JP6520043B2 - Molding material, method for producing the same, and molded article - Google Patents

Description

  The present invention provides a molding material which has good resin impregnatability to reinforcing fiber bundles, is excellent in process stability at the time of manufacture, and can obtain molded articles having excellent mechanical properties, and a method of manufacturing the same, and It relates to a molded article used.

  Molding materials consisting of reinforcing fibers and thermoplastics are widely used in sports goods applications, aerospace applications and general industrial applications because of their light weight and excellent mechanical properties. Reinforcing fibers used in these molding materials reinforce moldings in various forms depending on the use application. For these reinforcing fibers, metal fibers such as aluminum fibers and stainless steel fibers, organic fibers such as aramid fibers and PBO fibers, inorganic fibers such as silicon carbide fibers, carbon fibers, etc. are used. Carbon fiber is preferable from the viewpoint of balance between rigidity and lightness, and among these, polyacrylonitrile-based carbon fiber is preferably used.

  Furthermore, as a molding material having a continuous reinforcing fiber bundle and a thermoplastic resin as a matrix, a wide variety of forms such as thermoplastic prepreg, yarn, glass mat (GMT) and the like are known. Such a molding material utilizes the characteristics of a thermoplastic resin to facilitate molding, does not require a storage load such as a thermosetting resin, and has high toughness of a molded article obtained and excellent recyclability. There is a feature. In particular, molding materials processed into pellets can be applied to a molding method having excellent economy and productivity such as injection molding and stamping, and is useful as an industrial material.

  However, in the process of producing a molding material, there is a problem in terms of economy and productivity to impregnate a thermoplastic resin into a continuous reinforcing fiber bundle, and at present it is not widely used. For example, it is well known that the higher the melt viscosity of the resin, the more difficult it is to impregnate the reinforcing fiber bundle. Thermoplastic resins excellent in mechanical properties such as toughness and elongation are especially high molecular weight substances, which have high viscosity compared to thermosetting resins, and require a higher process temperature, which facilitates molding materials. In addition, it was unsuitable for manufacturing with good productivity.

  On the other hand, when a low molecular weight, low viscosity thermoplastic resin is used as the matrix resin because of ease of impregnation, there is a problem that the mechanical properties of the resulting molded article are significantly reduced.

  Patent Document 1 discloses a molding material in which a high molecular weight thermoplastic resin is disposed in contact with a composite composed of a low molecular weight thermoplastic polymer and a continuous reinforcing fiber.

  In this molding material, by using a low molecular weight polymer for impregnating continuous reinforcing fiber bundles and a high molecular weight polymer for the matrix resin, it is intended to achieve both economy, productivity and mechanical characteristics. Further, when this molding material is molded by injection molding, it is easily mixed with the matrix resin while minimizing breakage of the reinforcing fiber at the stage of material plasticization at the time of molding, and molding with excellent fiber dispersibility. Goods can be manufactured. Therefore, the obtained molded product can increase the fiber length of the reinforcing fiber more than before, and can have both good mechanical properties and excellent appearance quality.

  However, in recent years, the degree of attention of fiber reinforced composite materials has increased, and the use has been subdivided into various forms, so that the formability, handleability, and mechanical properties of the resulting molded article are more excellent. As molding materials are required, and also industrially, higher economic efficiency and productivity are required. For example, by increasing the impregnatability of low molecular weight substances, the process load can be reduced, the molding material with higher heat resistance can be proposed, or the fiber dispersibility can be further improved by molding. In order to further improve mechanical properties and to further improve the surface appearance, various technological developments are needed.

  Patent Document 2 discloses a molding material in which a high molecular weight thermoplastic resin is disposed in contact with a composite of reinforcing fibers continuous with a polyarylene sulfide prepolymer. Polyarylene sulfide prepolymers enhance the productivity of molding materials because they are easily impregnated into reinforcing fiber bundles, and also improve the dispersion of reinforcing fibers into moldings by being easily dispersed or compatible with the matrix resin in the molding process. Materials. However, the polyarylene sulfide prepolymer has a high melting temperature of about 200 to 260 ° C., and the impregnation into the reinforcing fiber requires a high temperature of 200 ° C. or more. When the impregnation temperature is high temperature of 200 ° C. or higher, reinforcing fiber fluff may be easily generated in the impregnating process, and productivity may be reduced due to the removal of fluff or fluff due to the fluff. In order to improve the productivity of the molding material, it is considered as one method to use a material having a low melting temperature instead of the polyarylene sulfide prepolymer.

  Patent Document 3 discloses a molding material in which a thermoplastic resin is adhered to a reinforcing fiber bundle obtained by heating and melting an epoxy resin satisfying a specific condition and impregnating the reinforcing fiber bundle with the epoxy resin. The disclosed epoxy resin has a relatively low melting temperature, and is impregnated into reinforcing fibers at about 150 ° C., and the productivity is improved as compared with the technique of Patent Document 2. However, mechanical properties of a molded article obtained by molding a molding material are not sufficient, and development of a molding material having both productivity and high mechanical properties has been required.

Japanese Patent Application Laid-Open No. 10-138379 JP, 2008-231291, A JP 2012-57277 A

  In view of the problems of the prior art, the present invention is a molding material having good impregnatability to a reinforcing fiber bundle at 200 ° C. or less and capable of achieving high productivity, and can produce a molded article having high mechanical properties. It aims at providing a molding material.

As a result of intensive studies, the present inventors have come to invent the following molding material and its manufacturing method, and a molded article which can solve the above-mentioned problems. That is, the total of the following components (A) to (C) is 100 parts by mass,
5 to 50 parts by mass of a reinforcing fiber (A) to which a sizing agent (s) is attached,
1 to 20 parts by mass of component (B) containing polycarbodiimide compound (B-1) liquid at 50 ° C.,
Composite molding material comprising 30 to 94 parts by mass of a thermoplastic resin (C) containing an element other than carbon in the repeating unit structure of the main chain, wherein the component (A) is impregnated with the component (B) (D) ) Is a molding material which is a composite coated with component (C).

  The molding material of the present invention has good impregnatability to a reinforcing fiber bundle even at 200 ° C. or less at the time of production, and can achieve high productivity. In addition, molded articles obtained by molding the molding material of the present invention have extremely high mechanical properties. Molded articles molded using the molding material of the present invention are extremely useful for various parts and members such as parts for electric and electronic devices, office automation equipment, home appliances, or automobiles, internal members and casings.

It is the schematic which shows an example of the cross-sectional form of the composite fiber bundle obtained by this invention. It is the schematic which shows an example of the preferable longitudinal cross-section form of the molding material of this invention. It is the schematic which shows an example of the preferable longitudinal cross-section form of the molding material of this invention. It is the schematic which shows an example of the preferable longitudinal cross-section form of the molding material of this invention. It is the schematic which shows an example of the preferable longitudinal cross-section 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.

  In the present invention, the total amount of components (A) to (C) is 100 parts by mass, 5 to 50 parts by mass of reinforcing fiber (A) to which the sizing agent (s) is attached, polycarbodiimide compound liquid at 50 ° C. (B A molding material comprising 1 to 20 parts by mass of component (B) containing -1) and 30 to 94 parts by mass of thermoplastic resin (C) containing an element other than carbon in the repeating unit structure of the main chain, component (A) And a composite fiber bundle (D) in which the component (B) is impregnated with the component (C). First, these components will be described.

  In the present invention, the composite fiber bundle (D) refers to a fiber in which the reinforcing fiber (A) is impregnated with the component (B) (hereinafter, also referred to as an impregnation agent).

  The reinforcing fibers constituting the component (A) used in the present invention are not particularly limited, and examples thereof include carbon fibers, glass fibers, aramid fibers, alumina fibers, silicon carbide fibers, boron fibers, metal fibers, PBO fibers, high High strength, high modulus fibers such as high strength polyethylene fibers can be used, and these may be used alone or in combination of two or more. Among them, carbon fibers such as PAN type, pitch type and rayon type are preferable from the viewpoint of improvement of mechanical properties and weight reduction effect of molded products, and from the viewpoint of balance between strength and elastic modulus of molded products obtained Fibers are further preferred. Further, for the purpose of imparting conductivity, it is also possible to use a reinforcing fiber coated with a metal such as nickel, copper or ytterbium.

  Furthermore, as the carbon fiber, the surface oxygen concentration ratio [O / C] which is the ratio of the number of oxygen (O) to the number of carbon (C) on the surface of the fiber measured by X-ray photoelectron spectroscopy is 0.05-0. That which is 5 is preferable, More preferably, it is 0.08-0.4, More preferably, it is 0.1-0.3. When the surface oxygen concentration ratio is 0.05 or more, the amount of functional groups on the surface of the carbon fiber can be secured, and firmer adhesion with the thermoplastic resin can be obtained. Further, the upper limit of the surface oxygen concentration ratio is not particularly limited, but in general, it can be exemplified as 0.5 or less from the balance of the handleability of the carbon fiber and the productivity.

The surface oxygen concentration ratio of carbon fiber is determined by X-ray photoelectron spectroscopy according to the following procedure. First, a carbon fiber bundle from which a sizing agent or the like adhering to the surface of the carbon fiber has been removed with a solvent is cut to 20 mm, spread on a copper sample support and arranged, and then A1K α ₁ , ₂ is used as an X-ray source , Keep in the sample chamber at 1 x 10 ⁸ Torr. The kinetic energy value (K.E.) of the main peak of C _1s is adjusted to 1202 eV as a correction value of the peak accompanying charging during measurement. C _1s peak area K. E. It calculates | requires by drawing a straight baseline in the range of 1191 to 1205 eV. O _1s peak area K. E. It calculates | requires by drawing a straight baseline in the range of 947-959 eV.

Here, the surface oxygen concentration ratio is calculated as an atomic ratio from the ratio of the above-mentioned O _1s peak area to the C _1s peak area using a sensitivity correction value unique to the apparatus. In the case of using Model ES-200 manufactured by Kokusai Electric Co., Ltd. as the X-ray photoelectron spectrometer, 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, methods such as electrolytic oxidation treatment, chemical oxidation treatment and gas phase oxidation treatment In particular, electrolytic oxidation treatment is preferred.

  The average fiber diameter of the reinforcing fiber is not particularly limited, but it is preferably in the range of 1 to 20 μm, and preferably in the range of 3 to 15 μm, from the viewpoint of mechanical properties and surface appearance of the molded article obtained. More preferable.

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

  Component (A) is also required to have a sizing agent (s) attached thereto. The adhesion of the sizing agent (s) improves the bundling ability, the bending resistance and the abrasion resistance, and in the impregnation step of the component (B), the generation of fuzz and thread breakage can be suppressed to improve the productivity. can do. In particular, in the case of carbon fiber, by applying a sizing agent, it can be adapted to surface characteristics such as functional groups on the surface of the carbon fiber to improve adhesion and composite overall characteristics.

  The adhesion amount of the sizing agent is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass or less, and 0.1 to 2% by mass, based on the mass of the reinforcing fiber alone. It is further preferable to apply. If the amount is less than 0.01% by mass, the effect of improving adhesion is unlikely to be exhibited, and if the amount is more than 10% by mass, the impregnation property of the component (B) may be affected to deteriorate the physical properties of the molded article.

  Furthermore, it is preferable that the mass of a sizing agent is 0.001-0.5 with respect to the mass 1 of a component (B). More preferably, it is 0.005 to 0.1, and still more preferably 0.01 to 0.05. By using the mass of the sizing agent in this range, interface adhesion, fiber dispersibility, and mechanical properties can be improved in a well-balanced manner, which is preferable.

  The sizing agent (s) is not particularly limited as long as it can suppress the occurrence of fuzz and thread breakage in the step of impregnating the component (B), but from the viewpoint of enhancing the adhesion between reinforcing fiber and matrix resin, carboxyl group It is preferable that it is a compound which has 2 or more of at least 1 sort (s) of functional groups chosen from the group which consists of a hydroxyl group, an amino group, and an epoxy group in 1 molecule. Two or more types of functional groups may be mixed in one molecule, and two or more types of compounds having one or more functional groups in one molecule may be used in combination. The sizing agent (s) is preferably an aliphatic compound. Making the sizing agent (s) into an aliphatic compound is preferable because the affinity with the component (A) and the component (B) is enhanced and a molded article having excellent mechanical properties can be obtained.

  Specific examples of the sizing agent (s) include polyfunctional epoxy resins, acrylic acid polymers, polyhydric alcohols, polyethylene imines, etc. In particular, both with the surface functional group of the component (A) and the component (B) Highly reactive polyfunctional epoxy resins are preferred.

  As a polyfunctional epoxy resin, trifunctional or more than trifunctional aliphatic epoxy resin, a phenol novolak-type epoxy resin, etc. are mentioned. Among them, trifunctional or higher aliphatic epoxy resins are preferable from the viewpoint of affinity with the fatty carbodiimide compound. The trifunctional or higher aliphatic epoxy resin means an aliphatic epoxy resin having three or more epoxy groups in one molecule.

  Specific examples of the trifunctional or higher aliphatic epoxy resin include, for example, glycerol triglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, arabitol polyglycidyl ether, trimethylolpropane triglycidyl ether And polyglycidyl ethers of aliphatic polyhydric alcohols such as pentaerythritol polyglycidyl ether. Among these aliphatic epoxy resins, glycerol triglycidyl ether and diglycerol poly are preferred because they contain many highly reactive epoxy groups in one molecule, are highly water soluble, and are easy to apply to reinforcing fibers (A). Glycidyl ether and polyglycerol polyglycidyl ether are preferably used in the present invention.

  As an acrylic acid type polymer, it is a polymer of acrylic acid, methacrylic acid, and maleic acid, and it is a general term for polymers containing three or more carboxyl groups in one molecule. Specifically, polyacrylic acid, a copolymer of acrylic acid and methacrylic acid, a copolymer of acrylic acid and maleic acid, or a mixture of two or more of these may be mentioned. Furthermore, as long as the number of the functional groups in the molecule is 3 or more in one molecule, the acrylic acid-based polymer may be one in which the carboxyl group is partially neutralized with alkali (that is, as a carboxylate). good. Examples of the alkali include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, and ammonium hydroxide. As the acrylic acid-based polymer, polyacrylic acid containing more carboxyl groups in one molecule is preferably used.

  Specific examples of polyhydric alcohols include polyvinyl alcohol, glycerol, diglycerol, polyglycerol, sorbitol, arabitol, trimethylolpropane, pentaerythritol and the like. Among them, polyvinyl alcohol containing more hydroxyl groups in one molecule is preferably used.

  Examples of polyethylene imine include polyamines having a branched structure by primary, secondary and tertiary amino groups obtained by ring-opening polymerization of ethylene imine, among which polyethylene imines containing more amino groups in one molecule Is preferably used.

  The sizing agent (s) preferably has a value of 40 to 150 obtained by dividing its mass average molecular weight by the number of the functional groups (total number of carboxyl group, hydroxyl group, amino group and epoxy group) in one molecule. With such a range, the density of the reaction points with the surface functional group of the reinforcing fiber (A) and the functional group of the component (B) can be made more uniform, and the dynamics such as the bending strength of the obtained fiber reinforced composite material Properties can be further enhanced.

  The means for applying the sizing agent (s) is not particularly limited. For example, a method of dipping in a sizing solution through a roller, a method of contacting a roller to which a sizing solution is attached, a method of spraying a sizing solution and so on. Further, either a batch system or a continuous system may be used, but a continuous system which can be reduced in variation with a high productivity is preferable. At this time, it is preferable to control the sizing solution concentration, temperature, yarn tension and the like so that the adhesion amount of the sizing agent active component to the reinforcing fiber adheres uniformly in an appropriate range. In addition, it is more preferable to vibrate the reinforcing fiber by ultrasonic wave at the time of applying the sizing agent.

  Drying temperature and drying time should be adjusted by the amount of adhesion of the compound, but complete removal of the solvent used for applying the sizing agent, shortening the time required for drying, while preventing thermal degradation of the sizing agent, sizing The drying temperature is preferably 150 ° C. or more and 350 ° C. or less, and 180 ° C. or more and 250 ° C. or less from the viewpoint of preventing the reinforcing fiber (A) to which the agent is attached becoming hard and deteriorating the spreadability of the bundle. It is more preferable that

  Examples of the solvent used for applying the sizing agent include water, methanol, ethanol, dimethylformamide, dimethyl acetamide, acetone and the like, but water is preferable from the viewpoint of easy handling and disaster prevention. Therefore, when a compound insoluble or poorly 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 surfactant, styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, formalin condensate of naphthalene sulfonate, anionic emulsifier such as sodium polyacrylate, It is possible to use cationic emulsifiers such as polyethyleneimine and polyvinyl imidazoline, nonionic emulsifiers such as nonylphenol ethylene oxide adduct, polyvinyl alcohol, polyoxyethylene ether ester copolymer, sorbitan ester ethyl oxide adduct, etc. Non-ionic emulsifiers are preferably used because they are difficult to inhibit the adhesive effect of the polyfunctional compound.

  Here, the content of the component (A) needs to be 5 to 50 parts by mass with respect to 100 parts by mass of the total of the components (A) to (C). Preferably it is 10-40 mass parts, More preferably, it is 13-33 mass parts. By using the component (A) in this range, the mechanical properties of a molded product obtained by molding the molding material are high, and the flowability in molding is sufficient, which is preferable.

  Component (B) contains a polycarbodiimide compound (B-1) which is liquid at 50 ° C.

  The term "liquid at 50 ° C" as used herein means a state in which sufficient fluidity is obtained at 50 ° C. Melt viscosity is an index for determining the presence or absence of fluidity. In the present invention, the viscosity is sufficiently less than 10000 Pa · s when melt viscosity measurement at 50 ° C. is performed at 0.5 Hz with a parallel plate of 40 mm using a viscoelasticity measuring instrument. Make it liquid at 50 ° C.

  In order to be liquid at 50 ° C., the melting point or softening point needs to be lower than 50 ° C., and a compound having a melting point or softening point of 50 ° C. or more may not be liquid at 50 ° C.

Examples of polycarbodiimide compounds (B-1) include aliphatic polycarbodiimides and aromatic polycarbodiimides. Aliphatic polycarbodiimides have the general formula -N = C = N-R _1- (wherein R ₁ is a divalent organic group of an alicyclic compound such as cyclohexylene, or methylene, ethylene, propylene, methyl And a repeating unit represented by the group consisting of a divalent organic group of an aliphatic compound such as ethylene and a carbon atom bonded to a nitrogen atom such as xylylene having a unsaturated bond) as a main constituent unit It is preferably a homopolymer or copolymer containing 70% by mol or more, more preferably 90% by mol or more, still more preferably 95% by mol or more of the repeating unit. An aromatic polycarbodiimide is a compound represented by the general formula -N = C = N-R _2- (wherein R ₂ is a divalent organic group of a cyclic unsaturated compound such as benzene, toluene, xylene, biphenyl, naphthalene or anthracene) Or a homopolymer or copolymer containing, as a main constituent unit, a repeating unit represented by: preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more of the repeating unit .

  Although aliphatic polycarbodiimides and aromatic polycarbodiimides are similar in structure, the reactivity of the carbodiimide group represented by the general formula -N = C = N- is largely different. Although there is an effect of steric hindrance due to the substituent around the carbodiimide group, it can not be generally said, but generally, the aromatic polycarbodiimide is less reactive than the aliphatic polycarbodiimide because of the resonance stabilization effect. It has been known. In the present invention, an aliphatic polycarbodiimide is preferably used as the polycarbodiimide compound (B-1) from the viewpoint of the reactivity with the thermoplastic resin (C).

  The polycarbodiimide compound (B-1) needs to be liquid at 50 ° C. If it is not liquid at 50 ° C., the melt viscosity of the component (B) becomes high, and in the process of impregnating the component (B) into the reinforcing fiber (A), a high temperature of 200 ° C. or more may be necessary. It is not preferable from the viewpoint of material productivity. In addition, it is not preferable because the mechanical properties of a molded product obtained by molding a molding material may be lowered.

  When a monocarbodiimide compound having only one carbodiimide group in a molecule, such as N, N'-dicyclohexylcarbodiimide, is used instead of the polycarbodiimide compound, a molding material having both high mechanical properties and high productivity is obtained. It can not be obtained.

  The synthesis method of the polycarbodiimide compound is not particularly limited. For example, an organic polyisocyanate is reacted in the presence of a catalyst that promotes the carbodiimidization reaction of an isocyanate group (hereinafter also referred to as "carbodiimidization catalyst"). Thus, polycarbodiimide compounds can be synthesized.

  As an organic polyisocyanate used for the synthesis | combination of this polycarbodiimide compound, organic diisocyanate is preferable. As such organic diisocyanates, for example, cyclobutylene-1,3-diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,3-diisocyanate, cyclohexylene-1 , 4-diisocyanate, 1-methylcyclohexylene-2,4-diisocyanate, 1-methylcyclohexylene-2,6-diisocyanate, 1-isocyanate-3,3,5-trimethyl-5-isocyanate Natomethylcyclohexane, cyclohexane-1,3-bis (methylisocyanate), cyclohexane-1,4-bis (methylisocyanate), dicyclohexylmethane-2,4'-diisocyanate, dicyclohexylmethane-4,4'- Diisocyanate, ethylene diisocyanate, tetramethylene Stoichiometry of 1,4-diisocyanate, hexamethylene-1,6-diisocyanate, dodecamethylene-1,12-diisocyanate, lysine diisocyanate methyl ester, etc. and organic diisocyanates thereof The both terminal isocyanate prepolymer etc. which are obtained by reaction with excess amount and the bifunctional active hydrogen containing compound can be mentioned. These organic diisocyanates can be used alone or in combination of two or more.

  Also, as other organic polyisocyanates optionally used together with organic diisocyanates, for example, cyclohexane-1,3,5-triisocyanate, cyclohexane-1,3,5-tris (methyl isocyanate), 3,5-Dimethylcyclohexane-1,3,5-tris (methyl isocyanate), 1,3,5-trimethylcyclohexane-1,3,5-tris (methyl isocyanate), dicyclohexylmethane-2,4,2 Stoichiometric excess of trifunctional or higher functional organic polyisocyanates such as' -triisocyanate, dicyclohexylmethane-2,4,4'-triisocyanate, and these trifunctional or higher organic polyisocyanates and 2 Terminal isocyanate pre obtained by the reaction with a functional or higher polyfunctional active hydrogen-containing compound Or the like can be mentioned Rimmer.

  The other organic polyisocyanates may be used singly or in combination of two or more, and the amount thereof used is preferably 0 to 40 per 100 parts by mass of organic diisocyanate. It is a mass part, More preferably, it is 0-20 mass parts.

  Furthermore, when synthesizing a polycarbodiimide compound, the molecular weight of the resulting aliphatic carbodiimide compound can be appropriately controlled by adding an organic monoisocyanate as necessary.

  Examples of such organic monoisocyanates include methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, n-butyl isocyanate, alkyl monoisocyanates such as lauryl isocyanate and stearyl isocyanate, cyclohexyl isocyanate, Mention may be made of cycloalkyl monoisocyanates such as 4-methylcyclohexyl isocyanate, 2,5-dimethylcyclohexyl isocyanate and the like.

  These organic monoisocyanates can be used singly or in combination of two or more, and the amount thereof used varies depending on the desired molecular weight of the polycarbodiimide compound, etc. It is preferably 0 to 40 parts by mass, and more preferably 0 to 20 parts by mass, per 100 parts by mass of the natto component.

  Moreover, as a carbodiimidation catalyst, for example, 1-phenyl-2-phospholene-1-oxide, 1-phenyl-3-methyl-2-phospholene-1-oxide, 1-phenyl-2-phospholene-1-sulfide, 1 -Phenyl-3-methyl-2-phospholene-1-sulfide, 1-ethyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene -1-sulfide, 1-ethyl-3-methyl-2-phospholene-1-sulfide, 1-methyl-2-phospholene-1-oxide, 1-methyl-3-methyl-2-phospholene-1-oxide, 1 -Methyl-2-phospholene-1-sulfide, 1-methyl-3-methyl-2-phospholene-1-sulfide and their 3-phospholene isomers Metal carbonyl complexes such as phospholene compounds, pentacarbonyliron, nonacarbonyldiiron, tetracarbonylnickel, hexacarbonyltungsten, hexacarbonylchromium, beryllium, acetylacetone complexes of metals such as beryllium, aluminum, zirconium, chromium, iron, trimethyl phosphate, Triethyl phosphate, triisopropyl phosphate, tri-t-butyl phosphate, phosphate esters such as triphenyl phosphate and the like can be mentioned.

  The carbodiimidization catalyst may be used singly or in combination of two or more. The amount of the catalyst used is preferably 0.001 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the organic polyisocyanate component.

  The temperature for the synthesis reaction of the polycarbodiimide compound is appropriately selected depending on the type of organic polyisocyanate, organic monoisocyanate, and carbodiimide forming catalyst, but is usually 20 to 200 ° C. In the synthesis reaction of the polycarbodiimide compound, the organic polyisocyanate and the organic monoisocyanate component may be added in total before the reaction, or in part or all thereof continuously or stepwise during the reaction. Good.

  In addition, a compound capable of reacting with an isocyanate group is added at an appropriate reaction step from the initial stage to the late stage of the synthesis reaction of the polycarbodiimide compound to seal the terminal isocyanate group of the polycarbodiimide compound, and an aliphatic obtained. The molecular weight of the carbodiimide compound can be adjusted, or it can be added at a later stage of the synthesis reaction of the aliphatic carbodiimide compound to regulate the molecular weight of the resulting polycarbodiimide compound to a predetermined value. Examples of the compound capable of reacting with such an isocyanate group include alcohols such as methanol, ethanol, isopropanol, cyclohexanol and polyethylene glycol, and amines such as dimethylamine, diethylamine and benzylamine.

  Moreover, as a polycarbodiimide compound (B-1) liquid at 50 ° C., “Carbodilite (registered trademark)” V-02B, V-04B, V-05 manufactured by Nisshinbo Chemical Co., Ltd., “Elastostab (registered trademark)” H01 and so on.

  Moreover, as a thing containing water in polycarbodiimide compound (B-1) liquid at 50 ° C., “Carbodilite (registered trademark)” V-02, V-04, V-06, V-02-L2 manufactured by Nisshinbo Chemical Co., Ltd. , E-01, E-02, E-03, E-04, E-05, and the like.

  If the component (B) contains water, water vapor may be generated in the impregnation step and the coating step, which may lower the productivity, so the polycarbodiimide compound (B-1) should not contain water. Preferably, in the case of containing water, it is desirable to use them dehydrated or to use one which does not contain water.

  The melt viscosity of the component (B) at 150 ° C. is preferably 0.001 to 10 Pa · s, more preferably 0.01 to 8 Pa · s. Furthermore, preferably, it is 0.1 to 5 Pa · s. If the melt viscosity at 150 ° C is less than 0.001 Pa · s, the mechanical strength of the component (B) may be low, which may impair the mechanical properties of the molded article, and if it exceeds 10 Pa · s, the component (B) In some cases, the viscosity is high and high productivity can not be obtained.

  The viscosity change rate of the component (B) after heating for 2 hours at 150 ° C. is preferably 1.5 or less, more preferably 1.3 or less. When the viscosity change rate after heating at 150 ° C. for 2 hours exceeds 2, production stability can not be secured, and adhesion unevenness may occur. By setting the viscosity change rate to 2 or less, stable production can be ensured.

Here, the viscosity change rate after heating at 150 ° C. for 2 hours is obtained from the following equation.
Viscosity change rate = Melt viscosity at 150 ° C. after heating for 2 hours at 150 ° C. Melt viscosity component at 150 ° C. for 2 hours before heating at 150 ° C. Component (B) to the extent that the effect of the present invention is not impaired An additive other than the polycarbodiimide compound (B-1) which is liquid at 50 ° C. can be included. Examples of additives include thermosetting resins, thermoplastic resins, or inorganic fillers, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, damping agents, antibacterial agents, insect repellents Agents, deodorants, color inhibitors, heat stabilizers, mold release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, foam stabilizers, viscosity modifiers, or coupling agents It can be mentioned.

  In particular, in the step of impregnating the reinforcing fiber (A) with the component (B), it is preferable to add a viscosity modifier from the viewpoint of adjusting the melt viscosity.

  The viscosity modifier is not particularly limited, but an epoxy resin having good compatibility with the liquid polycarbodiimide compound (B-1) at 50 ° C. and relatively low reactivity at 150 ° C. is preferably used.

  The epoxy resin mentioned here is a compound having a glycidyl group. In addition, the epoxy resin mentioned here does not substantially contain a curing agent, and refers to a resin which does not cure by so-called three-dimensional crosslinking even if it is heated.

  Here, as a compound which has a glycidyl group, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, an alicyclic epoxy resin is mentioned.

  As a glycidyl ether type epoxy resin, 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 Epoxy resin, aliphatic epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, biphenylaralkyl epoxy resin, dicyclopentadiene epoxy resin, etc. may be mentioned.

  As a glycidyl ester type epoxy resin, hexahydrophthalic acid glycidyl ester, dimer acid diglycidyl ether, etc. are mentioned.

  Examples of glycidyl amine type epoxy resins include triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl metaxylene diamine, aminophenol type epoxy resins and the like.

  As an alicyclic epoxy resin, 3, 4 epoxy 6 methylcyclohexyl methyl carboxylate, 3, 4 epoxy cyclohexyl methyl carboxylate etc. are mentioned.

  When the component (B) contains an additive other than the liquid polycarbodiimide compound (B-1) at 50 ° C., the component (B-1) is preferably 20 to 100% by mass in the component (B). More preferably, it is 30-100 mass%, More preferably, it is 50-100 mass%. That is, when the amount of the component (B-1) is 20% by mass or more, a molded article having high mechanical properties can be obtained, which is preferable.

  Moreover, content of a component (B) needs to be 1-20 mass parts by making the sum total of component (A)-(C) into 100 mass parts. Preferably, it is 2 to 15 parts by mass, more preferably 4 to 12 parts by mass. By using the component (B) in this range, the flowability of the component (A) is good during molding, and a molded article having high mechanical properties can be obtained, which is preferable.

  In addition, it is possible to efficiently improve the fiber dispersibility that the component (A) and the component (B) are in the range of component (A) / component (B) = 5/1 to 3/1 (mass ratio) It is preferable because a molded article having high mechanical properties can be obtained.

  The thermoplastic resin (C) needs to contain an element other than carbon in the repeating unit structure of the main chain from the viewpoint of enhancing the polarity and increasing the affinity with the reinforcing fiber (A) and the component (B). Yes, more specifically polycarbonate, polyester, polyarylene sulfide, polyamide, polyoxymethylene, polyetherimide, polyethersulfone, polyether from the viewpoint of interfacial adhesion to reinforcing fibers and the formability of fiber reinforced composite materials It is preferable that it is at least one thermoplastic resin selected from the group consisting of ketone polyetheretherketone and polyetherketoneketone. In addition, the thermoplastic resin (C) contains, in the molecule, at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an amino group from the viewpoint of adhesion to the reinforcing fiber (A) and the component (B). It is preferable to have at least one.

  The thermoplastic resin (C) preferably has a weight average molecular weight of 10,000 to 80,000, more preferably 10,000 to 60,000, and still more preferably 10,000 to 40,000. is there. The smaller the mass average molecular weight of the thermoplastic resin (C), the lower the melt viscosity, and the resulting fiber-reinforced composite material is preferred because it is excellent in molding processability.

  In the molding material of the present invention, mechanical properties such as bending strength of the obtained fiber-reinforced composite material tend to improve as the thermoplastic resin (C) having a smaller mass average molecular weight. The reason for this is that the functional group possessed by the thermoplastic resin (C) chemically reacts with the functional group of the polycarbodiimide compound (B-1) in the molding step of the molding material, and the thermoplastic resin having a small mass average molecular weight (C It is inferred that this is because the terminal functional group relatively increases and the reaction point with the polycarbodiimide compound (B-1) increases. For these reasons, in the molding material of the present invention, setting the mass average molecular weight of the thermoplastic resin (C) in the range of 10,000 to 40,000 achieves at a high level the mechanical properties of the obtained fiber-reinforced composite material It is particularly preferable because it is compatible with molding processability.

  The mass average molecular weight of the thermoplastic resin (C) can be measured by size exclusion chromatography (SEC). In SEC, it can obtain | require by calculating the mass mean molecular weight of polystyrene conversion.

  Here, a component (C) needs to be 30-94 mass parts, making the total of component (A)-(C) into 100 mass parts. Preferably, it is 45 to 88 parts by mass, more preferably 55 to 83 parts by mass. By using in this range, the molded article which is excellent in a dynamic characteristic can be obtained.

  Here, the molding material of the present invention needs to be a composite in which the composite fiber bundle (D) in which the component (A) is impregnated with the component (B) is coated with the component (C).

  Here, in the production process of the composite fiber bundle (D), the component (B) is supplied to the component (A), and the component (B) is brought into contact with the component (A) in a molten state at 50 to 300 ° C (I And component (A) in contact with component (B) to impregnate component (A) with 80 to 100% by mass of the feed amount of component (B) (step (II)). The molding material of the present invention can be efficiently produced by including the production process of the composite fiber bundle (D).

  A well-known manufacturing method can be used as process (I), Dipping or a coating is especially preferable, and a reverse roll, a positive rotation roll, a kiss roll, a spray, and a curtain are preferably used as a specific coating. .

  Here, dipping means a method of supplying the component (B) to a melting bath by a pump and passing the component (A) in 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) melted with the pump to a roll, and apply | coating the molten material of a component (B) to a component (A). Further, the reverse roll is a method in which two rolls rotate in opposite directions to apply the melted component (B) on the rolls, and in the forward rotating roll, the two rolls rotate in the same direction, It is a method of applying the melted component (B) on a roll. Usually, in the reverse roll and the forward rotation roll, a method is used in which the component (A) is sandwiched and the roll is further installed to reliably adhere the component (B). On the other hand, a kiss roll is a method of making a component (B) adhere, only by contacting a component (A) and a roll. Therefore, it is preferable to use a kiss roll having a relatively low viscosity, but using any roll method, a predetermined amount of the heated and melted component (B) is applied and the component (A) is run while contacting Thus, a predetermined amount of component (B) can be attached per unit length of the fiber bundle. Spraying is a method of utilizing the principle of atomization, in which the melted component (B) is atomized and sprayed onto the component (A), and the curtain drops the melted component (B) spontaneously from the small holes and is applied. Or a method of coating by overflowing from the melting tank. As it is easy to adjust the amount required for application, the loss of the component (B) can be reduced.

  Moreover, as a melting temperature at the time of supplying a component (B), 50-150 degreeC is preferable. If it is less than 50 ° C., the viscosity of the component (B) becomes high, and when it is supplied, uneven adhesion may occur. If the temperature is higher than 150 ° C., reinforcing fiber fluff may be easily generated in the step (II), and productivity may be reduced due to breakage of the fluff and removal of the fluff.

  Next, the component (A) in the state in contact with the component (B) obtained in the step (I) as the step (II) is heated to 80 to 100% by mass of the supply amount of the component (B) Impregnate into (A). Specifically, with respect to the component (A) in a state of being in contact with the component (B), tension is applied with a roll or a bar at a temperature at which the component (B) melts. This is a step of impregnating the component (B) to the inside of the component (A) by an operation such as addition. As a more specific example, there can be mentioned a method in which a fiber bundle is made to contact a surface of a plurality of heated rolls or bars to perform spreading, etc. Among them, a drawing die, drawing roll, roll press, double A method of impregnating using a belt press is preferably used. Here, the term “aperture nozzle” refers to a nozzle whose nozzle diameter narrows in the direction of travel, and while consolidating the reinforcing fiber bundle, a nozzle that promotes impregnation while scraping off the component (B) that has adhered excessively. It is. Moreover, a squeeze roll is a roller which promotes an impregnation simultaneously with scraping away the component (B) adhering to excess by tensioning a reinforcement fiber bundle with a roller. In addition, the roll press is a device that promotes impregnation simultaneously with the removal of air inside the reinforcing fiber bundle continuously by the pressure between the two rolls, and with the double belt press, the belt from above and below the reinforcing fiber bundle It is an apparatus which accelerates | stimulates impregnation by pressing through.

  Moreover, it is preferable that 80-100 mass% of supply_amount | feed_rate of a component (B) is impregnated with a component (A) in process (II). As it directly affects the yield, the higher, from the viewpoint of economy and productivity, the better. More preferably, it is 85-100 mass%, More preferably, it is 90-100 mass%. If the amount is less than 80% by mass, not only from the economical point of view but also the component (B) may generate volatile components in the step (II), and voids remain inside the component (A) There is a case.

  Moreover, in process (II), it is preferable that the maximum temperature of a component (B) is 50-200 degreeC, More preferably, it is 50-150 degreeC. If the temperature is less than 50 ° C., the component (B) can not be melted sufficiently and there is a possibility that the impregnated fiber bundle becomes insufficient. If the temperature exceeds 200 ° C., reinforcing fiber fluff may be easily generated. And, there are times when it loses productivity because of the removal of the fluff.

  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 performing heating and pressurization simultaneously using a hot roller can be illustrated.

  Moreover, it is preferable to heat in non-oxidative atmosphere from a viewpoint of suppressing generation | occurrence | production of the undesirable side reaction of the crosslinking reaction of a component (B), decomposition reaction, etc. 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 oxygen-free, ie, an inert gas atmosphere such as nitrogen, helium or argon. Among them, a nitrogen atmosphere is particularly preferable in terms of economy and ease of handling.

  In addition, since the take-up speed of the composite fiber bundle (D) directly affects the process speed, the higher the cost and productivity, the better. Specifically, the take-up speed is preferably 10 to 100 m / min. More preferably, it is 20 to 100 m / min, still more preferably 30 to 100 m / min. As a pulling method, a pulling method by a nip roller, a winding method by a drum winder, a method by which a composite fiber bundle (D) is pulled while being cut into a predetermined length by a direct strand cutter or the like can be mentioned.

  FIG. 1 is a schematic view showing an example of the cross-sectional form of the composite fiber bundle (D) in the present invention. In the present invention, the cross section means a cross section in a plane perpendicular to the axial direction. The composite fiber bundle (D) obtained from the steps (I) and (II) is formed by applying and impregnating the component (A) to the component (B). 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, in the sea of component (B), each single fiber of component (A) is dispersed like an island.

  By forming the composite fiber bundle (D) in which the component (B) is well impregnated into the component (A), for example, when it is injection molded together with the thermoplastic resin (C), it is melt-kneaded in the cylinder of the injection molding machine Component (B) diffuses into component (C) and helps component (A) disperse into component (C), while at the same time helping component (C) replace and impregnate component (A) It has a role as an impregnation aid and a dispersion aid.

Moreover, in the composite fiber bundle (D), it is desirable that the component (A) is completely impregnated with the component (B), but it is practically difficult, and the composite fiber bundle (D) has a certain degree of There are voids (portions where neither component (A) nor component (B) is present). In particular, when the content of the component (A) is large, the number of voids increases, but even when there is a certain amount of voids, the effect of impregnation and fiber dispersion promotion is shown. However, if the porosity exceeds 40%, the effect of the impregnation / fiber dispersion promotion is significantly reduced, so the porosity is preferably less than 40%. A more preferable porosity range is 20% or less. The porosity is measured by the composite fiber bundle (D) by the ASTM D2734 (1997) test method, or formed by the component (A) and the component (B) in the cross section of the composite fiber bundle (D) or the composite From the total area of the composite part and the total area of the void part, it can be calculated using the following equation.
Void ratio (%) = total area of void / (total area of composite part + total area of void) × 100.

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

  The method of coating the composite fiber bundle (D) with the component (C) is not particularly limited, but specifically, using the extruder and the coating die for the wire coating method, the composite fiber bundle (D) is continuously formed. The film-like component (C) is disposed by using an extruder and a T-die from both sides of the method of coating the component (C) around, or from both sides of the composite fiber bundle (D) flattened with a roll etc. Can be mentioned.

  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 cross section means a cross section in a plane including the axial direction. In an example of the molding material of the present invention, as shown in FIG. 2, 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. The same length.

  Here, "arranged substantially in parallel" indicates that the axis of the major axis of the component (A) and the axis of the major axis of the molding material are directed in the same direction, The deviation of the angle is preferably 20 ° or less, more preferably 10 ° or less, and still more preferably 5 ° or less. In addition, “substantially the same length” means, for example, that in the pellet-like molding material, the component (A) is cut midway inside the pellet, or the component (A) that is significantly shorter than the entire pellet length is substantially Not included in In particular, the amount of the component (A) shorter than the total pellet length is not specified, but the content of the component (A) having a length of 50% or less of the total pellet length is 30% by mass or less In the evaluation, it is evaluated that the component (A) significantly shorter than the full length of the pellet is not substantially 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. When the component (A) has a length equivalent to that of the molding material, the length of the reinforcing fiber in the molded product can be increased, so that excellent mechanical properties can be obtained.

  3 to 5 schematically show an example of the longitudinal sectional form of the molding material of the present invention, and FIGS. 6 to 9 schematically show an example of the transverse 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 composite fiber bundle (D) consisting of the component (A) and the component (B) is coated with the component (C). It is preferable that the composite fiber bundle (D) serves as a core material and is sandwiched between the components (C) and arranged in layers as shown in (5) to (5).

  Moreover, as shown in FIGS. 6-8, the structure arrange | positioned in the core-sheath structure which is coat | covered with a component (C) by making the composite fiber bundle into a core structure is preferable. When a plurality of composite fiber bundles as shown in FIG. 9 are coated with the component (C), the number of composite fiber bundles (D) is preferably about 2 to 6.

  The boundary between the composite fiber bundle (D) and the component (C) is adhered, and the component (C) partially penetrates into a part of the composite fiber bundle (D) near the boundary to form the component fiber bundle (D) It may be in a state of being compatible with (B), or in a state of being impregnated into the reinforcing fiber (A).

  The molding material of the present invention preferably has a length in the range of 1 to 50 mm. Therefore, in the above-mentioned production method, the composite fiber bundle (D) is contacted with the component (C) to obtain a composite It is preferable to include the process of cutting into a length of 1 to 50 mm later. By adjusting to this length, the flowability at the time of molding and the handleability can be sufficiently improved. An embodiment particularly preferable as a molding material cut to a suitable length in this way can be exemplified by long fiber pellets for injection molding.

  The molding method using the molding material obtained in the present invention is not particularly limited, but it can be applied to a molding method having excellent productivity such as injection molding, autoclave molding, press molding, stamping molding, etc., and these are used in combination You can also. In addition, integrated molding such as insert molding and outsert molding can be easily performed. Furthermore, even after molding, it is possible to utilize an adhesion method that is excellent in productivity, such as heat treatment, vibration welding, ultrasonic welding, and the like by heat treatment.

  The molded article obtained by molding the molding material of the present invention is suitably used in the following applications.

  The above-mentioned molded article is suitable as a housing for an electronic device, and is suitably used for a housing of a computer (including a personal computer), a cellular phone, a television, a camera, an audio player, etc. It is suitably used also for members for electrical and electronic devices represented by a keyboard support which is a supporting member. In particular, when a carbon fiber bundle having conductivity is used as a reinforcing fiber, such a member for electric and electronic devices is more preferably used because it provides electromagnetic wave shielding properties.

  The above-mentioned molded articles are suitable for electric and electronic parts applications, and connectors, LED lamps, sockets, optical pickups, terminal boards, printed boards, speakers, small motors, magnetic heads, power modules, generators, motors, motors, transformers, It is suitably used for a flow device, a voltage regulator, a rectifier, an inverter and the like.

  The above-mentioned molded products are suitable for home / office electric appliance parts, and are used for telephones, facsimiles, VTRs, copiers, TVs, microwave ovens, audio equipment, toiletries, "Laser Disc (registered trademark)", refrigerators, air conditioners, etc. It is preferably used.

  The above-mentioned molded articles are suitable for automobile parts, vehicle-related parts, members and outer plates, and safety belt parts, instrument panels, console boxes, pillars, roof rails, fenders, bumpers, door panels, roof panels, hood panels, trunks Lid, door mirror stay, spoiler, hood louver, wheel cover, wheel cap, garnish, intake manifold, fuel pump, engine coolant joint, window washer nozzle, wiper, battery peripheral parts, wire harness connector, lamp housing, lamp reflector, lamp Socket, door beam, undercover, pedal housing, radiator support, spare tire cover, front end, cylinder head cover, bearing litte Na, is preferably used, such as the pedal.

  The molded articles are suitable for aircraft related parts, members and skins, and are suitably used for landing gear pods, winglets, spoilers, edges, rudders, facings, ribs and the like.

  The above-mentioned molded articles are suitable as building materials, and wall, roof, ceiling material related parts, window material related parts, insulation material related parts, floor material related parts, seismic isolation member related parts, lifeline related parts for civil engineering buildings It is suitably used for parts and the like.

  The above-mentioned molded article is suitable as a tool, and is suitably used for a monkey, a wrench and the like.

  The above-mentioned molded articles are suitable as sporting goods, and golf club shafts, golf related products such as golf balls, sports racquet related products such as tennis racquets and badminton racquets, American football and baseball, masks such as softballs, helmets, It is suitably used for sports personal protection products such as chest pads, elbow pads and knee pads, fishing gear related products such as fishing rods, reels and lures, and winter sports related products such as skis and snowboards.

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

  First, methods of measuring various characteristics used in the present embodiment will be described.

(1) Melt Viscosity Measurement The sample to be measured was measured with a viscoelasticity measuring device. The melt viscosity was measured at 50 ° C. or 150 ° C. at 0.5 Hz using a 40 mm parallel plate.

(2) Measurement of viscosity change rate after heating at 150 ° C. for 2 hours After leaving a sample to be measured in a hot air drier at 150 ° C. for 2 hours, the same melt viscosity measurement as in (1) is carried out. Calculated.

(3) Measurement of porosity of composite fiber bundle The porosity (%) of the composite fiber bundle was calculated according to the ASTM D2734 (1997) test method. Judgment of the porosity of a composite fiber bundle was performed on the following reference | standard, and made AC a pass.
A: 0 to 5% B: 5% to 20% C: 20% to 40% D: 40% or more.

(4) Bending test of molded product obtained using molding material According to ASTM D 790 (1997), the support span is set to 100 mm using a 3-point bending test jig (indenter 10 mm, fulcrum 10 mm), crosshead The flexural strength was measured under the test conditions of a speed of 5.3 mm / min. As a tester, "Instron (registered trademark)" universal tester 4201 (manufactured by Instron) was used.

Judgment of bending strength was performed on the following reference | standard, and made AC the pass.
A: 300 MPa or more B: 270 MPa or more and less than 300 MPa C: 240 MPa or more and less than 270 MPa D: less than 240 MPa.

  Subsequently, materials used in the present embodiment will be described.

  The reinforcing fibers (A) used in Examples and Comparative Examples are as follows.

(Reinforcing Fiber-1) A continuous carbon fiber strand having a total number of 12,000 single filaments was obtained by performing spinning, baking treatment, and surface oxidation treatment using a copolymer containing polyacrylonitrile as a main component. . The properties of this carbon fiber were as follows.
Tensile strength: 4,900MPa
Tensile modulus of elasticity: 240 GPa
Tensile elongation: 2%
Specific gravity: 1.8
Single yarn diameter: 7 μm
Surface oxygen concentration ratio [O / C]: 0.12

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, and spread and arranged on a copper sample support, and then A1Kα1, ₂ was used as an X-ray source, and the inside of the sample chamber was kept at 1 × 10 ⁸ Torr. The kinetic energy value (K.E.) of the main peak of C _1s was adjusted to 1202 eV as a correction value of the peak associated with charging during measurement. C _1s peak area K. E. It determined by drawing a straight baseline in the range of 1191 to 1205 eV. O _1s peak area K. E. It determined by drawing a straight baseline in the range of 947-959 eV. From the ratio of the O _1s peak area to the C _1s peak area, the atomic number ratio was calculated using the device-specific sensitivity correction value. As an X-ray photoelectron spectrometer, model ES-200 manufactured by International Electric Co., Ltd. was used, and the sensitivity correction value was set to 1.74.

The sizing agents (s) used in Examples and Comparative Examples are as follows.
(S) -1 glycerol triglycidyl ether (manufactured by Wako Pure Chemical Industries, Ltd.)
Mass average molecular weight: 260
Number of epoxy groups per molecule: 3
Weight average molecular weight divided by the total number of carboxyl group, amino group, hydroxyl group, epoxy group and hydroxyl group per molecule: 87
(S) -2 bisphenol A diglycidyl ether (manufactured by SIGMA-ALDRICH)
Mass average molecular weight: 340
Number of epoxy groups per molecule: 2
The mass average molecular weight divided by the total number of carboxyl group, amino group, hydroxyl group, epoxy group and hydroxyl group per molecule: 170
(S) -3 (3-glycidyloxypropyl) triethoxysilane (manufactured by SIGMA-ALDRICH)
Mass average molecular weight: 278
Number of epoxy groups per molecule: 1
Weight average molecular weight divided by the total number of carboxyl group, amino group, hydroxyl group, epoxy group and hydroxyl group per molecule: 278
(S) -4 N, N'-dicyclohexylcarbodiimide (manufactured by Wako Pure Chemical Industries, Ltd.) (carbodiimide group equivalent 206, mass average molecular weight 206).

The component which comprises the component (B) used for the Example and the comparative example is as follows. The viscosity at 50 ° C. was measured according to the measurement method (1), and the softening temperature was the value described in the catalog.
(B-1) Polycarbodiimide Compound Liquid at 50 ° C. (B-1) -1 Aliphatic Polycarbodiimide “Carbodilite (registered trademark)” V-02B (manufactured by Nisshinbo Chemical Co., Ltd.) (viscosity 1 50 Pa at 50 ° C.) s)
(B-1) -2 Aliphatic polycarbodiimide "Carbodilite (registered trademark)" V-04K (manufactured by Nisshinbo Chemical Co., Ltd.) (viscosity 0.68 Pa · s at 50 ° C)
(B-1) -3 Aliphatic polycarbodiimide "Elastostab (registered trademark)" H01 (manufactured by Nisshinbo Chemical Co., Ltd.) (viscosity 2.81 Pa · s at 50 ° C)
(B-2) Other Components Constituting Component (B) (B-2) -1 Bisphenol A Type Epoxy Resin "jER (registered trademark)" 828 (manufactured by Mitsubishi Chemical Corporation) (viscosity of 50 ° C. 69 Pa · s)
(B-2) -2 Aliphatic Polycarbodiimide "Carbodilite (registered trademark)" HMV-15CA (manufactured by Nisshinbo Chemical Co., Ltd.) (solid at 50 ° C, softening temperature 70 ° C)
(B-2) -3 Aromatic Polycarbodiimide "Stabacsol (registered trademark)" P (manufactured by Rhine Chemie Co., Ltd.) (solid at 50 ° C, softening temperature 60 ° C to 90 ° C)
(B-2) -4 N, N'-dicyclohexylcarbodiimide (manufactured by Wako Pure Chemical Industries, Ltd.) (viscosity 0.02 Pa · s at 50 ° C) (the same compound as (s) -4)
(B-2) -5 15 parts by mass of dicyandiamide DICY7T (manufactured by Mitsubishi Chemical Corporation) with respect to 100 parts by mass of bisphenol A type epoxy resin “jER (registered trademark)” 828 (manufactured by Mitsubishi Chemical Corporation) -Mixture obtained by mixing 2 parts by mass of (3,4-dichlorophenyl) -1,1-dimethylurea DCMU 99 (manufactured by Hodogaya Chemical Industry Co., Ltd.) (viscosity 1.12 Pa · s at 50 ° C.)

The (C) component used for the Example and the comparative example is as follows.
(C) -1 Melting point 285 ° C., weight average molecular weight 30,000, acid-terminated product, chloroform extracted amount 0.5 mass% of polyphenylene sulfide (C) -2 polycarbonate “Eupilon (registered trademark)” H-4000 (Mitsubishi Engineering Corp. Plastics Co., Ltd.) (glass transition temperature 145 ° C., mass average molecular weight 34, 500).

(Reference Example 1) A method for applying a sizing agent to reinforcing fibers A fiber bundle of reinforcing fibers (A) is continuously taken, dipped in a water-based sizing mother liquor containing 1% by mass of a sizing agent (s), and then at 230 ° C. By heating and drying, a reinforcing fiber (A) to which the sizing agent (s) was attached was obtained. The adhesion amount of sizing agent (s) -1 after drying was adjusted to 0.5 parts by mass with respect to 100 parts by mass of the reinforcing fiber (A).

(Reference Example 2) Manufacturing Method of Composite Fiber Bundle (D) A film of a liquid obtained by heating and melting an impregnating agent (component (B)) was formed on a roll heated to a coating temperature. A reverse roll was used to form a coating of constant thickness on the roll. The component to be impregnated was deposited by passing the component (A) in continuous contact on the roll. Then, it was passed between five sets of 50 mm diameter roll presses in a chamber heated to the impregnation temperature. By this operation, the to-be-impregnated agent was impregnated to the inside of a fiber bundle, and the composite fiber bundle (D) made into the predetermined | prescribed compounding quantity was formed. In addition, the take-up speed at the time of composite fiber bundle (D) manufacture was 30 m / min.

(Reference Example 3) Manufacturing Method of Molding Material The composite fiber bundle (D) obtained in Reference Example 2 was treated with Japan Steel Works Ltd. TEX-30 α-type twin screw extruder (screw diameter 30 mm, L / D = 32). Through the coating die for wire coating method installed at the tip of the die, discharge the melted component (C) from the extruder into the die to continuously coat the periphery of the composite fiber bundle (D) Placed in Under the present circumstances, the amount of composite fiber bundle (D) and component (C) was adjusted so that it might become a desired reinforcement fiber content. After cooling the obtained continuous molding material, it was cut with a cutter to obtain a 7 mm long fiber pellet molding material. The take-up speed at the time of producing the molding material was 30 m / min.

(Reference Example 4) Molding Method of Molded Article The obtained molding material was dried under vacuum at 140 ° C for 5 hours or more. The molding material obtained by drying was molded using a mold for each test piece using a J150 EII-P injection molding machine manufactured by Japan Steel Works, Ltd. Injection molding conditions are as follows: cylinder temperature: 320 ° C., mold temperature: 150 ° C. when component (C) is polyphenylene sulfide, cylinder temperature: 300 ° C., mold temperature: 120, when component (C) is polycarbonate It went at ° C. Moreover, the maximum pressure in the case of injection molding was made into the injection molding pressure. After annealing at 120 ° C. for 3 hours, evaluations were performed on dry test pieces stored for 3 hours at room temperature in a desiccator.

(Examples 1 to 13, Comparative Examples 1 to 4 and Comparative Examples 6 to 10)
With respect to the compositions described in Table 1 and Table 2, long-fiber pellets are produced according to Reference Examples 1 to 3 under various conditions shown in the table, and test pieces for evaluation of characteristics (molded articles) according to Reference Example 4 are injection molded. did. In any of Examples and Comparative Examples, the process of Reference Example 2 and the process of Reference Example 3 were continuously performed online. Examples 10 and 11 are replaced with Experimental Examples 10 and 11, respectively.

  The evaluation results are summarized in Tables 1 and 2.

  In Comparative Example 1, the viscosity of the component (B) was high, and the composite fiber bundle (D) could not be obtained, and a molding material could not be obtained. In addition, in Comparative Example 10, the component (B) is cured in the coating / impregnation step (the viscosity change rate after heating at 150 ° C. for 2 hours exceeds 2), and the composite fiber bundle (D) can be obtained. It was not possible to obtain a molding material.

(Comparative example 5)
With respect to the composition described in Table 2, the reinforcing fiber (A) to which the sizing agent was attached according to Reference Example 1 under the various conditions shown in the table, the component (B) was not used, and the composite fiber bundle of Reference Example 3 was used as it was. In place of (D), production of long fiber pellets was attempted. The impregnatability of the component (C) into the reinforcing fiber bundle was poor, and a large amount of fluff was generated at the time of pelletizing, so that a molding material could not be obtained.

  As mentioned above, in Examples 1-13, the impregnation property of the component (B) to a reinforced fiber (A) was favorable also at 200 degrees C or less, and the molding material excellent in productivity was obtained. Moreover, the molded article which shape | molded the obtained molding material showed high bending strength, and had the outstanding dynamic characteristic.

  On the other hand, in Comparative Examples 1 to 10, when the impregnation temperature is 200 ° C. or lower, the bending strength of the molded product is lower than in Examples 1 to 13, even if the molding material can not be manufactured or manufactured. A molding material compatible with productivity and good mechanical properties was not obtained.

  In the molding material of the present invention, a composite fiber bundle in which a reinforcing fiber is impregnated with a component containing a polycarbodiimide compound liquid at 50 ° C. is coated with a thermoplastic resin containing an element other than carbon in the repeating unit structure of the main chain. Thereby, the impregnatability to the reinforcing fiber bundle at 200 ° C. or less is good, and the productivity is extremely excellent. In addition, the molding material of the present invention is excellent in molding processability and can obtain a molded article excellent in mechanical properties, particularly bending strength, and can be developed into various applications. In particular, it is suitable for automobile parts, electric / electronic parts, home / office electric appliance parts.

1 Reinforcement fiber single fiber 2 components (B)
3 Composite fiber bundle (D)
4 Thermoplastic resin (C)

Claims (10)

The total of the following components (A) to (C) is 100 parts by mass,
5 to 50 parts by mass of a reinforcing fiber (A) to which a sizing agent (s) is attached,
1 to 20 parts by mass of component (B) containing polycarbodiimide compound (B-1) liquid at 50 ° C.,
A molding material comprising 30 to 94 parts by mass of a thermoplastic resin (C) containing an element other than carbon in the repeating unit structure of the main chain,
The component (B) contains 100% by mass of the component (B-1),
Component (C) is at least one thermoplastic resin selected from the group consisting of polycarbonate and polyphenylene sulfide,
A core / sheath coated with the component (C) around a composite fiber bundle (D) in which the component (B) is impregnated with the component (A) having a single fiber number of 1,000 to 250,000 as a core structure A molding material which is a composite placed in a structure . The molding material according to claim 1, which has a length of 1 to 50 mm. The molding material according to claim 1 or 2, wherein component (A) and component (B) are in the range of component (A) / component (B) = 5/1 to 3/1 (mass ratio). Polycarbodiimide compound (B-1) is an aliphatic polycarbodiimide, molding material according to any of claims 1-3. The molding according to any one of claims 1 to 4 , wherein the component (C) is a thermoplastic resin having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an amino group in the molecule. material. The sizing agent (s) attached to the component (A) is a compound having two or more functional groups of at least one selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group and an epoxy group in one molecule. The molding material in any one of claim 1-5 . The molding material in any one of Claims 1-6 whose component (A) is carbon fiber. The method for producing a molding material according to any one of claims 1 to 7 , wherein component (B) is brought into contact with component (A) in a molten state at 50 to 150 ° C, and is further heated to supply component (B). A method for producing a molding material, comprising the step of bringing component (C) into contact with composite fiber bundle (D) in which component (A) is impregnated with 80 to 100% by mass of the amount to obtain a composite. The method for producing a molding material according to claim 8 , comprising cutting the composite fiber bundle (D) into a length of 1 to 50 mm after contacting the component (C) to obtain a composite. The molding according to claim 8 or 9 , wherein the melt viscosity at 150 ° C of component (B) is 0.001 to 10 Pa · s, and the viscosity change rate after heating at 150 ° C for 2 hours is 2 or less. Method of manufacturing material.