JP2013173810A - Resin composition, molding material and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a resin composition which exhibits good impregnation ability into reinforcing fibers, has few voids, and generates a small amount of gas during molding, and to provide a molding material using the resin composition and capable of producing a molded article in which good fiber dispersion is achieved.SOLUTION: This resin composition comprises 5-50 pts.wt. of reinforcing fibers (A), 1-20 pts.wt. of a compound (B) comprising an epoxy resin (B-1) and a terpene-based resin (B-2), and 30-94 pts.wt. of a thermoplastic resin (C), with respect to 100 pts.wt. in total of the components (A)-(C), wherein the weight ratio of the component (B-1) to the component (B-2) is within a range of 1/9 to 9/1. A molding material using the resin composition and a method for producing the molding material are provided.

Description

  The present invention relates to a resin composition, a molding material, and a method for producing the same. More specifically, the present invention relates to a resin composition, a molding material, and a method for producing the same, which can obtain a molded article that has good dispersibility during injection molding and generates less gas during molding.

  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. The reinforcing fibers used in these resin compositions are reinforced in various forms depending on their usage. 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.

  Further, various forms such as thermoplastic prepregs, yarns, glass mats (GMT) and the like are known as molding materials using a continuous reinforcing fiber and a thermoplastic resin 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. There are features. In particular, a molding material processed into a pellet can be applied to a molding method having excellent economic efficiency and productivity such as injection molding and stamping molding, and is useful as an industrial material.

  However, impregnating a continuous reinforcing fiber with a thermoplastic resin in the process of producing a molding material has problems in terms of economy and productivity and is not widely used at present. For example, it is well known that the higher the melt viscosity of the resin, the more difficult it is to impregnate the reinforcing fibers. Thermoplastic resins with excellent mechanical properties such as toughness and elongation are high molecular weight polymers and require high process temperatures, making them unsuitable for producing molding materials easily and with high productivity. It was. Therefore, a method of kneading with a thermoplastic resin using a composite reinforcing fiber impregnated with a low molecular weight compound has been used because of easy impregnation. However, a low molecular weight compound is more easily decomposed than a high molecular weight compound, and in molding at a high temperature, gas is likely to be generated at the time of molding, mold fouling may occur, and the appearance of the molded product may be deteriorated.

  Patent Document 1 discloses a resin composition containing an inorganic filler in a propylene-based resin composition containing a terpene resin having a Tg of 90 ° C. or less, but it does not relate to gas reduction during molding. Absent.

  Patent Document 2 discloses a metal-coated carbon fiber chopped strand having a styrene / methyl methacrylate copolymer resin content of 2 to 40% by mass and treated with a sizing agent. The styrene / methyl methacrylate copolymer resin is used as a solvent. It has been disclosed that a metal-coated carbon fiber strand is introduced into a solution of a sizing agent dissolved in a solution and dried. The obtained chopped strand has a property that fibers can be stably supplied to the molding machine without being dispersed during dry blending, and the fibers can be easily dispersed in the molding machine.

  In Patent Document 3, a chopped fiber of high elastic modulus fiber is dipped in a thermosetting resin solution, the chopped fiber is impregnated with the resin solution, and the impregnated chopped fiber is separated, and then is immersed in an aqueous medium. Stir to disperse the impregnated chopped fiber and remove the solvent from the resin solution impregnated in the chopped fiber into the aqueous medium, and then separate and dry the chopped fiber coated with the resin after desolvation from the aqueous medium Thus, a method of coating high-modulus fiber chopped fibers is disclosed. Here, as the thermosetting resin, a novolac type phenol resin is used. However, since both Patent Documents 1 and 2 use a sizing agent dissolved in a solvent, the solvent tends to remain inside the reinforcing fiber bundle, and voids inside the reinforcing fiber bundle tend to be generated, and the drying is difficult. If it is used as a molding material with an insufficient amount, it is not preferable because it may have a large amount of volatile components during molding or may cause defects in the molded product. Moreover, in order to perform sufficient drying, it is difficult to improve a line speed, and it may be inferior from the surface of economical efficiency and productivity.

  In such a situation, the resin composition, the molding material, and the impregnation property of the thermoplastic resin into the reinforcing fiber, the amount of gas generated at the time of injection molding is small, the fiber dispersion is good, and there are few voids inside the injection molded product. There was a need to develop manufacturing methods.

JP 2008-274265 A JP-A-6-322665 Japanese Patent Publication No. 64-202

  In view of the problems of the prior art, the present invention provides a resin composition, a molding material, and a resin composition that has good fiber dispersibility at the time of injection molding, less voids inside the injection molded product, and less generated gas at the time of molding. It aims at manufacturing a manufacturing method.

  As a result of intensive studies, the present inventors have invented the following resin composition that can solve the above problems. That is, the compound (B) consisting of reinforcing fiber (A) 5 to 50 parts by weight, epoxy resin (B-1) and terpene resin (B-2), with the total of components (A) to (C) being 100 parts by weight. ) 1-20 parts by weight, thermoplastic resin (C) 30-94 parts by weight of resin composition, component (B-1) / component (B-2) = 1 / 9-9 / 1 (weight ratio) ).

  In addition, as a result of intensive studies, the present inventors have invented the following molding material that can solve the above-described problems. That is, it is a molding material in which a thermoplastic resin (C) is bonded to a composite fiber bundle (D) in which the component (A) is impregnated with the component (B).

  With the resin composition of the present invention, a resin composition having good fiber dispersibility at the time of injection molding, less voids inside the injection molded product, and less generated gas at the time of injection molding can be obtained. The molded product injection-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 the schematic which shows an example of the cross-sectional form of the composite reinforcing fiber bundle obtained by this invention. It is the schematic which shows an example of the preferable longitudinal cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable longitudinal cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable longitudinal cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable longitudinal cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable longitudinal cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable cross-sectional form of the molding material of this invention.

  The present invention relates to a compound comprising reinforcing fiber (A) 5 to 50 parts by weight, epoxy resin (B-1) and terpene resin (B-2), with the total of components (A) to (C) being 100 parts by weight. (B) A resin composition consisting of 1 to 20 parts by weight and 30 to 94 parts by weight of a thermoplastic resin (C). Component (B-1) / Component (B-2) = 1/9 to 9/1 ( It is a resin composition within the range of (weight ratio). First, these components will be described.

  The reinforcing fiber constituting the component (A) used in the present invention is not particularly limited, but for example, high strength such as carbon fiber, glass fiber, aramid fiber, alumina fiber, silicon carbide fiber, boron fiber, metal fiber, High elastic modulus fibers can be used, and these may be used alone or in combination of two or more. Among these, PAN-based, pitch-based and rayon-based carbon fibers are preferable from the viewpoint of improving the mechanical properties and reducing the weight of the molded product, and from the viewpoint of the balance between the strength and elastic modulus of the molded product obtained. More preferred are fibers. For the purpose of imparting conductivity, reinforcing fibers coated with a metal such as nickel, copper, or ytterbium can also be used.

  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 can be illustrated to 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. When the model ES-200 manufactured by Kokusai Electric Inc. is used as the X-ray photoelectron spectroscopy apparatus, 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 reinforcing fibers is not particularly limited, but is preferably in the range of 1 to 20 μm and in the range of 3 to 15 μm from the viewpoint of mechanical properties and surface appearance of the obtained molded product. More preferred.

  There is no restriction | limiting in particular in the number of single fibers of a reinforced fiber bundle, It can use within the range of 100-350,000, It is preferable to use within the range of 1,000-250,000 especially. Further, according to the present invention, even a reinforcing fiber bundle having a large number of single fibers can be obtained in a range of 20,000 to 100,000 since a sufficiently impregnated composite reinforcing fiber bundle can be obtained. It is also preferable from the viewpoint of productivity.

  In addition, the component (A) is provided with a sizing agent, which improves the bundling property, bending resistance and scratch resistance, and can suppress the occurrence of fluff and yarn breakage in a higher processing step. As a sizing agent, higher workability can be improved, which is preferable. In particular, in the case of carbon fiber, by applying a sizing agent, 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.

  Although the adhesion amount of a sizing agent is not specifically limited, 0.01-10 mass% or less is preferable with respect to the mass of only a reinforced fiber, 0.05-5 mass% or less is more preferable, 0.1-2 mass % Or less is more preferable. If the amount is less than 0.01% by mass, the effect of improving adhesiveness is hardly exhibited, and if the amount of adhesion exceeds 10% by mass, the physical properties of the matrix resin may be lowered.

  Furthermore, when a sizing agent is provided to the component (A), the mass ratio of the sizing agent to the component (B) is preferably 0.001 to 0.5 / 1. More preferably, it is 0.005-0.1 / 1, More preferably, it is 0.01-0.05 / 1. Use of each component within the range is preferable because the interfacial adhesiveness, fiber dispersibility, and mechanical properties can be improved in a balanced manner.

  Examples of the sizing agent include epoxy resin, polyethylene glycol, polyurethane, polyester, emulsifier, and surfactant. Moreover, these may use together 1 type, or 2 or more types.

  Moreover, it is preferable that the epoxy equivalent of a sizing agent is smaller than the epoxy equivalent of a component (B). Here, the small epoxy equivalent means that the number of epoxy groups per molecular weight is large. By making the epoxy equivalent of the sizing agent smaller than the epoxy equivalent of the component (B), the interfacial adhesion, fiber dispersibility, and mechanical properties can be improved in a well-balanced manner.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, phenol novolac type epoxy resin, and the like. Among these, an aliphatic epoxy resin that easily exhibits adhesiveness with the matrix resin is preferable. In general, when an epoxy resin has a large number of epoxy groups, the crosslinking density after the crosslinking reaction becomes high, and therefore it tends to be a structure with low toughness, and even if it exists between the reinforcing fiber and the matrix resin, it is fragile. It is easy to peel off and the strength of the fiber reinforced composite material may not be expressed. On the other hand, since the aliphatic epoxy resin has a flexible skeleton, it tends to have a high toughness structure even if the crosslinking density is high. When it exists between a reinforced fiber and matrix resin, in order to make it soft and it is hard to peel, it is easy to improve the intensity | strength of a fiber reinforced composite material, and is preferable.

  Specific examples of the aliphatic epoxy resin include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-diglycidyl ether compound, and 1,4- Examples include butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, and polyalkylene glycol diglycidyl ether. Also, in the polyglycidyl ether compound, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, arabitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane Examples thereof include glycidyl ethers, pentaerythritol polyglycidyl ethers, polyglycidyl ethers of aliphatic polyhydric alcohols, and the like.

  Among the aliphatic epoxy resins, it is preferable to use a trifunctional or higher polyfunctional aliphatic epoxy resin, and it is more preferable to use an aliphatic polyglycidyl ether compound having three or more highly reactive glycidyl groups. . Among these, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, and polypropylene glycol glycidyl ether are more preferable. Aliphatic polyglycidyl ether compounds are preferred because they have a good balance of flexibility, crosslink density, and compatibility with the matrix resin and effectively improve adhesion.

  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 From the viewpoint of preventing the component (A) formed of the treated carbon fiber from becoming hard and deteriorating the spreadability of the bundle, the drying temperature is preferably 150 ° C. or higher and 350 ° C. or lower. It is more preferable that the temperature is not lower than 250 ° C and not higher than 250 ° C.

  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.

  Here, as for the resin composition of this invention, it is preferable that a component (A) is 5-50 weight part by making the sum total of a component (A)-(C) into 100 weight part. More preferably, it is 10-40 mass parts, More preferably, it is 13-33 mass parts. If the component (A) is less than 5 parts by mass, the mechanical properties of the obtained molded product may be insufficient, and if it exceeds 50 parts by mass, the fluidity may be lowered during the molding process.

  The compound which comprises the component (B) used for this invention is a component containing an epoxy resin (B-1) and a terpene resin (B-2).

  The epoxy resin (B-1) here is a compound having a glycidyl group. By having a glycidyl group, it becomes easy to interact with a reinforcing fiber, and it is easy to become familiar with a reinforcing fiber at the time of impregnation and to be easily impregnated. Moreover, the fiber dispersibility at the time of a shaping | molding process becomes good.

  In addition, the epoxy resin (B-1) referred to herein means a resin that does not substantially contain a curing agent and does not cure by so-called three-dimensional crosslinking even when heated.

  Here, examples of the compound having a glycidyl group include glycidyl ether type epoxy resins, glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, and alicyclic epoxy resins.

  The glycidyl ether type epoxy resin includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, halogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, resorcinol type epoxy resin, hydrogenated bisphenol A type. Examples thereof include epoxy resins, aliphatic epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, and dicyclopentadiene type epoxy resins.

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

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

  Examples of the alicyclic epoxy resin include 3,4 epoxy-6 methyl cyclohexyl methyl carboxylate, 3,4 epoxy cyclohexyl methyl carboxylate, and the like. These epoxy resins may be used alone or as a mixture of two or more.

  Among these, glycidyl ether type epoxy resins are preferable because of excellent balance between viscosity and heat resistance, and bisphenol A type and bisphenol F type are particularly preferable.

  Moreover, it is preferable that the number average molecular weights of a component (B-1) are 500-5000. More preferably, it is 800-4000, More preferably, it is 1000-3000. When the number average molecular weight is less than 500, the mechanical properties of the component (B-1) are low, and the mechanical properties of the molded product may be impaired. On the other hand, when it exceeds 5000, the viscosity of the component (B-1) is high and impregnation and fiber dispersibility may not be improved.

  The number average molecular weight can be measured using gel permeation chromatography (GPC).

  Further, the terpene resin (B-2) used in the present invention is co-polymerized with a terpene monomer alone or with a terpene monomer and an aromatic monomer in the presence of a Friedel-Crafts type catalyst in an organic solvent. Examples thereof include a resin made of a polymer obtained by coalescence.

  As the terpene monomer, α-pinene, β-pinene, dipentene, d-limonene, myrcene, alloocimene, ocimene, α-ferrandrene, α-terpinene, γ-terpinene, terpinolene, 1,8-cineole, 1, Examples include monocyclic monoterpenes such as 4-cineole, α-terpineol, β-terpineol, γ-terpineol, sabinene, paramentadienes, and carenes. Examples of the aromatic monomer include styrene and α-methylstyrene.

  Among these, α-pinene, β-pinene, dipentene, and d-limonene are preferable because of good compatibility with the thermoplastic resin (C), and a homopolymer of the compound is more preferable. Further, a hydrogenated terpene resin obtained by hydrogenation treatment of the terpene resin is preferable because the compatibility with the thermoplastic resin (C), particularly, the polypropylene resin is improved.

  Moreover, the glass transition temperature of a component (B-2) is although it does not specifically limit, It is preferable that it is 30-100 degreeC. This is for improving the handleability of the resin composition of the present invention. When the glass transition temperature is 30 ° C. or lower, the component (B-2) becomes semi-solid or liquid during the molding process, and the material may not be quantitatively charged. On the other hand, when the glass transition temperature is 100 ° C. or higher, the component (B-2) is rapidly solidified during the molding process, and the moldability may not be improved.

  Moreover, it is preferable that the number average molecular weights of a component (B-2) are 500-5000. More preferably, it is 500-1000. When the number average molecular weight is 500 or less, the mechanical properties of the molded product may be impaired because the mechanical strength of the terpene resin is low. On the other hand, when the number average molecular weight is less than 500, the mechanical properties of the molded product may be impaired because the mechanical strength of the component (B-2) is low. On the other hand, when it exceeds 5000, the viscosity of the component (B-2) is so high that impregnation and fiber dispersibility may not be improved.

  The number average molecular weight can be measured using gel permeation chromatography (GPC).

  Here, the compound which comprises a component (B) exists in the range of a component (B-1) / component (B-2) = 1 / 9-9 / 1 (weight ratio). By using within this range, the balance between workability and heat resistance is better than using each of component (B-1) and component (B-2) alone, and from the viewpoint of compatibility with thermoplastic resins. preferable. More preferably, it is component (B-1) / component (B-2) = 4/6 to 8/2, and more preferably 5/5 to 7/3. The number average molecular weights of the component (B-1) and the component (B-2) are such that the component (B-1)> the component (B-2), and the balance between heat resistance, workability, and compatibility is more. It is preferable because it is easy to maintain.

  In addition, the component (B) preferably has a weight loss rate at 280 ° C. of 5% or less when heated from 30 ° C. to 10 ° C./min (in air). More preferably, it is 3% or less. When the weight reduction rate exceeds 5%, decomposition gas is likely to be generated when impregnating the reinforcing fiber, and may be a void when molded. In molding at a high temperature, a large amount of gas is generated. May be.

  The rate of change in melt viscosity after heating for 2 hours at 200 ° C. of component (B) is preferably 1.5 or less, and more preferably 1.3 or less. When the rate of change in melt viscosity after heating at 200 ° C. for 2 hours exceeds 2, production stability cannot be ensured, and uneven adhesion may occur. By making the rate of change in melt viscosity 2 or less, stable production can be ensured.

Here, the rate of change in melt viscosity after heating at 200 ° C. for 2 hours is obtained from the following equation.
Viscosity change rate = melt viscosity at 200 ° C. after heating for 2 hours at 200 ° C./melt viscosity at 200 ° C. before heating for 2 hours at 200 ° C.

  The melt viscosity at 200 ° C. is preferably 0.01 to 10 Pa · s, more preferably 0.1 to 8 Pa · s. Furthermore, it is preferably 2 to 5 Pa · s. If the melt viscosity at 200 ° C. is less than 0.001 Pa · s, the mechanical strength of the component (B) is low, so the mechanical properties of the molded product may be impaired. If it exceeds 10 Pa · s, the component (B) The viscosity is high and the dispersibility of the reinforcing fibers may not be ensured.

  Moreover, you may mix an additive with a component (B) in the range which does not impair the objective of this invention. Examples of additives include thermosetting resins, thermoplastic resins, or inorganic fillers, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents Agents, deodorants, anti-coloring agents, heat stabilizers, mold release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, or coupling agents.

  Moreover, it is preferable that a component (B) is 1 to 20 weight%. More preferably, it is 2 to 15% by weight, and further preferably 4 to 12% by weight. When the component (B) is less than 1% by weight, the fluidity of the component (A) is insufficient during the molding process, and the dispersibility may be inferior.

  In addition, it is possible to improve the fiber dispersibility efficiently when the component (A) and the component (B) are within the range of component (A) / component (B) = 5/1 to 3/1 (weight ratio). Therefore, it is preferable. When the component (A) is more than the component (B) out of the range, the fiber dispersibility may not be ensured. When the component (A) is less than the component (B), the fiber dispersibility may be insufficient. Is sufficient, but it is not preferable because there are many gases at the time of injection molding and the strength of the molded product may be insufficient.

  The thermoplastic resin (C) used in the present invention is not particularly limited, but polycarbonate resin (PC resin), styrene resin, polyamide resin, polyester resin, polyphenylene sulfide resin (PPS resin), modified polyphenylene. Acrylic resins such as ether resin (modified PPE resin), polyacetal resin (POM resin), liquid crystal polyester, polyarylate, polymethyl methacrylate resin (PMMA), vinyl chloride, polyimide (PI), polyamideimide (PAI), polyether Polyimide such as imide (PEI), polysulfone, polyethersulfone, polyketone, polyetherketone, polyetheretherketone (PEEK), polyethylene, polypropylene, modified polyolefin, phenolic resin, Enoxy resin, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / diene copolymer, ethylene / carbon monoxide / diene copolymer, ethylene / ethyl (meth) acrylate copolymer Polymer, ethylene / glycidyl (meth) acrylate, ethylene / vinyl acetate / glycidyl (meth) acrylate copolymer, polyether ester elastomer, polyether ether elastomer, polyether ester amide elastomer, polyester amide elastomer, polyester ester elastomer Various elastomers such as these may be mentioned, and one or more of these may be used in combination. In particular, polypropylene resins, polyamide resins, polycarbonate resins, and polyphenylene sulfide resins that are highly versatile are preferable. Of these, polypropylene resins and polycarbonate resins are preferred from the viewpoint of impact resistance. In addition, when using a polypropylene resin, it is preferable to use an acid-modified polypropylene resin because the adhesiveness is easily improved.

  Here, the acid-modified polypropylene resin is, for example, a polymer main chain mainly composed of hydrocarbon such as propylene, a carboxyl group formed by unsaturated carboxylic acid, or a side chain including a metal salt or ammonium salt thereof. The thing which has these. The polymer main chain may be a random copolymer obtained by copolymerizing propylene and an unsaturated carboxylic acid, or may be a graft copolymer obtained by grafting an unsaturated carboxylic acid on propylene. Further, it may be copolymerized with a copolymerizable copolymer component such as α-olefin, conjugated diene, non-conjugated diene or 1-butene.

  Unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, isocrotonic acid, citraconic acid, allyl succinic acid, mesaconic acid, glutaconic acid, nadic acid, methyl nadic acid, tetrahydrophthalic acid And methyltetrahydrophthalic acid. In particular, maleic acid, acrylic acid, and methacrylic acid are preferable because they are easily copolymerized. Only one type of unsaturated carboxylic acid may be used for copolymerization with propylene or graft copolymerization with propylene, or two or more types of unsaturated carboxylic acids may be used.

  Moreover, since it has two or more functional groups, it is preferable that the total amount is 0.05 to 5 mmol equivalent in terms of a group represented by -C (= O) -O- per 1 g of the acid-modified polypropylene resin. More preferably, it is 0.1-4 mmol equivalent, More preferably, it is 0.3-3 mmol equivalent. As a method for analyzing the content of the carboxylate as described above, there is a method of quantifying the carbonyl carbon of the carboxylic acid using IR, NMR, elemental analysis or the like. When the total amount is 0.05 mmol equivalent or less in terms of a group represented by —C (═O) —O—, the adhesiveness tends to be hardly exhibited, and when it is 5 mmol equivalent or more, the acid-modified polypropylene resin may be brittle. is there.

  Moreover, a component (C) may contain another filler and additive in the range which does not impair the objective of this invention. Examples of these include inorganic fillers, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, anti-coloring agents, heat stabilizers. , Release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, or coupling agents.

  Here, the component (C) is preferably 30 to 94 parts by weight, with the total of the components (A) to (C) being 100 parts by weight. By using within this range, a molded product having excellent mechanical properties can be obtained.

  Here, as a molding material using the resin composition of the present invention, a composite obtained by coating a composite fiber bundle (D) impregnated with the component (B) into the component (A) with the component (C) is 1 to 50 mm. A molding material cut by length is preferred.

  Here, the composite fiber bundle (D) is a step (I) of supplying the component (B) to the component (A) and bringing the component (B) into contact with the component (A) in a molten state at 100 to 300 ° C. There is a step (II) in which the component (A) in contact with the component (B) is heated to impregnate the component (A) with 80 to 100% by mass of the supply amount of the component (B).

  Although it does not specifically limit with process (I), The well-known manufacturing method which provides an oil agent, a sizing agent, and matrix resin to a fiber bundle can be used, Especially, dipping or coating is preferable, and concrete As the coating, a reverse roll, a normal rotation roll, a kiss roll, a spray, and a curtain are preferably used.

  Here, dipping refers to a method in which the component (B) is supplied to the melting bath by a pump and the component (A) is passed through the melting bath. By immersing the component (A) in the melting bath of the component (B), the component (B) can be reliably attached to the component (A). Moreover, a reverse roll, a normal rotation roll, and a kiss roll mean the method of supplying the component (B) fuse | melted with the pump to a roll, and apply | coating the melt of a component (B) to a component (A). Furthermore, the reverse roll is a method in which two rolls rotate in opposite directions to each other and apply the melted component (B) on the roll, and the normal roll has two rolls rotated in the same direction, In this method, the molten component (B) is applied onto a roll. Usually, in the reverse roll and the forward rotation roll, a method is used in which the component (A) is sandwiched, and a roll is further installed so that the component (B) adheres securely. On the other hand, the kiss roll is a method of attaching the component (B) only by contacting the component (A) and the roll. Therefore, the kiss roll is preferably used when the viscosity is relatively low. However, any roll method is used, and a predetermined amount of the heated and melted component (B) is applied, and the component (A) is allowed to run. Thus, a predetermined amount of the component (B) can be adhered per unit length of the fiber bundle. Spray is a method that uses the principle of spraying, and is a method of spraying molten component (B) into component (A) and spraying it onto component (A). The curtain is applied by letting molten component (B) fall naturally from a small hole. Or a method of applying by overflowing from the melting tank. Since it is easy to adjust the amount required for coating, the loss of component (B) can be reduced.

  Moreover, as a melting temperature at the time of supplying a component (B), 100-300 degreeC is preferable. In order to adhere more stably, it is preferable that it is 180-230 degreeC. If it is less than 100 degreeC, the viscosity of a component (B) will become high and an adhesion nonuniformity may generate | occur | produce when supplying. Moreover, when it exceeds 300 degreeC, when manufacturing over a long time, a component (B) may thermally decompose. By contacting the component (A) in a molten state at 100 to 300 ° C., the component (B) can be stably supplied.

  Next, as the step (II), the component (A) obtained in the step (I) in contact with the component (B) is heated to make 80 to 100% by mass of the supply amount of the component (B). Impregnation into (A). Specifically, with respect to component (A) in contact with component (B), at a temperature at which component (B) melts, tension is applied with a roll or bar, widening and focusing are repeated, pressure and vibration are applied. In this step, the component (B) is impregnated into the component (A) by an operation such as addition. As a more specific example, there can be mentioned a method of widening by passing the fiber bundle so as to contact the surface of a plurality of heated rolls or bars, among which, a drawing base, a drawing roll, a roll press, a double A method of impregnation using a belt press is preferably used. Here, the squeezing base is a base whose diameter decreases in the direction of travel. The base that promotes impregnation at the same time as scraping off the extra component (B) while converging the reinforcing fiber bundle. It is. Further, the squeeze roll is a roller that promotes impregnation at the same time as scraping off the excessively adhered component (B) by applying tension to the reinforcing fiber bundle with a roller. The roll press is a device that continuously removes the air inside the reinforcing fiber bundle by the pressure between the two rolls and at the same time promotes the impregnation. The double belt press is a device that pushes the belt from above and below the reinforcing fiber bundle. It is a device that promotes impregnation by pressing through.

  In step (II), it is necessary that 80 to 100% by mass of the supply amount of component (B) is impregnated in component (A). Since the yield is directly affected, the higher the yield from the viewpoints of economy and productivity, the better. More preferably, it is 85-100 mass%, More preferably, it is 90-100 mass%. Moreover, if it is less than 80 mass%, not only from an economical viewpoint, but a component (B) may have generated the volatile component in process (II), and a void remains in a component (A) inside. .

  Moreover, in process (II), it is preferable that the maximum temperature of a component (B) is 150-400 degreeC. Preferably it is 180-380 degreeC, More preferably, it is 200 degreeC-350 degreeC. If it is less than 150 degreeC, a component (B) cannot fully be melt | dissolved and it may become a reinforcing fiber bundle with insufficient impregnation, and if it is 400 degreeC or more, undesirable side reactions, such as causing a decomposition reaction of a component (B), occur. May occur.

  Although it does not specifically limit as a heating method in process (II), Specifically, the method of using a heated chamber and the method of heating and pressurizing simultaneously using a hot roller can be illustrated.

  Moreover, it is preferable to heat in non-oxidizing atmosphere from a viewpoint of suppressing generation | occurrence | production of undesirable side reactions, such as a crosslinking reaction of a component (B), and a decomposition reaction. 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.

  Moreover, since the take-up speed of the composite fiber bundle (D) directly affects the process speed, it is preferably as high as possible from the viewpoints of economy and productivity. Specifically, the take-up speed is preferably 10 to 100 m / min. More preferably, it is 20-100 m / min, More preferably, it is 30-100 m / min. Examples of the pulling method include a method of drawing with a nip roller, a method of winding with a drum winder, and a method of pulling the composite fiber bundle (D) while cutting it to a certain length directly with a strand cutter or the like.

  FIG. 1 is a schematic view showing an example of a cross-sectional form of a composite reinforcing fiber bundle obtained by the present invention. In the present invention, the transverse section means a section in a plane orthogonal to the axial direction. The composite fiber bundle (D) obtained from the steps (I) and (II) is formed as a composite in which the component (A) is coated and impregnated with the component (A). The form of this composite fiber bundle (D) is as shown in FIG. 1, and the component (B) is filled between the single fibers of the component (A). That is, each single fiber of component (A) is dispersed like islands in the sea of component (B).

  In the composite, the composite fiber bundle (D) in which the component (B) is satisfactorily impregnated with the component (A), for example, when injection molding is performed together with the thermoplastic resin (C), in the cylinder of the injection molding machine The melt-kneaded component (B) diffuses into the component (C) and helps the component (A) to be dispersed in the component (C). At the same time, the component (C) is substituted and impregnated with the component (A). It plays the role of so-called impregnation aid and dispersion aid.

In the composite fiber bundle (D), it is desirable that the component (A) is completely impregnated with the component (B). However, in reality, this is difficult, and the composite has a certain amount of voids (component ( A portion where neither A) nor component (B) is present. In particular, when the content of component (A) is large, the number of voids increases, but even when a certain amount of voids are present, the effect of promoting impregnation and fiber dispersion of the present invention is shown. However, if the porosity exceeds 40%, the effect of promoting impregnation and fiber dispersion is remarkably reduced, so the porosity is preferably less than 40%. A more preferable range of the porosity is 20% or less. The porosity is determined by measuring the composite according to ASTM D2734 (1997) test method, or the total area of the composite part formed by component (A) and component (B) in the cross section of the composite fiber bundle (D). It can be calculated from the total area of the gap using the following formula.
Porosity (%) = total area of void part / (total area of composite part + total area of void part) × 100.

  Furthermore, the smaller the volatile content of the obtained composite fiber bundle (D), the less the volatile content during molding, which is preferable. The weight loss after drying at 200 ° C. for 2 hours is preferably less than 5%, more preferably less than 3%, and even more preferably less than 1%.

  Furthermore, the molding material of the present invention is constituted by adhering the component (C) to the composite fiber bundle (D) obtained as described above. In the present invention, the molding material means a raw material used when molding a molded product by injection molding or the like.

  In the molding material of the present invention, the composite fiber bundle (D) and the component (C) are appropriately disposed and bonded. As the disposing step, the molten component (C) is used as the composite fiber bundle (D). Arrange to touch. Although not particularly limited, more specifically, using an extruder and a coating die for a wire coating method, the composite fiber bundle (D) is continuously disposed around the composite fiber bundle (D). Examples thereof include a method and a method in which a film-like component (C) melted using an extruder and a T-die is disposed from one side or both sides of a composite flattened by a roll or the like and integrated by a roll or the like.

  FIG. 2 is a schematic view showing an example of a preferred longitudinal sectional form of the molding material of the present invention. In the present invention, the longitudinal section means a section in a plane including the axial direction. As shown in FIG. 2, an example of the molding material of the present invention is that the component (A) is arranged substantially parallel to the axial direction of the molding material, and the length of the component (A) is substantially equal to the length of the molding material. Are the same length.

  Here, “arranged substantially in parallel” means that the major axis of the component (A) and the major axis of the molding material are oriented in the same direction, The angle deviation is preferably 20 ° or less, more preferably 10 ° or less, and further preferably 5 ° or less. In addition, “substantially the same length” means that, for example, in a pellet-shaped molding material, the component (A) is cut in the middle of the pellet, or the component (A) significantly shorter than the total length of the pellet is substantially Is not included. In particular, the amount of the component (A) shorter than the total length of the pellet is not specified, but the content of the component (A) having a length of 50% or less of the total length of the pellet is 30% by mass or less. Evaluates that the component (A) significantly shorter than the whole pellet length is substantially not contained. Furthermore, the content of the component (A) having a length of 50% or less of the total length of the pellet is preferably 20% by mass or less. In addition, a pellet full length is the length of the component (A) orientation direction in a pellet. Since the component (A) has a length equivalent to that of the molding material, the reinforcing fiber length in the molded product can be increased, and thus excellent mechanical properties can be obtained.

  3 to 6 each schematically show an example of the longitudinal cross-sectional form of the molding material of the present invention, and FIGS. 7 to 11 schematically show examples of the cross-sectional form of the molding material of the present invention. It is a representation.

  The cross-sectional form of the molding material is not limited to that shown in the figure as long as the component (C) is disposed so as to adhere to the composite composed of the component (A) and the component (B). As shown in 3 to 5, a configuration in which the composite is a core material and is sandwiched and arranged in layers with the component (C) is preferable.

  Moreover, as FIG. 7-9 shows, the structure arrange | positioned at the core sheath structure which makes the composite_body | complex a core structure and the circumference | surroundings coat | covers a component (C) is preferable. Moreover, when arrange | positioning so that a component (C) may coat | cover several composite_body | complexes as shown in FIG. 11, the number of composite_body | complexes is about 2-6.

  The boundary between the composite fiber bundle (D) and the component (C) is bonded, and the component (C) partially enters a part of the composite near the boundary and is compatible with the component (B) constituting the composite. Or a state in which the reinforcing fiber is impregnated.

  The molding material of the present invention is kneaded by, for example, injection molding to become a final molded product. From the viewpoint of handleability of the molding material, it is important that the composite fiber bundle (D) and the component (C) are not separated while being bonded until molding is performed, and the shape as described above is maintained. The composite and component (C) are completely different in shape (size, aspect ratio), specific gravity, and mass, so they are classified at the time of transporting, handling, and transferring materials in the molding process. In some cases, the fluidity may be lowered, the mold may be clogged, and blocking may occur in the molding process.

  From such a viewpoint, the configuration arranged in the core-sheath structure as illustrated in FIGS. If it is such arrangement | positioning, a component (C) will restrain a composite fiber bundle (D), and a stronger composite can be performed. In addition, as to which of the core-sheath structure as illustrated in FIGS. 7 to 9 or the layered arrangement as illustrated in FIG. From the viewpoint of ease, a core-sheath structure is more preferable.

  The molding material of the present invention is preferably cut to a certain length in the axial direction, and is preferably cut to a length in the range of 1 to 50 mm. It is good to be. By adjusting to this length, the fluidity and handleability during molding can be sufficiently enhanced. A particularly preferred embodiment of the molding material cut into an appropriate length in this way can be exemplified by long fiber pellets for injection molding.

  The molding method of the molding material obtained in the present invention is not particularly limited, but can be applied to molding methods having excellent productivity such as injection molding, autoclave molding, press molding, filament winding molding, stamping molding, etc. It can also be used. 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.

  Molded products obtained by the above molding methods include instrument panels, door beams, under covers, lamp housings, pedal housings, radiator supports, spare tire covers, front end and other various modules, cylinder head covers, bearing retainers, intake manifolds, pedals Aircraft parts such as automobile parts, parts and skins, landing gear pods, winglets, spoilers, edges, ladders, failings, ribs, etc., parts and skins, tools such as monkeys, wrenches, telephones, facsimiles , VTRs, photocopiers, televisions, microwave ovens, audio equipment, toiletries, laser discs (registered trademark), refrigerators, air conditioners, and other home / office electrical product parts. Further, there may be mentioned a housing used for a personal computer, a mobile phone or the like, or a member for electric / electronic equipment represented by a keyboard support which is a member for supporting a keyboard inside the personal computer. In this invention, when the carbon fiber bundle which has electroconductivity is used as a component (A), in such a member for electrical / electronic devices, since electromagnetic wave shielding property is provided, it is more preferable.

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

  The following materials were used as raw materials used in this example.

The following were used as the epoxy resin (B-1).
Component (B-1) -1 Phenol novolac type epoxy resin N-775 manufactured by DIC Corporation
Ingredient (B-1) -2 Mitsubishi Chemical Corporation bisphenol A type epoxy resin jER1007
Component (B-1) -3 Bisphenol F type epoxy resin jER4010P manufactured by Mitsubishi Chemical Corporation

The following were used as the terpene resin (B-2).
Component (B-2) -1 YS Resin PX1250 manufactured by Yasuhara Chemical Co., Ltd.
Ingredient (B-2) -2 Yashara Chemical Co., Ltd. P125

The following were used as the thermoplastic resin (C).
Component (C) -1 Primer Polymer Co., Ltd. Polypropylene Resin J105G
Ingredient (C) -2 Acid-modified polypropylene resin QE840 manufactured by Mitsui Chemicals, Inc.
Component (C) -3 Polycarbonate resin A1900 manufactured by Idemitsu Co., Ltd.

  A method for measuring various characteristics used in this embodiment will be described.

(1) Number average molecular weight measurement The sample to be measured was measured by gel permeation chromatography (GPC). A GPC column packed with polystyrene cross-linked gel was used. Measurement was performed at 150 ° C. using chloroform as a solvent. The molecular weight was calculated in terms of standard polystyrene.

(2) Melt viscosity measurement, viscosity change rate measurement The sample to be measured was measured with a viscoelasticity meter. The melt viscosity was measured at 200 ° C. at 0.5 Hz using a 40 mm parallel plate. Similarly, the viscosity of the sample to be measured was measured after standing in a hot air dryer at 200 ° C. for 2 hours, and the viscosity change rate was calculated.

(3) Weight loss measurement The sample to be measured was measured by thermogravimetric analysis (TGA). Using a platinum sample pan, measurement was performed at an air temperature of 10 ° C./min in an air atmosphere, and the weight loss rate at 280 ° C. was measured.

(4) Porosity of Composite Fiber Bundle (D) The porosity (%) of the composite was calculated based on the ASTM D2734 (1997) test method.

Determination of the porosity of the composite was performed according to the following criteria, and A to C were determined to be acceptable.
A: 0 to less than 5% B: 5% to less than 20% C: 20% to less than 40% D: 40% or more

(5) Measurement of generated gas 10 g of the obtained molding material was placed on a hot plate heated to 280 ° C. in air, and the generated gas after heating for 60 minutes was judged visually. Judgment of generated gas was performed with the following reference products, and A to B were set as acceptable. Moreover, when it became between reference | standard goods, it was set as the lower evaluation, for example, when it was judged as the generated gas between B and C, it evaluated as C.
A: Gas generation amount equivalent to polycarbonate resin (reference product: A1900 manufactured by Idemitsu Co., Ltd.)
B: Generated gas equivalent to polypropylene resin (reference product: J105G manufactured by Prime Polymer Co., Ltd.)
C: Gas generation amount equivalent to terpene resin (reference product: YS resin PX1250 resin manufactured by Yasuhara Chemical Co., Ltd.)

(6) Fiber dispersibility of molded product A molded product of 100 mm x 100 mm x 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, the fiber dispersibility was determined for the total number based on the following criteria, and A to C were set as 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

(7) Bending test of molded product obtained using molding material In accordance with ASTM D790 (1997), a support span is set to 100 mm using a three-point bending test jig (indenter 10 mm, fulcrum 10 mm), and crosshead Bending strength and flexural modulus were measured under the test conditions of a speed of 5.3 mm / min. An “Instron (registered trademark)” universal testing machine 4201 type (manufactured by Instron) was used as a testing machine.

Judgment of bending strength was performed according to the following criteria, and A to C were set as acceptable.
A: 150 MPa or more B: 130 MPa or more and less than 150 MPa C: 100 MPa or more and less than 130 MPa D: less than 100 MPa.

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 fibers. 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]: 0.05
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.

Reference Example 2 Carbon fiber-2
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 single fibers of 48,000. The characteristics of this continuous carbon fiber were as follows. Furthermore, glycerol triglycidyl ether is dissolved or dispersed in water, adjusted as a sizing agent mother liquor, sizing agent is applied to the reinforcing fiber by a method of dipping in the sizing agent mother liquor via a roller, and drying is performed at 230 ° C It was. In addition, the adhesion amount of the sizing agent was 0.5 mass%.
Single fiber diameter: 7μm
Mass per unit length: 1.6 g / m
Specific gravity: 1.8
Surface oxygen concentration ratio [O / C]: 0.14
Tensile strength: 4600 MPa
Tensile modulus: 220 GPa.

Reference Example 3. Composite fiber bundle (D)
A liquid film obtained by heating and melting the impregnating agent was formed on a roll heated to the coating temperature. A reverse roll was used to form a film having a constant thickness on the roll. The continuous component (A) was passed through this roll while being in contact with it, and the impregnating agent was adhered. Next, it passed between 5 sets of 50 mm diameter roll presses in the chamber heated to the impregnation temperature. By this operation, the impregnating agent was impregnated to the inside of the fiber bundle to form a composite having a predetermined blending amount.

Reference Example 4 2. Production of molding material (pellet) from composite fiber bundle (D) and production of test piece for characteristic evaluation (molded product) Reference Example 3 The composite fiber bundle (D) obtained in (1) was cut into a length of 6 mm by a strand cutter to obtain a chopped strand. Subsequently, the component (C) and the chopped strand were melt-kneaded using a Nippon Steel Works TEX-30α type twin screw extruder (screw diameter 30 mm, L / D = 32). At this time, the amount of the composite fiber bundle (D) and the component (C) was adjusted so as to obtain a desired reinforcing fiber content. Furthermore, it was cut with a cutter to obtain a pellet-shaped molding material. Next, the obtained pellet-shaped molding material was molded into a characteristic evaluation test piece (molded product) at a predetermined cylinder temperature and mold temperature using a J350EIII type injection molding machine manufactured by Nippon Steel Co., Ltd. . Here, the cylinder temperature indicates a portion where the molding material of the injection molding machine is heated and melted, and the mold temperature indicates a mold for injecting a resin for forming a predetermined shape. The obtained test piece was subjected to a characteristic evaluation test after being left in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours. Next, the obtained test piece for characteristic evaluation (molded product) was evaluated according to the above-described injection molded product evaluation method.

Reference Example 5 2. Production of molding material (long fiber pellet) from composite fiber bundle (D) and production of test piece for characteristic evaluation (molded product) Reference Example 3 The composite fiber bundle (D) obtained in the above is coated with a coating die for a wire coating method installed at the tip of a TEX-30α type twin screw extruder (screw diameter 30 mm, L / D = 32). The melted component (C) was discharged from the extruder into the die and continuously disposed so as to cover the periphery of the composite. At this time, the amount of the composite fiber bundle (D) and the component (C) was adjusted so as to obtain a desired reinforcing fiber content. The obtained continuous molding material was cooled and then cut with a cutter to obtain a 7 mm long fiber pellet molding material. Next, the obtained pellet-shaped molding material was molded into a characteristic evaluation test piece (molded product) at a predetermined cylinder temperature and mold temperature using a J350EIII type injection molding machine manufactured by Nippon Steel Co., Ltd. . Here, the cylinder temperature indicates a portion where the molding material of the injection molding machine is heated and melted, and the mold temperature indicates a mold for injecting a resin for forming a predetermined shape. The obtained test piece was subjected to a characteristic evaluation test after being left in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours. Next, the obtained test piece for characteristic evaluation (molded product) was evaluated according to the above-described injection molded product evaluation method.

Examples 1-2 and Comparative Examples 1-3
For the compositions shown in Table 1, pellets were prepared according to Reference Examples 3 and 4 under various conditions shown in the table, and test pieces for characteristic evaluation (molded products) were injection molded. The evaluation results are collectively shown in Table 1.

  In Comparative Example 1, the reinforcing fibers could not be obtained as chopped strands and could not be molded.

Examples 3-5
With respect to the composition shown in Table 1, long fiber pellets were produced in accordance with Reference Examples 3 and 5 under various conditions shown in the table, and test pieces for characteristic evaluation (molded products) were injection molded. The evaluation results are collectively shown in Table 1.

  As described above, in Examples 1 to 5, the resin composition according to the present invention provides a molding material with good impregnation and less voids, and the obtained molding material is a gas generated during molding. There was little, and dispersion | distribution in the molded article of a reinforced fiber was favorable.

  On the other hand, Comparative Examples 1 to 3 were resin compositions with a large amount of gas generated during molding, even though they could not be molded or could be molded and had good fiber dispersion.

  The resin composition of the present invention is a resin that has a good impregnation property of thermoplastic resin into reinforcing fibers and good dispersibility during injection molding, and that can obtain a molded product with less voids and less generated gas during molding. It is a composition. Furthermore, it is a molding material using the resin composition of the present invention and a method for producing the same, and a molded product excellent in dispersion of reinforcing fibers in the molded product can be obtained and can be developed for various uses. It is particularly suitable for automobile parts, electrical / electronic parts, household / office electrical product parts.

1 Reinforcing fiber (A) single fiber 2 Component (B) (impregnated agent)
3 Composite fiber bundle (D)
4 Thermoplastic resin (C)

Claims (8)

Compound (B) 1 comprising reinforcing fiber (A) 5 to 50 parts by weight, epoxy resin (B-1) and terpene resin (B-2), with the total of components (A) to (C) being 100 parts by weight ~ 20 parts by weight, thermoplastic resin (C) 30-94 parts by weight of resin composition, component (B-1) / component (B-2) = 1/9 to 9/1 (weight ratio) The resin composition which is in the range. The resin composition according to claim 1, wherein the component (A) and the component (B) are in the range of component (A) / component (B) = 5/1 to 3/1 (weight ratio). The resin composition according to claim 1 or 2, wherein the weight reduction rate at 280 ° C of the component (B) when the temperature is increased from 30 ° C to 10 ° C / min in air is 5% or less. . The resin composition according to any one of claims 1 to 3, wherein the component (B-1) is a bisphenol A type epoxy resin and / or a bisphenol F type epoxy resin. The resin composition according to any one of claims 1 to 4, wherein the component (B-2) is a hydrogenated terpene resin. The resin composition according to any one of claims 1 to 5, wherein the component (C) comprises an acid-modified polypropylene resin and / or a polycarbonate resin. The resin composition according to any one of claims 1 to 6, wherein a composite obtained by coating the composite fiber bundle (D) impregnated with the component (A) into the component (A) with the component (C) is cut to a length of 1 to 50 mm. Molding material composed of objects. The component (A) is brought into contact with the component (A) in a molten state at 100 to 300 ° C., and further heated to impregnate the composite fiber bundle (D) impregnated with 80 to 100% by weight of the supply amount. The manufacturing method of the molding material of Claim 7 made to contact and cut by the length of 1-50 mm.

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