ultrasonic waves when applying the sizing agent.

  The drying temperature and drying time should be adjusted according to the amount of the compound attached, but the time required for complete removal of the solvent used to apply the sizing agent and drying is shortened, while the thermal deterioration of the sizing agent is prevented and sizing is performed. From the viewpoint of preventing the carbon fiber bundle formed of the treated carbon fiber (A) from becoming hard and deteriorating the spreadability of the bundle, the drying temperature is preferably 150 ° C. or higher and 350 ° C. or lower. More preferably, the temperature is 180 ° C. or higher and 250 ° C. or lower.

  Examples of the solvent used for the sizing agent include water, methanol, ethanol, dimethylformamide, dimethylallylacetamide, and acetone. Water is preferable from the viewpoint of easy handling and disaster prevention. Accordingly, when a compound insoluble or hardly soluble in water is used as a sizing agent, it is preferable to add an emulsifier and a surfactant and disperse in water. Specifically, as an emulsifier and a surfactant, styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, formalin condensate of naphthalene sulfonate, anionic emulsifier such as sodium polyacrylate, Nonionic emulsifiers such as cationic emulsifiers such as polyethyleneimine and polyvinylimidazoline, nonylphenol ethylene oxide adducts, polyvinyl alcohol, polyoxyethylene ether ester copolymers, sorbitan ester ethyl oxide adducts, etc. can be used. A nonionic emulsifier having a small size is preferable because it hardly inhibits the adhesive effect of the polyfunctional compound.

  Moreover, as a form of carbon fiber used as a molding material, a continuous fiber may be sufficient and a discontinuous fiber may be sufficient. When used as a continuous fiber, it may be unidirectionally processed or woven such as plain weave, braid, and multiaxial woven fabric. When used as a discontinuous fiber, a chopped yarn or a nonwoven fabric may be used. The term “nonwoven fabric” as used herein refers to a fiber sheet or web in which fibers are oriented in one direction or randomly and the fibers are bonded by any of entanglement, fusion, or adhesion.

  As length of the carbon fiber used as a discontinuous fiber, 2-50 mm is preferable, More preferably, it is 4-25 mm, More preferably, it is 5-15 mm. If it is 2 mm or less, the strength improvement effect may be small when it is formed into a molded product, and if it is 50 mm or more, it may be difficult to orient the carbon fibers randomly. The orientation referred to here can be easily obtained by comparing the strength ratio in the vertical and horizontal directions of the molded product. The closer the vertical and horizontal strength ratio is to 1, the more isotropic and the easier it is to handle. preferable. The intensity ratio is calculated using the direction of higher intensity as the denominator. Specifically, 0.5 to 1 is preferable, 0.7 to 1 is more preferable, and 0.9 to 1 is more preferable.

  Specific methods for producing the nonwoven fabric include a dry method and a wet method. Also, in order to produce random nonwoven fabrics, the dry method uses a method of providing a fiber opening bar, a method of vibrating the fiber opening bar, a method of finer card eyes, and a card rotation speed adjustment. There are ways to do it. In the wet method, there are a method of adjusting the stirring conditions when dispersing the carbon fibers, a method of diluting the concentration, a method of adjusting the solution viscosity, and a method of suppressing eddy currents when transferring the dispersion.

  The (B) PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula, and a polymer containing a repeating unit represented by the following structural formula is 70 mol% or more from the viewpoint of heat resistance. More preferably, it contains 90 mol% or more.

  From the viewpoint of heat resistance, a polymer containing 70 mol% or more, particularly 90 mol% or more of the repeating unit represented by the above structural formula is preferable. In addition, the PPS resin can comprise 30 mol% or less of the repeating units with repeating units having the following structural formula.

  The PPS resin used in the present invention is composed of 17 to 99.99% by mass. By using the PPS resin in the range of 17 to 99.99% by mass, the PPS resin having excellent characteristics such as heat resistance, chemical resistance, and flame retardancy can be obtained. Preferably it is 30-95 mass%, More preferably, it is 40-90 mass%.

  The PPS resin used in the present invention is a known method, that is, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or JP-B-52-12240, It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in JP-A-61-7332.

  In the present invention, the PPS resin obtained as described above is subjected to crosslinking / polymerization by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, organic solvent, hot water, acid aqueous solution, etc. It can be used after various treatments such as washing, activation with functional group-containing compounds such as acid anhydrides, amines, isocyanates, functional group-containing disulfide compounds, and more than two types of these treatments. Of course it is also possible to do. Of course, it is possible to use two or more kinds of PPS resins subjected to these treatments. As a specific method of using two or more types of mixture, PPS resin crosslinked by heating in air and PPS resin not subjected to heat treatment are mixed, PPS resin washed with acid aqueous solution and washing with organic solvent are performed. Examples thereof include mixing of PPS resin, mixing of PPS resin washed with an organic solvent and PPS resin not washed with an organic solvent, and the like.

Although there is no restriction | limiting in particular about the molecular weight of PPS resin used by this invention, in order to influence the below-mentioned dispersion diameter, it is necessary to select suitably, About melt viscosity which is a parameter regarding this molecular weight, usually 5-1, 000 Pa · s (320 ° C., shear rate 1000 sec ⁻¹ ) is used, and 10 to 500 Pa · s is preferably used.

  As a specific method for crosslinking / high molecular weight by heating PPS resin, it can be performed in an oxidizing gas atmosphere such as air or oxygen, or in a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. Examples of the method include heating until a desired melt viscosity is obtained at a predetermined temperature. The heat treatment temperature is usually selected from 170 to 280 ° C., preferably from 200 to 270 ° C., and the time is usually selected from 0.5 to 100 hours, preferably from 2 to 50 hours. The target viscosity level can be obtained by appropriately controlling the time. The heat treatment apparatus may be a normal hot air dryer with reduced pressure specifications or a high-sealing specification, or a heating apparatus with a rotary type or a stirring blade, but it is rotated when it is processed efficiently and more uniformly. It is more preferable to use a heating device with a formula or a stirring blade.

  As a specific method for heat-treating the PPS resin under an inert gas atmosphere such as nitrogen or under reduced pressure, a heat treatment temperature of 150 to 280 ° C., preferably 200 to 200 ° C. under an inert gas atmosphere such as nitrogen or under reduced pressure. A method of heat treatment at 270 ° C. and a heating time of 0.5 to 100 hours, preferably 2 to 50 hours can be exemplified. The heat treatment apparatus may be a stationary heating apparatus or a rotary type or a heating apparatus with a stirring blade. However, in the case of efficient and more uniform processing, a heating apparatus with a rotary type or a stirring blade may be used. More preferably it is used.

  The following method can be illustrated as a specific method when the PPS resin is washed with an organic solvent. That is, the organic solvent used for washing is not particularly limited as long as it does not have an action of decomposing the PPS resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and the like. , Sulfoxide / sulfone solvents such as dimethylsulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, ether solvents such as dimethyl ether, dipropyl ether, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane , Halogen solvents such as tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol Call, phenol, cresol, alcohol phenol based solvents such as polyethylene glycol, benzene, toluene, and aromatic hydrocarbon solvents such as xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform or the like is preferable. Moreover, these organic solvents can also be used by 1 type or in mixture of 2 or more types. As a method of washing with an organic solvent, there is a method of immersing a PPS resin in an organic solvent, and if necessary, stirring or heating can be appropriately performed. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning PPS resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C.

  The PPS resin that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

  The following method can be illustrated as a specific method when the PPS resin is treated with hot water. That is, it is preferable that the water used is distilled water or deionized water in order to express the preferable chemical modification effect of the PPS resin by hot water washing. The operation of the hot water treatment is usually performed by putting a predetermined amount of PPS resin into a predetermined amount of water and heating and stirring at normal pressure or in a pressure vessel. The ratio of the PPS resin to water is preferably larger, but usually a bath ratio of 200 g or less of PPS resin is selected for 1 liter of water.

  The following method can be illustrated as a specific method in the case of acid-treating PPS resin. That is, there is a method of immersing a PPS resin in an acid or an aqueous solution of an acid, and stirring or heating can be performed as necessary. The acid used is not particularly limited as long as it does not have an action of decomposing PPS resin, and is saturated with aliphatic monocarboxylic acid such as formic acid, acetic acid, propionic acid and butyric acid, and halo-substituted aliphatic such as chloroacetic acid and dichloroacetic acid. Aliphatic unsaturated monocarboxylic acids such as saturated carboxylic acid, acrylic acid and crotonic acid, 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, sulfuric acid Inorganic acid compounds such as phosphoric acid, hydrochloric acid, carbonic acid and silicic acid. Of these, acetic acid and hydrochloric acid are more preferably used. The acid-treated PPS resin is preferably washed several times with water or warm water in order to remove residual acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the effect of preferable chemical modification of the PPS resin by acid treatment.

  In addition, the shape of the PPS resin used in the present invention is not particularly limited, and examples thereof include pellets, flakes, granules, and powders.

  Examples of the (C) polyalkylene terephthalate used in the present invention include polyalkylene terephthalate, copolyester of alkylene terephthalate, and a mixture of polyalkylene terephthalate.

  Examples of the polyalkylene terephthalate include polymers obtained using a diol component and a terephthalic acid component. Examples of the diol component include ethylene glycol, 1,4 butanediol, propylene glycol, trimethylene glycol, tetramethylene glycol, Hexamethylene glycol, neopentyl glycol, diethylene glycol, polyethylene glycol, cyclohexanedimethanol, 2,2-bis (2′-hydroxyethoxyphenyl) propane, and the like and derivatives thereof having ester-forming ability include 1,4 butanediol, Obtained by polycondensation of an ester-forming derivative thereof, ethylene glycol or an ester-forming derivative thereof and terephthalic acid or an ester-forming derivative thereof Polybutylene terephthalate and polyethylene terephthalate is preferably used.

  Among these, polyethylene terephthalate is more preferable because it is excellent in thermal stability and is a relatively inexpensive polymer.

  Moreover, the fluidity | liquidity and crystallinity of a resin composition improve drastically by making the polyalkylene terephthalate used by this invention into the range of 0.01-8 mass% (refer figure). If it is 0.01% by mass or less, fluidity may not be improved, and if it is 8% by mass or more, chemical resistance may be inferior.

  The intrinsic viscosity of the polyalkylene terephthalate is preferably 0.5 to 1.1. The intrinsic viscosity mentioned here can be replaced with the molecular weight of polyalkylene terephthalate, and the molecular weight corresponding to the intrinsic viscosity of 0.5 to 1.1 is 10,000 to 30,000. When the intrinsic viscosity is less than 0.5, the crystallinity tends to be lowered, and when it exceeds 1.1, the dispersibility is lowered and the mechanical properties of the resin composition tend to be lowered. More preferably, it is 0.6-1.0.

  The shape of the polyalkylene terephthalate used in the present invention is not particularly limited, and examples thereof include pellets, flakes, granules, and powders.

  The carbon fiber reinforced polyphenylene sulfide resin composition of the present invention contains reinforcing fillers such as glass fibers, ceramic fibers such as alumina fibers, aramid fibers, wholly aromatic polyester fibers, metal fibers, potassium titanate whiskers, etc. And calcium carbonate, mica, talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nepheline cinnite, attapulgite, wollastonite, PMF, ferrite, calcium silicate, magnesium carbonate Inorganic fillers such as dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloon, quartz, quartz glass, and organic, It is also possible to blend a machine pigments.

  Examples of the glass fiber include a chopped strand having a fiber length of 1.5 to 12 mm, a fiber diameter of 3 to 24 μm, a milled fiber having a fiber diameter of 3 to 8 μm, and glass flakes and glass powder of 325 mesh or less.

  Also, release agents such as wax, silane and titanate coupling agents, lubricants, heat stabilizers, weathering stabilizers, crystal nucleating agents, foaming agents, rust inhibitors, ion trap agents, flame retardants, flame retardants An auxiliary agent or the like may be added as necessary.

  Furthermore, it is also possible to add a small amount of another polymer to the resin composition of the present invention to impart other physical properties. Polymers to be added include polyethylene, polybutadiene, polyisoprene, polychloroprene, polystyrene, polybutene, poly α-methylstyrene, polyvinyl acetate, polyvinyl chloride, polyacrylic ester, polymethacrylic ester, polyacrylonitrile, nylon 6, Polyamide such as nylon 66, nylon 610, nylon 12, nylon 11, nylon 46, polyester such as polyarylate, polyurethane, polyacetal, polycarbonate, polyphenylene oxide, polysulfone, polyethersulfone, polyallylsulfone, polyphenylene sulfide sulfone, polyetherketone , Polyphenylene sulfide ketone, polyetheretherketone, polyimide, polyamideimide, silicone resin, Carboxymethyl resins, homopolymers, such as fluorine resin, random or block, graft copolymers and mixtures thereof or a reformate, and the like.

  The (D) polymer alloy constituting one embodiment of the present invention is obtained by melt-kneading (B) a PPS resin and (C) polyarylene terephthalate at a temperature of 280 to 350 ° C.

  The method of melt kneading is not particularly limited, and a known heat melt mixing apparatus can be used. Specifically, a single-screw extruder, a twin-screw extruder, a combination twin-screw extruder, a kneader / ruder, or the like can be used as the heat-melt mixing device. Among these, a twin screw extruder is preferably used because the dispersibility of the PPS resin and the polyalkylene terephthalate is improved. More preferably, a twin screw extruder having two or more kneading zones is used.

  The method of supplying the PPS resin and polyalkylene terephthalate to the kneader during kneading is not particularly limited. For example, the method of previously blending the PPS resin and polyalkylene terephthalate and supplying them to the kneader, each of the PPS resin and polyalkylene terephthalate Examples thereof include a method of feeding to a kneader while measuring and a method of feeding polyalkylene terephthalate by side feed to a kneader supplied with a PPS resin.

  The kneading temperature is characterized by melt kneading at a temperature of 280 to 350 ° C. The temperature referred to here is the temperature of the resin measured at the discharge unit. When the temperature is kneaded at a temperature lower than 280 ° C., the melt viscosity of the PPS resin becomes high or the PPS resin becomes unmelted, so that dispersibility is deteriorated and the mechanical properties of the molded product may be lowered. On the other hand, when the temperature exceeds 350 ° C., the polyalkylene terephthalate is decomposed, and a decomposed product adheres to the die of the kneader, resulting in a decrease in productivity and a decrease in the strength of the molded product. Preferably, it is 285-330 degreeC, More preferably, it is 290-320 degreeC.

  The kneading time is not particularly limited, but is preferably 0.5 to 30 minutes. If the kneading time exceeds 30 minutes, the thermal decomposition reaction may proceed and the physical properties may deteriorate. On the other hand, if it is shorter than 0.5 minutes, the dispersion becomes insufficient, and the strength of the molded product may be lowered.

  Originally, the PPS resin has a high melting point of 285 ° C., and it is necessary to heat it to 300 ° C. or higher in order to obtain fluidity. However, the (D) polymer alloy obtained by the kneading method does not change the melting point but is higher than the melting point. It has been found that the fluidity of the polymer alloy is drastically improved, fluidized even at 290 ° C., and surprisingly, the viscosity of the polymer alloy is lower than that of either the PPS resin or the polyalkyl terephthalate. . By using such a polymer alloy, it was possible to achieve both moldability and dimensional stability.

  The cause of this is not clear, but it is thought that polyalkylene terephthalate enters between PPS molecules to plasticize and fluidize the polymer alloy. Further, it is considered that the polyalkylene terephthalate enters between the PPS molecules, whereby the benzene ring of the polyalkylene terephthalate and the benzene ring of the PPS resin are stacked, and the crystallinity during cooling is improved. For this reason, if the content of polyalkylene terephthalate is less than 0.01% by mass, the effect of improving fluidity and crystallinity may not be obtained. On the other hand, if it is more than 8% by mass, the excellent properties of the PPS resin, such as heat resistance, chemical resistance and flame retardancy, may not be obtained. Further, the dispersion diameter of the polyalkylene terephthalate tends to increase, and the strength of the molded product may decrease. Preferably it is 0.1-5 mass%. More preferably, it is 1-3 mass%. Note that polyalkylene terephthalate can be expected to obtain heat resistance, chemical resistance, flame retardancy and other properties as well as improved fluidity compared to the case where oligomeric esters are used. An increase in strength is also observed.

  The polymer alloy (D) constituting one embodiment of the present invention has a cooling crystallization temperature (Tc ′) of 230 to 250 ° C. measured at a cooling rate of 16 ° C./min by differential scanning calorimetry (DSC) measurement. Is preferred. By setting it as such a range, the heat resistance of a resin composition improves and the mechanical strength of the molded article using this resin composition improves. Preferably it is 240-250 degreeC.

  The (D) polymer alloy constituting one embodiment of the present invention is not particularly limited in the temperature rising crystallization temperature measured at a temperature rising rate of 16 ° C./min by DSC measurement, but the temperature rising crystallization temperature (Tc) is 130 ° C. The molding processability is improved by the following.

The polymer alloy (D) constituting one embodiment of the present invention preferably has a melt viscosity of 200 Pa · sec or less measured at a shear rate of 1216 sec ^{−1 at} 290 ° C. If it exceeds 200 Pa · sec, an unstable flow state tends to occur during molding, and stable productivity during molding may not be ensured. By reducing the melt viscosity at the molding temperature, the flow state can be stabilized and the productivity can be improved.

  The melt viscosity is a value measured by a capillary rheometer (Toyo Seiki Seisakusho Co., Ltd. Capillograph Type 1B).

  The dispersion diameter of (C) polyarylene terephthalate contained in (D) the polymer alloy constituting one embodiment of the present invention can be observed by a molded product obtained by molding the molding material of the present invention. Is preferably 0.4 μm or less. In the present invention, the dispersion diameter of (C) polyarylene terephthalate is the polydisperse in the case where the phase mainly composed of PPS resin and the phase mainly composed of polyarylene terephthalate have a phase separation structure of 0.01 μm or more. It is the diameter of the island part of the phase structure mainly composed of arylene terephthalate. When the island phase is elliptical, indeterminate, or a circle or ellipse of two or more layers, the average value of the longest distance and the shortest distance of the island phase shall be used. On the other hand, in a state where they are uniformly mixed at the molecular level, that is, when the phase mainly composed of polyarylene terephthalate has a phase separation structure period of less than 0.01 μm, it is regarded as a compatible state. In the present invention, the dispersion diameter of 0.4 μm or less may have a phase separation structure or a compatible state. On the other hand, when the thickness is 0.4 μm or more, the strength of the molded product may decrease. More preferably, it is 0.3 μm or less.

  In addition, the dispersion diameter of (C) polyarylene terephthalate can observe the cross section of the molded article obtained by shape | molding the molding material of this invention with a scanning electron microscope or a transmission electron microscope. You may dye | stain with osmium etc. as needed. Dyeing can be performed by a usual method.

  (D) The polymer alloy constituting one aspect of the present invention has a crystallizing rate that is significantly faster than that of conventional PPS resins. Therefore, even if a low-temperature mold is used, it is sufficiently crystallized by injection molding and has excellent heat resistance. Goods can be obtained. In addition, the polymer alloy of the present invention can lower the spinning temperature when it is formed into a fiber, and since the crystallization speed is fast, the heat setting temperature in the drawing process can also be lowered, so that energy saving in the spinning process can be achieved. Great effect. Further, since molding and spinning can be performed at a low temperature, the contamination of the die is reduced as compared with the conventional PPS resin, and the productivity is improved.

  The molding material in the present invention is a composite of (A) carbon fiber, (B) PPS resin, and (C) polyarylene terephthalate, preferably (A) carbon fiber, (B) PPS resin, and ( C) A composite with (D) a polymer alloy obtained by melting and kneading polyarylene terephthalate at a temperature of 280 to 350 ° C., which can be processed into a final product by various known molding methods It is. The method of compounding is not particularly limited, but the following four methods (1) to (4) are exemplified depending on the form of each component.

  (1) A method in which (A) carbon fiber, (B) PPS resin, and (C) polyarylene terephthalate are melt-kneaded at a temperature of 280 to 350 ° C. to form a composite. The method of melt kneading is not particularly limited, and a known heat melt mixing apparatus can be used. Specifically, a single-screw extruder, a twin-screw extruder, a combination twin-screw extruder, a kneader / ruder, or the like can be used as the heat-melt mixing device. Among these, a twin screw extruder is preferably used because the dispersibility of carbon fibers is improved. More preferably, a twin screw extruder having two or more kneading zones is used.

  The method of supplying each component to the kneading machine at the time of kneading is not particularly limited, and examples thereof include a method of feeding carbon fibers by side feed to a kneading machine in which a PPS resin and polyalkylene terephthalate are previously blended and supplied to the kneading machine. . In addition, the fluidity at the time of shaping | molding can be improved also by the method of melt-kneading carbon fiber and PPS resin and mix | blending polyalkylene terephthalate at the time of shaping | molding.

  (2) (D) A method in which a polymer alloy is heated and melted and (A) is combined with carbon fiber. For the heating and melting here, a known apparatus such as an extruder, a plunger, a melting bath or the like can be used, but it is preferable to have a function of transferring a molten polymer alloy such as a screw or a gear pump.

  For example, a polymer alloy is melted using an extruder and supplied to a die die such as a T die or a slit die, and a carbon fiber bundle is passed through the die die. A method in which a carbon fiber bundle is squeezed and passed in the melting bath, a polymer alloy melted by a plunger pump is supplied to a kiss coater, and a polymer alloy melt is applied to the carbon fiber, and the like. Further, there can be exemplified a method in which a polymer alloy melted on a heated rotating roll is supplied and a carbon fiber bundle is passed through the roll surface.

  Further, the molding material of the present invention can be used depending on the molding method even if it is continuous or long. For example, as a yarn prepreg, it can be wound around a mandrel while heating to obtain a roll-shaped molded product. Examples of such molded products include liquefied natural gas tanks. It is also possible to produce a unidirectional thermoplastic prepreg by heating and fusing a plurality of molding materials of the present invention in one direction. Such a prepreg can be applied to fields where lightness, high strength, elastic modulus, and impact resistance are required, such as automobile members.

  The manufactured molding material may be used after being cut into a predetermined length by a device such as a pelletizer or a strand cutter. This cutting step may be continuously provided after passing through the die die. If the molding material is flat or sheet-like, it may be slit and elongated before cutting. A sheet pelletizer that simultaneously performs slitting and cutting may be used.

  The molding material of the present invention is preferably used after being cut to a length in the range of 2 to 25 mm. By adjusting to the above length, the fluidity and handleability during molding can be sufficiently enhanced. A particularly preferred embodiment of the molding material cut to an appropriate length in this way can be exemplified by long fiber pellets for injection molding.

  (3) At least one type of (D) polymer alloy selected from the group consisting of particles, fibers, flakes, films, sheets, and nonwoven fabrics is disposed so as to be in contact with (A) carbon fibers. It is a method to make it. Here, the film shape means a thickness having an average thickness of 200 μm or less, and the sheet shape means a thickness having an average thickness exceeding 200 μm. The non-woven fabric is a fiber sheet or web, in which fibers are oriented in one direction or randomly, and the fibers are bonded by any of entanglement, fusion, or adhesion. The average thickness can be obtained by stacking a plurality of sheets or films, measuring arbitrary 10 points with calipers, and dividing the obtained thickness by the number of stacked sheets.

  Specifically, particle, fiber, and flaky polymer alloys are dispersed in the gas phase and adhered by passing carbon fiber, and particle, fiber, and flaky polymer alloys are dispersed in the liquid phase. A method of adhering by drying after passing, a method of moving carbon fibers to a conveyor and laminating a film-like polymer alloy on one or both sides with a hot roller, a method of fixing a non-woven polymer alloy by punching Examples thereof include a method in which carbon fibers and a nonwoven polymer alloy are entangled with an air jet.

  Moreover, it is preferable that any form is roll-processed from a viewpoint of economical efficiency and productivity. When the polymer alloy is difficult to roll, it is possible to exemplify one of preferable methods that the polymer alloy is coated on a release paper after being processed into each form and then rolled.

  Here, the form of the carbon fiber may be one direction, or a woven fabric such as a plain weave, a braid, or a multiaxial woven fabric. Moreover, the discontinuous fiber cut | disconnected by specific length may be sufficient and a nonwoven fabric form may be sufficient.

  (4) (D) A method in which fibers made of polymer alloy and (A) carbon fibers are mixed and compounded. The mixed weave in the present invention is a composite yarn made of a polymer alloy fiber and a carbon fiber, and may be a unidirectional, woven fabric such as a plain weave, a braid, and a multiaxial woven fabric. Moreover, a nonwoven fabric shape may be sufficient.

  A fiber made of a polymer alloy (hereinafter referred to as a polymer alloy fiber) is prepared by melt-kneading (B) PPS resin and (C) polyarylene terephthalate at a temperature of 280 to 350 ° C, and a spinning temperature of 285 to 310 ° C. It is preferable to perform melt spinning. When the spinning temperature exceeds 310 ° C., organic low-polymerization products such as oligomers contained in PPS resin, polyalkylene terephthalate decomposition products and oligomers volatilize, and the die frequently breaks due to dirt, etc. Stable spinning becomes difficult. It is preferable to melt-spin at a lower temperature because the amount of organic low polymerization products generated can be reduced by lowering the spinning temperature, and the amount of volatilization of polyalkylene terephthalate decomposition products and oligomers can be suppressed. If it is less than 285 ° C., the flowability of the resin is poor and stable melt spinning becomes difficult. By setting it as the range of the present invention, both the fluidity of the polymer and the generation amount of volatile components such as organic low polymerization degree products and decomposition products can be achieved, and the polymer alloy fiber can be produced stably. A more preferable spinning temperature is 285 to 300 ° C.

  In the method for producing a polymer alloy fiber, there is no particular limitation as long as it is melt-spun by the melt spinning step after the melt-kneading step. For example, pellets obtained by melt-kneading PPS resin and polyalkylene terephthalate in an extruder in advance may be used, or a master batch containing polyalkylene terephthalate at a high concentration is prepared and diluted to an arbitrary concentration in the spinning process. You may do it. Further, the kneading machine may be directly connected to the spinning machine, and the kneaded melt may be directly spun without obtaining pellets.

  In the spinning process, in order to prevent gelation due to thickening, it is desirable to heat to the spinning temperature in a nitrogen atmosphere and discharge from the die. A die used for ordinary melt spinning, for example, one having a discharge hole diameter D of 0.15 to 0.5 mmφ and a discharge hole depth L of about 0.2 to 2.0 mm is preferably used.

  The yarn discharged from the die is usually cooled after being spun by a chimney wind with a wind speed of 5 to 100 m / min, provided with an appropriate amount of oil as a bundling agent, and obtained by winding. The take-up speed is not particularly limited, but is usually in the range of 500 m / min to 7000 m / min. In addition, the manufacturing process is UY (low speed spinning) or POY (high speed spinning), and is wound once. UY-DT (drawn twisted yarn) is drawn using a known drawing machine, POY-DT method, without winding. A process such as a DSD (direct spinning drawing) method in which the spinning drawing process is continuously performed can be applied. It is also possible to apply a process such as a POY-false twist process or a DT-false twist process.

  Furthermore, when producing short fibers, if necessary, the yarn obtained by spinning is drawn in a warm water bath or on a hot plate at an appropriate magnification, and then, if necessary, a stuffing box type crimper. Then, crimping is performed, relaxation heat treatment is performed at a predetermined temperature, and after the oil agent is applied, the fiber is cut into a predetermined length to obtain a short fiber. The properties of the obtained yarn are not particularly limited, but usually the single yarn fineness is 0.5 to 10.0 dtex, the strength is 2.0 cN / dtex or more, preferably 3.0 cN / dtex or more, more preferably 3.1 cN / Although it is not less than dtex and the upper limit of the strength is not particularly limited, a fiber having usually 10.0 cN / dtex or less, an elongation of 10 to 100%, and a dry heat shrinkage of 0 to 20.0% is obtained.

  In addition, the cross-sectional shape of the PPS fiber of the present invention is not particularly limited, and is not limited to a normal circular cross section, but also a Δ cross section, a Y-shaped cross section, a □ cross section, a cross section, a hollow cross section, a C-shaped cross section, and a rice field cross section Any irregular cross section can be adopted.

  In addition, by heating and pressurizing the composite composed of (A) carbon fiber and (D) polymer alloy obtained by the methods (3) to (4), (D) polymer alloy is applied to (A) carbon fiber. A molding material impregnated with may be used.

  First, it is important to heat a composite made of carbon fiber and a polymer alloy, and to melt the polymer alloy by the heating. The heating temperature at this time is 280-400 degreeC, Preferably it is 285-380 degreeC, More preferably, it is 290 degreeC-360 degreeC, More preferably, it is 295-340 degreeC. If it is less than 280 ° C., the polymer alloy cannot be sufficiently melted and the molding material becomes insufficiently impregnated, and if it is 400 ° C. or more, an undesirable side reaction such as causing a decomposition reaction of the polymer alloy may occur.

  As a heating method, specifically, a method in which a plurality of pressure rollers are arranged in a heated chamber to pass the composite, a method in which calendar rolls are similarly arranged up and down to pass the composite, a hot roller, The method of performing heating and pressurization simultaneously using can be illustrated.

  Moreover, it is preferable to heat in non-oxidizing atmosphere from a viewpoint of suppressing generation | occurrence | production of unfavorable side reactions, such as a crosslinking reaction and decomposition reaction of a polymer alloy. Here, the non-oxidizing atmosphere is an atmosphere having an oxygen concentration of 5% by volume or less, preferably 2% by volume or less, more preferably an oxygen-free atmosphere, that is, an inert gas atmosphere such as nitrogen, helium or argon. Of these, a nitrogen atmosphere is particularly preferred from the standpoints of economy and ease of handling.

  Furthermore, it is preferable to apply the pressure simultaneously with heating or after heating, because the impregnation of the polymer alloy into the carbon fibers can be further enhanced. The applied pressure here is preferably 0.5 to 10 MPa, more preferably 1 to 8 MPa, and further preferably 2 to 6 MPa from the viewpoint of the balance between impregnation and productivity.

  Specifically, in a system substituted with nitrogen, a method of passing the composite while applying pressure from above and below by a double belt press, or a combination of calender rolls arranged in multiple in a nitrogen-substituted heating furnace A method of passing the body while pressing, or placing the composite in a high-temperature press mold, sealing and pressurizing between the press molds, simultaneously replacing the inside of the mold with nitrogen, and releasing the space between the press molds after completion of impregnation as a decompression condition Thus, a method of pulling out the composite can be exemplified.

  In addition, the method for cooling the obtained composite is not particularly limited, and includes a method of cooling by jetting air, a method of spraying cooling water, a method of passing through a cooling bath, and passing over a cooling plate. A known method such as a method for causing the above can be used.

  When the production of the molding material is on-line, the take-up speed directly affects the process speed. Therefore, the take-up speed is preferably as high as possible from the viewpoints of economy and productivity. The take-up speed is preferably 5 to 100 m / min, more preferably 10 to 100 m / min, and still more preferably 20 to 100 m / min.

  Specific examples include a method of pulling out with a nip roller, a method of winding up with a drum winder, and a method of gripping a base material with a fixing jig and pulling up the jig together. Moreover, when picking up, a base material may be cut through a slitter, a sheet may be cut into a predetermined length with a guillotine cutter or the like, or it may be cut into a fixed length with a strand cutter or the like. Alternatively, it may be a roll shape.

  In addition, it is more preferable that the carbon fiber bundle is opened in advance in the stage before manufacturing the molding materials (2) to (4). Opening is an operation of dividing the converged carbon fiber bundle, and an effect of further improving the impregnation property of the PPS resin can be expected. By the opening, the thickness of the carbon fiber bundle is reduced, the width of the carbon fiber bundle before opening is b1 (mm), the thickness is a1 (μm), the width of the carbon fiber bundle after opening is b2 (mm), When the thickness is a2 (μm), the spread ratio = (b2 / a2) / (b1 / a1) is preferably 2.0 or more, and more preferably 2.5 or more.

  There are no particular restrictions on the method of opening the carbon fiber bundle. For example, a method in which concave and convex rolls are alternately passed, a method using a drum-type roll, a method of applying tension fluctuation to axial vibration, and two reciprocating vertically A method of changing the tension of the carbon fiber bundle by the friction body and a method of blowing air to the carbon fiber bundle can be used.

  In addition, the molding material of this invention can combine another process within the range which does not impair the effect. For example, an electron beam irradiation process, a plasma treatment process, a strong magnetic field application process, a skin material laminating process, a protective film attaching process, and the like can be mentioned.

  In the molding material of the present invention, mass distribution of each component can be easily carried out by controlling the take-up speed and the feeder supply amount.

The void ratio of the molding material of the present invention obtained after impregnation of (2), (3) or (4) is preferably in the range of 0 to 20%. A more preferable void ratio range is less than 10%. The void ratio is determined by measuring the composite part by the ASTM D2734 (1997) test method, or observing voids present in the cross section of the molding material, and calculating the following formula from the total area of the molding material and the total area of the void portion. Can be used to calculate.
Void ratio (%) = total area of void part / (total area of composite part + total area of void part) × 100.

  The molding method of the molding material obtained in the above (1) to (4) of the present invention is not particularly limited, but molding with excellent productivity such as injection molding, autoclave molding, press molding, filament winding molding, stamping molding, etc. It can be applied to the method and can be used in combination. Also, integrated molding such as insert molding and outsert molding can be easily performed. Furthermore, it is possible to utilize an adhesive method having excellent productivity such as a correction treatment by heating, heat welding, vibration welding, ultrasonic welding, etc. after molding. The obtained molded product reflects the characteristics of the PPS resin, is excellent in heat resistance, chemical resistance, mechanical characteristics, and flame retardancy, and can be developed for various uses.

  Molded products obtained by the above molding methods include cylinder head covers, bearing retainers, intake manifolds, pedals and other automotive parts, members and outer plates, landing gear pods, winglets, spoilers, edges, ladders, failings, ribs, etc. Aircraft related parts, members and outer panels, tools such as monkeys, wrenches, electrical or electronic equipment such as personal computers, displays, mobile phones, personal digital assistants, OA equipment housings, members, various rackets, golf club shafts, yachts It is useful in a wide range of applications such as sports-related parts such as boards, ski equipment, fishing rods, industrial materials such as members, rods, panels, floors, joints, hinges, gears, and satellite-related parts. Moreover, since it is excellent in fluidity | liquidity, the thin molded product whose thickness of a molded product is 0.5-2 mm can be obtained. Such thin-wall molding is required to be represented by, for example, a casing used for a personal computer, a mobile phone, or a keyboard support that is a member that supports the keyboard inside the personal computer. Examples of members for electrical and electronic equipment. Such a member for electrical / electronic equipment uses carbon fiber having conductivity, and is more preferable because it imparts electromagnetic wave shielding properties.

  The molded product molded using the molding material of the present invention preferably has a strength retention of 90% or more after being immersed in a 30% NaOH aqueous solution at 93 ° C. for 24 hours. More preferably, it is 95% or more. Originally, PPS resin is excellent in alkali resistance, but when polyalkyl terephthalate or the like having low alkali resistance is mixed, the polyalkyl terephthalate is decomposed by alkali and the strength of the molded product tends to decrease. However, in the molded article of the present invention, by blending 0.01 to 8% by mass of polyalkyl terephthalate, not only the moldability is improved, but also the decrease in alkali resistance can be suppressed.

  EXAMPLES The present invention will be described more specifically with reference to examples below, but the present invention is not limited to the description of these examples.

(1) Differential scanning calorimetry Measurement and calculation were performed according to JIS-K-7122 (1987) using differential scanning calorimetry (DSC). First, after maintaining at 320 ° C. for 2 minutes to completely melt, it was quenched with liquid nitrogen so that no crystals remained in the resin. Subsequently, the exothermic peak observed when the temperature was raised from 50 ° C. to 320 ° C. at 16 ° C./min was defined as Tc, followed by holding at 320 ° C. for 2 minutes and then from 320 ° C. to 50 ° C. at 16 ° C./min. The temperature of the exothermic peak observed when the temperature was lowered at a temperature lowering rate was determined as Tc ′.
Equipment: DS Instruments Q2000 manufactured by TA Instruments
Data analysis: Universal Analysis 2000 from TA Instruments.

(2) Melt viscosity Using a capillary rheometer, the melt viscosity was measured at a shear rate of 1216 sec ⁻¹ using a die having a pore diameter of 1 mmφ and L / D = 10.
Apparatus: Capillograph type 1B manufactured by Toyo Seiki Seisakusho Co., Ltd.

(3) Intrinsic viscosity [η]
The value calculated by the following formula was used from the solution viscosity measured at 25 ° C. at a concentration of 0.1 g / ml in orthochlorophenol.
ηsp / C = [η] + K [η] 2 · C

  Here, ηsp = (solution viscosity / solvent viscosity) −1, C is the dissolved polymer mass per 100 ml of solvent (g / 100 ml), and K is the Huggins constant (assuming 0.343). The solution viscosity and solvent viscosity were measured using an Ostwald viscometer.

(4) Strength (cN / dtex) and elongation (%) of polymer alloy fiber
In accordance with the method of JIS L 1013, the measurement was performed under conditions of a test length of 25 cm and a tensile speed of 30 cm / min.

(5) Thermal shrinkage rate of polymer alloy fiber The thermal shrinkage rate was determined as the thermal shrinkage rate (%) relative to the initial length after standing for 30 minutes in a hot water bath whose temperature was adjusted to 98 ° C. as an index of thermal stability.

(6) MFR
The measurement temperature was 315.5 ° C. and the load was 5000 g, and the measurement was performed by a method according to ASTM-D1238-70.

(7) Void Rate Void rate (%) was calculated based on the ASTM D2734 (1997) test method. The void ratio was determined according to the following criteria: A to C were acceptable for the molding material, and A and B were acceptable for the molded product.
A: 0 to less than 5% B: 5% or more and less than 10% C: 10% or more and less than 20% D: 20% or more.

(8) Fiber dispersibility of molded product obtained using molding material A molded product of 100 mm × 100 mm × 2 mm was molded, and the number of undispersed CF bundles present on the front and back surfaces was counted visually. The evaluation was performed on 50 molded products, and the fiber dispersibility of the total number was determined according to the following criteria, and A and B were determined to be acceptable.
A: 1 or less undispersed CF bundle B: 1 or more and less than 5 undispersed CF bundles C: 5 or more and less than 10 undispersed CF bundles D: 10 or more undispersed CF bundles

(9) NaOH treatment strength retention As a measure of alkali resistance, the molded product was immersed in a 30% NaOH aqueous solution. Thereafter, the aqueous NaOH solution was heated, the strength of the fiber after heat treatment at 93 ° C. for 24 hours was measured, and the strength retention rate (%) with respect to the initial strength was determined.
A: 0 to less than 5% B: 5 to less than 10% C: 10% to less than 20% D: 20% or more.

Reference Example 1 Carbon fiber 1
Spinning, firing treatment, and surface oxidation treatment were carried out from a copolymer containing polyacrylonitrile as a main component to obtain continuous carbon fibers having a total number of 24,000 single yarns. The characteristics of this continuous carbon fiber were as follows.
Single fiber diameter: 7μm
Mass per unit length: 1.6 g / m
Specific gravity: 1.8
Surface oxygen concentration ratio [O / C]: 0.06
Tensile strength: 4600 MPa
Tensile modulus: 220 GPa.

Here, the surface oxygen concentration ratio was determined according to the following procedure by X-ray photoelectron spectroscopy using the carbon fiber after the surface oxidation treatment. First, the carbon fiber bundle was cut to 20 mm, spread and arranged on a copper sample support, and then A1Kα1 and 2 were used as X-ray sources, and the inside of the sample chamber was kept at 1 × 10 ⁸ Torr. The kinetic energy value (KE) of the main peak of C _1s was adjusted to 1202 eV as a peak correction value associated with charging during measurement. C _1s peak area E. As a linear base line in the range of 1191 to 1205 eV. O _1s peak area E. As a linear base line in the range of 947 to 959 eV. The atomic ratio was calculated from the ratio of the O _1s peak area to the C _1s peak area using the sensitivity correction value unique to the apparatus. As an X-ray photoelectron spectroscopy apparatus, Kokusai Denki Co., Ltd. model ES-200 was used, and the sensitivity correction value was set to 1.74.

  Each raw material polymer and oligomer were synthesized according to the following reference examples.

Reference Example 2 Production and Synthesis of PPS Resin-1 In an autoclave with a stirrer and a valve at the bottom, 8267 g (70.00 mol) of 47.5% aqueous sodium hydrosulfide solution, 2925 g (70.20 mol) of 96% sodium hydroxide, N-methyl 2-Pyrrolidone (NMP) 13860.00 g (140.00 mol), sodium acetate 2187 g (26.67 mol), and ion-exchanged water 10500 g were charged and gradually increased to 240 ° C. over about 3 hours under nitrogen at normal pressure. Then, after distilling 14740 g of water and 280.0 g of NMP, the reaction vessel was cooled to 160 ° C. The residual water content in the system per 1 mol of the charged alkali metal sulfide was 1.08 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.023 mol per mol of the alkali metal sulfide charged.

  Next, 10324 g (70.24 mol) of p-dichlorobenzene (p-DCB) and 6452 g (65.17 mol) of NMP are added, the reaction vessel is sealed under nitrogen gas, and the mixture is stirred at 240 rpm with a temperature of 200 to 250 ° C. The temperature was raised to 0.8 ° C. at a rate of 0.8 ° C./min and held at 250 ° C. for 70 minutes. Next, the temperature was raised from 250 ° C. to 278 ° C. at a rate of 0.8 ° C./min, and maintained at 278 ° C. for 78 minutes. The extraction valve at the bottom of the autoclave was opened, the contents were flushed into a vessel equipped with a stirrer over 15 minutes while being pressurized with nitrogen, and stirred for a while at 250 ° C. to remove most of the NMP.

  The obtained solid and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70 ° C. for 30 minutes, and then suction filtered through a glass filter. Next, 76 liters of ion-exchanged water heated to 70 ° C. was poured into a glass filter, and suction filtered to obtain a cake.

  The obtained cake and 90 liters of ion-exchanged water were charged into an autoclave equipped with a stirrer, and the interior of the autoclave was replaced with nitrogen, and then the temperature was raised to 192 ° C. and held for 30 minutes. Thereafter, the autoclave was cooled and the contents were taken out.

The contents were subjected to suction filtration with a glass filter, and then 76 liters of ion-exchanged water at 70 ° C. was poured into the contents, followed by suction filtration to obtain a cake. The obtained cake was dried at 120 ° C. under a nitrogen stream to obtain dry PPS resin granules. The obtained PPS resin-1 had an MFR of 298 g / 10 min. The melt viscosity measured at 290 ° C. and a shear rate of 1216 sec ⁻¹ was 220 Pa · s.

Reference Example 3. Production of PPS resin-2 The same procedure as in Reference Example 2 was conducted except that the amount of p-DCB charged was changed to 10250 g (69.76 mol). The obtained PPS resin-2 had an MFR of 168 g / 10 min. The melt viscosity measured at 290 ° C. and a shear rate of 1216 sec ⁻¹ was 150 Pa · s.

Reference Example 4 Production of PET A slurry of 1000 g of high-purity terephthalic acid (manufactured by Mitsui Chemicals) and 450 g of ethylene glycol (manufactured by Nippon Shokubai Co., Ltd.) is charged in advance with about 1230 g of bis (hydroxyethyl) terephthalate, temperature 250 ° C., pressure 1.2 × 10 ^The esterification reaction tank maintained at ⁵ Pa was sequentially supplied over 4 hours, and after completion of the supply, the esterification reaction was further performed over 1 hour, and 1230 g of this esterification reaction product was transferred to the polycondensation tank.

  Subsequently, antimony trioxide is added to the polycondensation reaction tank to which the esterification reaction product has been transferred so that the amount of antimony trioxide becomes 230 ppm, and then the reaction system is heated from 250 ° C. to 285 ° C. while stirring the low polymer at 30 rpm. While gradually raising the temperature to 0 ° C., the pressure was reduced to 40 Pa.

The time to reach the final temperature and final pressure was both 60 minutes. When the predetermined stirring torque was reached, the reaction system was purged with nitrogen and returned to normal pressure, the polycondensation reaction was stopped, discharged into cold water in the form of a strand, and immediately cut to obtain 1000 g of a PET chip. The obtained polymer had an MFR of 158 g / 10 min. The melt viscosity measured at 290 ° C. and a shear rate of 1216 sec ⁻¹ was 140 Pa · s.

Reference Example 5 Production of BHT (PET oligomer (hereinafter referred to as BHT)) A slurry of 1000 g of high-purity terephthalic acid (Mitsui Chemicals) and 450 g of ethylene glycol (Nippon Shokubai Co., Ltd.) was previously charged with about 1230 g of bis (hydroxyethyl) terephthalate, and the temperature The esterification reaction tank maintained at 250 ° C. and a pressure of 1.2 × 10 ⁵ Pa was sequentially supplied over 4 hours, and the esterification reaction was performed over an additional hour after the completion of the supply.

After completion of the reaction, 1230 g was discharged into a stainless steel bat, air cooled, and then pulverized to obtain a PET oligomer powder. The obtained polymer had an MFR of 80 g / 10 min. The melt viscosity measured at 290 ° C. and a shear rate of 1216 sec ⁻¹ was 65 Pa · s.

Example 1
A bent type twin-screw kneading extruder containing 40% by mass of carbon fiber, 58.2% by mass of PPS resin-1 and 1.8% by mass of PET, and having two kneading zones heated to 300 ° C. The mixture was melt-extruded at a shear rate of 100 sec ⁻¹ and a residence time of 1 minute. The resin temperature during kneading was 300 ° C. From the kneader, it was discharged into cold water in a strand shape and immediately cut to obtain a molding material. The obtained molding material was cooled and then cut with a cutter to obtain a pellet-shaped molding material.

  Next, the obtained pellet-shaped molding material was vacuum-dried at 150 ° C. for 10 hours, and using a J350EIII type injection molding machine manufactured by Nippon Steel, Ltd., cylinder temperature: 320 ° C., mold temperature: 150 ° C. A characteristic evaluation test piece (molded product) was molded. Next, the obtained test piece for characteristic evaluation (molded product) was evaluated according to the above-described molded product evaluation method. The characteristic evaluation results are collectively shown in Table 1. The ratio of the carbon fiber in the obtained molded product was 40% by mass.

Example 2
A molding material and a molded product were obtained in the same manner as in Example 1 except that PET was blended at the time of injection molding. The characteristic evaluation results are collectively shown in Table 1.

Example 3
The carbon fiber was passed through a die die installed at the tip of a bent type biaxial kneading extruder having two kneading zones, and PPS resin-1 melted at 320 ° C. from the extruder into the die was 79. A polymer alloy comprising 2% by mass and 0.8% by mass of PET was discharged to impregnate the carbon fiber with the polymer alloy. At this time, the amount of polymer alloy was adjusted so that the content of carbon fiber alone was 20% by mass. The obtained molding material was cooled and then cut with a cutter to obtain a pellet-shaped molding material. The obtained molding material was obtained in the same manner as in Example 1 to obtain a molded product. The characteristic evaluation results are collectively shown in Table 1.

Example 4
A molding material and a molded product were obtained in the same manner as in Example 3 except that the blending amounts of PPS resin-1 and PET were 77.6% by mass and 2.4% by mass, respectively. The characteristic evaluation results are collectively shown in Table 1.

Example 5
A molding material and a molded product were obtained in the same manner as in Example 3 except that the blending amounts of PPS resin-1 and PET were 73.6% by mass and 6.4% by mass, respectively. The characteristic evaluation results are collectively shown in Table 1.

Example 6
A molding material and a molded product were obtained in the same manner as in Example 4 except that PPS resin-2 was used. The characteristic evaluation results are collectively shown in Table 1.

Example 7
A molding material and a molded product were prepared in the same manner as in Example 4 except that the carbon fiber content was 10% by mass, and the blending amounts of PPS resin-1 and PET were 87.3% by mass and 2.7% by mass, respectively. Obtained. The characteristic evaluation results are collectively shown in Table 1.

Example 8
A molding material and a molded product were prepared in the same manner as in Example 4 except that the carbon fiber content was 30% by mass and the blending amounts of PPS resin-1 and PET were 67.9% by mass and 2.1% by mass, respectively. Obtained. The characteristic evaluation results are collectively shown in Table 1.

Example 9
A molding material was obtained in the same manner as in Example 4 except that the carbon fiber content was 50% by mass and the prepreg was not cut with a cutter. The obtained molding material was vacuum-dried at 150 ° C. for 10 hours, and a characteristic evaluation test piece (molded product) was molded at a mold temperature of 320 ° C. using a 70 t press. Next, the obtained test piece for characteristic evaluation (molded product) was evaluated according to the above-described molded product evaluation method. The characteristic evaluation results are collectively shown in Table 1. The characteristic evaluation results are collectively shown in Table 1.

Example 10
PPS resin-1 48.5% by mass and 1.5% by mass of PET were supplied to a vented twin-screw kneader / extruder having two kneading zones heated to 300 ° C., shear rate 100 sec ⁻¹ , retention It was melt extruded in 1 minute. The resin temperature during kneading was 300 ° C. From the kneader, it was discharged into cold water in a strand shape and immediately cut to obtain a molding material. The obtained molding material was cooled and then cut with a cutter to obtain a pellet-shaped polymer alloy. Next, the obtained polymer alloy was vacuum-dried at 150 ° C. for 10 hours and supplied to a spinning machine connected to a twin-screw kneading extruder. The twin-screw kneading extruder connected to the spinning machine was set to a set temperature of 300 ° C. and a shear rate of 100 sec ⁻¹ . Further, spinning was performed under the conditions of a spinning temperature of 295 ° C., a nozzle diameter of 0.23 mm, a nozzle hole number of 24 holes, and 1000 m / min to obtain an undrawn yarn. As a result of spinning for 5 hours, the number of yarn breaks was 0 and the spinnability was good.

  Next, the obtained undrawn yarn was drawn at a drawing temperature of 90 ° C., a heat treatment temperature of 170 ° C., and a draw ratio of 2.6 times. The number of yarn breaks during stretching was 0, and the stretchability was good.

  The obtained drawn yarn had a strength of 3.8 cN / dtex, an elongation of 35%, a heat shrinkage rate of 5.1%, and had good dimensional stability.

  The obtained polymer alloy fiber was used as a weft and a carbon fiber was used as a warp to produce a mixed woven molding material. The ratio of the carbon fiber in the obtained molding material was 50 mass%. Furthermore, the molding material which impregnated the polymer alloy in the carbon fiber was obtained by the double belt press which set the impregnation part temperature to 320 degreeC. The obtained molding material was vacuum-dried at 150 ° C. for 10 hours, and a characteristic evaluation test piece (molded product) was molded at a mold temperature of 320 ° C. using a 70 t press. Next, the obtained test piece for characteristic evaluation (molded product) was evaluated according to the above-described molded product evaluation method. The characteristic evaluation results are collectively shown in Table 1. The characteristic evaluation results are collectively shown in Table 1.

Example 11
PPS resin-1 47.5% by mass and 2.5% by mass of PET are blended and supplied to a vented twin-screw kneading extruder having two kneading zones heated to 300 ° C., and a shear rate of 100 sec ⁻¹ Then, melt extrusion was performed at a residence time of 1 minute. The resin temperature during kneading was 300 ° C. From the kneader, it was discharged into cold water in a strand shape and immediately cut to obtain a molding material. The obtained molding material was cooled and then cut with a cutter to obtain a pellet-shaped polymer alloy. Next, the obtained polymer alloy was vacuum-dried at 150 ° C. for 10 hours to obtain a nonwoven fabric.

  The obtained polymer alloy nonwoven fabric and carbon fiber were laminated. The proportion of carbon fibers in the laminated molding material was 50% by mass. Furthermore, the molding material which impregnated the polymer alloy in the carbon fiber was obtained by the double belt press which set the impregnation part temperature to 320 degreeC. The obtained molding material was vacuum-dried at 150 ° C. for 10 hours, and a characteristic evaluation test piece (molded product) was molded at a mold temperature of 320 ° C. using a 70 t press. Next, the obtained test piece for characteristic evaluation (molded product) was evaluated according to the above-described molded product evaluation method. The characteristic evaluation results are collectively shown in Table 1. The characteristic evaluation results are collectively shown in Table 1.

Example 12
The carbon fiber 1 obtained in Reference Example 1 was cut to 6 mm with a cartridge cutter to obtain chopped carbon fiber. A dispersion liquid having a concentration of 0.1% by mass composed of water and a surfactant (manufactured by Nacalai Tex Co., Ltd .: polyoxyethylene lauryl ether (trade name)) is prepared, and this dispersion liquid and the chopped carbon fiber are used. A carbon fiber nonwoven fabric was produced. The manufacturing apparatus includes a cylindrical container having a diameter of 1000 mm having an opening cock at the bottom of the container as a dispersion tank, and a linear transport unit that connects the dispersion tank and the papermaking tank. The carbon fiber concentration in the dispersion was 0.05% by mass, and the obtained carbon fiber nonwoven fabric was dried in a drying furnace at 200 ° C. for 30 minutes.

  The carbon fiber base material and the polymer alloy nonwoven fabric obtained in Example 11 were laminated. The proportion of carbon fibers in the laminated molding material was 50% by mass. Furthermore, the molding material which impregnated the polymer alloy in the carbon fiber was obtained by the double belt press which set the impregnation part temperature to 320 degreeC. The obtained molding material was vacuum-dried at 150 ° C. for 10 hours, and a characteristic evaluation test piece (molded product) was molded at a mold temperature of 320 ° C. using a 70 t press. Next, the obtained test piece for characteristic evaluation (molded product) was evaluated according to the above-described molded product evaluation method. The characteristic evaluation results are collectively shown in Table 1. Further, the vertical / horizontal strength ratio of the obtained molded product was 0.90.

Example 13
A molded product was obtained in the same manner as in Example 12 except that the polymer alloy was used as a film. The characteristic evaluation results are collectively shown in Table 1.

Example 14
The carbon fiber 1 obtained in Reference Example 1 was cut to 50 mm with a cartridge cutter to obtain chopped carbon fiber. The cut carbon fiber was put into a cotton opening machine, and after opening the carbon fiber, it was put into the cotton opening machine again to obtain a cotton-like carbon fiber. Moreover, the polymer alloy fiber obtained in Example 10 was cut into 50 mm with a cartridge cutter to obtain discontinuous fibers. Cotton-like carbon fibers and polymer alloy discontinuous fibers were mixed at a mass ratio of 50:50. This mixture was again put into a cotton opening machine to obtain a mixed raw cotton composed of carbon fibers and polymer alloy fibers.

  This mixed raw cotton was put into a carding apparatus having a cylinder roll having a diameter of 600 mm to obtain a sheet-shaped molding material composed of carbon fibers and polymer alloy fibers. The proportion of carbon fiber in the molding material was 50% by mass. Furthermore, the molding material which impregnated the polymer alloy in the carbon fiber was obtained by the double belt press which set the impregnation part temperature to 320 degreeC. The obtained molding material was vacuum-dried at 150 ° C. for 10 hours, and a characteristic evaluation test piece (molded product) was molded at a mold temperature of 320 ° C. using a 70 t press. Next, the obtained test piece for characteristic evaluation (molded product) was evaluated according to the above-described molded product evaluation method. The characteristic evaluation results are collectively shown in Table 1. The characteristic evaluation results are collectively shown in Table 1.

Comparative Example 1
A molding material and a molded product were obtained in the same manner as in Example 1 except that 60% by mass of PPS resin-1 was used without using PET. The characteristic evaluation results are collectively shown in Table 1.

Comparative Example 2
A molding material and a molded product were obtained in the same manner as in Example 3 except that 80% by mass of PPS resin-1 was used without using PET. The characteristic evaluation results are collectively shown in Table 1.

Comparative Example 3
A molding material and a molded product were obtained in the same manner as in Example 3 except that 40% by mass of PPS-1 and 40% by mass of PET were used. The characteristic evaluation results are collectively shown in Table 1.

Comparative Example 4
A molding material and a molded product were obtained in the same manner as in Example 3 except that BHT was used instead of PET. The characteristic evaluation results are collectively shown in Table 1.

Comparative Example 5
A molding material and a molded product were obtained in the same manner as in Example 9 except that 50% by mass of PPS resin-1 was used without using PET. The results of the characteristic evaluation are summarized in Table 1 Comparative Example 6
Melt spinning was carried out in the same manner as in Example 10 except that PET was not used, but no PPS resin-1 fiber was obtained at a spinning temperature of 295 ° C., and a molding material similar to that in Example 10 was not obtained. It was.

Comparative Example 7
A molding material and a molded product were obtained in the same manner as in Example 11 except that PET was not used. The characterization results are summarized in Table 1.

  As mentioned above, in Examples 1-11, the molding material in this invention is excellent in the impregnation property to carbon fiber, is excellent in fiber dispersibility by using this molding material, and was excellent in mechanical characteristics. Could get.

  On the other hand, in the comparative example, there was insufficient impregnation of the molding material into the carbon fiber, or there were many voids in the molded product, and a molding material having excellent mechanical properties of the molded product could not be obtained.

  The carbon fiber reinforced polyphenylene sulfide resin composition of the present invention uses a polyphenylene sulfide resin with improved processability during heating, so that the impregnation property of the polyphenylene sulfide resin into the carbon fiber and the dispersion of the carbon fiber in the molded product It is possible to obtain a molded article having good properties and excellent mechanical properties, and can be developed for various uses. It is particularly suitable for automobile parts, electrical / electronic parts, and household / office electrical products.

1: Example 1 PPS resin / PET Heating temperature curve 2: Comparative Example 1 PPS resin Heating temperature curve 3: Example 1 PPS resin / PET Heating temperature curve 4: Comparative Example 1 PPS resin Heating curve

Claims (23)

A carbon fiber reinforced polyphenylene sulfide resin composition comprising the following components (A) to (C).
(A) Carbon fiber 1-75 mass%
(B) Polyphenylene sulfide resin 17 to 99.99% by mass
(C) Polyalkylene terephthalate 0.01-8 mass% (D) a polymer alloy obtained by melt-kneading (B) and (C) at a temperature of 280 to 350 ° C., the viscosity of (D) being higher than any of the melt viscosities of (B) and (C) The carbon fiber reinforced polyphenylene sulfide resin composition according to claim 1, which is low. (B) and (C) obtained by melt-kneading (B) and (C) at a temperature of 280 to 350 ° C., and a temperature drop rate of 16 ° C./min in the suggested scanning calorimetry (DSC) measurement of (D) The carbon fiber reinforced polyphenylene sulfide resin composition according to claim 1 or 2, wherein the temperature-falling crystallization temperature measured by the measurement is 230 to 250 ° C. (D) containing a polymer alloy obtained by melt-kneading (B) and (C) at a temperature of 280 to 350 ° C., and the melt viscosity measured at 290 ° C. and a shear rate of 1216 sec ⁻¹ is 200 Pa · The fiber-reinforced polyphenylene sulfide resin composition according to any one of claims 1 to 3, which is s or less. It comprises (D) a polymer alloy obtained by melt-kneading (B) and (C) at a temperature of 280 to 350 ° C., and the dispersion diameter of (C) contained in (D) is 0.4 μm or less. The carbon fiber reinforced polyphenylene sulfide resin composition according to any one of claims 1 to 4. The carbon fiber reinforced polyphenylene sulfide resin composition according to any one of claims 1 to 5, wherein (C) is polyethylene terephthalate. The carbon fiber reinforced polyphenylene sulfide resin composition according to any one of claims 1 to 6, wherein the intrinsic viscosity of (C) is 0.5 to 1.1. The carbon fiber reinforced polyphenylene according to any one of claims 1 to 7, wherein the surface oxygen concentration ratio (O / C) measured by X-ray photoelectron spectroscopy (ESCA) of (A) is 0.05 to 0.5. A sulfide resin composition. The carbon fiber reinforced polyphenylene sulfide resin composition according to any one of claims 1 to 8, wherein (A) is a carbon fiber bundle composed of 20,000 to 100,000 single fibers. A molding material using the fiber-reinforced polyphenylene sulfide resin composition according to any one of claims 1 to 9, wherein the molding material is obtained by melt-kneading (A) to (C) at 280 to 350 ° C. material. A molding material using the fiber-reinforced polyphenylene sulfide resin composition according to any one of claims 1 to 9, wherein (E) carbon obtained by melt-kneading (A) and (B) at 280 to 350 ° C A molding material comprising a fiber-reinforced polyphenylene sulfide resin composition and (C). It is a molding material using the carbon fiber reinforced polyphenylene sulfide resin composition according to any one of claims 1 to 9, and obtained by melt-kneading (B) and (C) at a temperature of 280 to 350 ° C ( D) A molding material obtained by impregnating (A) with a polymer alloy. The molding material which cut the molding material of Claim 12 by 2-25 mm. A molding material using the carbon fiber-reinforced polyphenylene sulfide resin composition according to any one of claims 1 to 9, wherein (A) and (B) and (C) are melt-kneaded at a temperature of 280 to 350 ° C. (D) A molding material obtained by compounding with a polymer alloy. The molding material of Claim 14 whose (D) is a nonwoven fabric. The molding material of Claim 14 whose (D) is a fiber. The molding material according to claim 16, wherein (D) is melt-spun at 285-310 ° C. The molding material of Claim 14 whose (A) is a discontinuous fiber. The molding material of Claim 14 whose (A) is a nonwoven fabric form. A molding material obtained by impregnating (A) with (D) by heating and pressurizing the molding material according to claim 14. The molding material according to any one of claims 12, 13, and 20 having a void ratio of less than 10%. A molded product molded using the molding material according to claim 10. The molded article according to claim 22, wherein the strength retention after immersion in a 30% NaOH aqueous solution at 93 ° C for 24 hours is 90% or more.

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