WO2018216524A1 - 成形材料、および繊維強化複合材料 - Google Patents
成形材料、および繊維強化複合材料 Download PDFInfo
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- WO2018216524A1 WO2018216524A1 PCT/JP2018/018491 JP2018018491W WO2018216524A1 WO 2018216524 A1 WO2018216524 A1 WO 2018216524A1 JP 2018018491 W JP2018018491 W JP 2018018491W WO 2018216524 A1 WO2018216524 A1 WO 2018216524A1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- C08K7/06—Elements
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Definitions
- the present invention relates to a molding material and a fiber-reinforced composite material.
- This application claims priority based on Japanese Patent Application No. 2017-103062 filed in Japan on May 24, 2017, the contents of which are incorporated herein by reference.
- this application claims priority based on Japanese Patent Application No. 2017-145253 filed in Japan on July 27, 2017, the contents of which are incorporated herein by reference.
- thermosetting resin used in the manufacture of fiber reinforced composite materials (FRP), in particular, sheet molding compounds (hereinafter also referred to as “SMC”), were put into practical use in the early 1970s.
- FRP fiber reinforced composite materials
- SMC sheet molding compounds
- thermosetting resin used for SMC
- high mechanical properties stress, elastic modulus
- thermal properties heat resistance
- Epoxy resins have high adhesion to other materials, and interfacial adhesion between prepregs using an epoxy resin composition as a matrix resin is particularly strong. Therefore, when the thermosetting resin is an epoxy resin, a fiber-reinforced composite material that is unlikely to cause interface fracture, which is a conventional problem, can be obtained.
- An epoxy resin composition comprising an aromatic epoxy resin, an amino compound represented by a specific formula, a dicyandiamide, and an imidazole compound that can be easily B-staged (Patent Document 1).
- an epoxy resin composition used for semiconductor sealing (2) In an epoxy resin composition containing an epoxy resin, a curing agent, and an inorganic filler, a compatibilizer such as a surfactant and a release agent such as carnauba wax and stearic acid (hereinafter also referred to as an internal release agent). And an epoxy resin composition excellent in demoldability after continuous molding (Patent Document 2).
- a fiber-reinforced composite material obtained by curing SMC is manufactured continuously by molding SMC with molds having various shapes and using the same mold. Therefore, the fiber reinforced composite material obtained by curing SMC is required to have excellent mold release properties from the mold.
- the epoxy resin composition used for SMC has high adhesiveness and adheres firmly to the mold. Therefore, a fiber reinforced composite material obtained by curing SMC using an epoxy resin composition has a poor mold release property from a mold.
- a fiber-reinforced composite material with poor demoldability increases the mold occupation time and decreases productivity. Further, when trying to demold the fiber reinforced composite material firmly bonded to the mold, a load is applied to the fiber reinforced composite material.
- An external mold release agent can be used to improve the demoldability of the fiber reinforced composite material from the mold, but the mold release agent is transferred to the surface of the fiber reinforced composite material after demolding, and after painting, etc. It is feared that the process will be adversely affected, and it is not uncommon for the mold release agent to remain on the mold surface to adversely affect the moldings of other materials. Furthermore, in the case of a complicatedly shaped mold, there may be a part where it is difficult to apply the external mold release agent or a spot of application. Also, an internal mold release agent can be used to improve the demolding property, but in the conventional internal mold release agent, the eluted internal mold release agent is transferred to the mold and adversely affects the subsequent process. There is a problem that the eluted internal mold release agent aggregates in the appearance of the fiber-reinforced composite material and affects the appearance.
- the epoxy resin composition (1) can be easily B-staged and is suitable for SMC. However, the epoxy resin composition of (1) does not consider the mold release properties of the fiber reinforced composite material from the mold.
- the epoxy resin composition (2) is said to be excellent in demoldability after continuous molding in semiconductor encapsulation.
- the epoxy resin composition (2) uses carnauba wax, metal soap and the like conventionally used as a release agent. However, when the epoxy resin composition of (2) is used for SMC, the conventional mold release agent does not provide an effect as an internal mold release agent, and the releasability from the mold of the fiber reinforced composite material is insufficient. It is.
- the present invention provides a fiber-reinforced composite material that has excellent mold releasability, excellent surface appearance of the fiber-reinforced composite material, little mold surface contamination after molding, and excellent mechanical properties and heat resistance.
- the present invention provides a molding material that can be molded, and a fiber-reinforced composite material that is excellent in demoldability and surface appearance from a mold, has little contamination on the mold surface after molding, and has excellent mechanical properties and heat resistance.
- Component (A) an epoxy resin
- Component (B) an epoxy resin curing agent
- Component (C) a compound having a solubility parameter of 11.2 or less and a melting point of 115 ° C. or less, A molding material containing reinforcing fibers.
- At least one of the compounds contained as component (C) is an ester compound of a fatty acid and an aliphatic alcohol, an ester compound of a polycarboxylic acid and an aliphatic alcohol, an ester compound of a polyhydric alcohol and a fatty acid, an aliphatic alcohol ,
- a reinforced composite material can be obtained.
- the fiber-reinforced composite material of the present invention is excellent in mold release from the mold and surface appearance, has little dirt on the mold surface after molding, and is excellent in mechanical properties and heat resistance.
- epoxy resin is a compound having one or more epoxy groups in a molecule.
- the monofunctional epoxy resin is a compound having one epoxy group
- the bifunctional epoxy resin is a compound having two epoxy groups
- the trifunctional epoxy resin is a compound having three epoxy groups
- the tetrafunctional epoxy resin is a compound having four epoxy groups.
- the “solubility parameter” is obtained by the Fedors method, which is one of the methods obtained from the molecular structure. Specifically, both the cohesive energy density and the molar molecular volume are considered to depend on the type and number of substituents, and the following formula (2) and R.I. F. Fedors, Polym. Eng. Sci. , 14 [2], 147-154 (1974).
- ⁇ [ ⁇ Ecoh / ⁇ V] 1/2 (2) Where ⁇ is the solubility parameter, ⁇ Ecoh is the cohesive energy, and ⁇ V is the molar molecular volume.
- Melting point is the temperature corresponding to the intersection of the base line on the endothermic start side and the tangent of the inflection point at the lowest temperature peak due to the melting point on the DSC exothermic curve by differential scanning calorimetry (DSC). .
- the “ ⁇ carbon of the amino group” is a carbon atom adjacent to the carbon atom ( ⁇ carbon) to which the amino group is bonded.
- the “curing agent” in component (B) is an additive that can be cured at an atmospheric temperature of 100 to 200 ° C. for 2 to 300 minutes, for example. Some of the components (B) can act as “thickeners”.
- the thickener is an additive capable of thickening to a desired viscosity value in 1 to 200 hours at an ambient temperature of 20 to 80 ° C. and then stabilizing the viscosity value.
- a “polyamine compound” is a compound having two or more amino groups in the molecule.
- a “reinforcing fiber substrate” is an aggregate of reinforcing fibers.
- Specific examples of the reinforcing fiber base material include sheet-like materials in which reinforcing fiber bundles and chopped reinforcing fiber bundles are stacked two-dimensionally at random.
- “ ⁇ ” indicating a numerical range means that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
- the molding material of one aspect of the present invention is Component (A): an epoxy resin, Component (B): an epoxy resin curing agent, Component (C): An epoxy resin composition containing a compound having a solubility parameter of 11.2 or less and a melting point of 115 ° C. or less, and reinforcing fibers.
- the molding material of another aspect of the present invention is: Component (A): an epoxy resin, Component (B): an epoxy resin curing agent, Component (C): an epoxy resin composition containing at least one of an ester compound having an alkyl group having 5 to 40 carbon atoms or an aliphatic alcohol having an alkyl group having 5 to 40 carbon atoms, a reinforcing fiber, Containing.
- the epoxy resin composition contained in the molding material of the present invention refers to components contained in the molding material of the present invention other than the reinforcing fibers.
- Molding materials include prepreg, tow prepreg, SMC, BMC, and the like. Since the viscosity characteristics of the epoxy resin composition of the present invention and the physical properties of the thickened material are suitable for SMC or BMC, SMC or BMC is preferable as the molding material, and SMC is particularly preferable.
- the above epoxy resin composition may further contain other components as necessary within the range not impairing the effects of the present invention.
- the viscosity at 25 ° C. of the epoxy resin composition is preferably 0.1 to 10 Pa ⁇ s, and more preferably 0.5 to 5 Pa ⁇ s.
- the viscosity at 25 ° C. of the epoxy resin composition is 0.1 to 10 Pa ⁇ s, the reinforcing fiber base material is satisfactorily impregnated. If the viscosity at 25 ° C. of the epoxy resin composition is 0.5 to 5 Pa ⁇ s, in addition to the impregnation property to the reinforcing fiber substrate, the coating accuracy on the carrier film is high in the production of SMC and the like (weight per unit area) Is small).
- the viscosity at 25 ° C. of the epoxy resin composition is measured using an E-type viscometer.
- Component (A) is an epoxy resin.
- Component (A) includes glycidyl ethers of bisphenols (bisphenol A, bisphenol F, bisphenol AD, halogen substituted products thereof, etc.); glycidyl polyhydric phenols obtained by condensation reaction of phenols and aromatic carbonyl compounds Ethers; glycidyl ethers of polyhydric alcohols (polyoxyalkylene bisphenol A and the like); polyglycidyl compounds derived from aromatic amines, and the like.
- the component (A) it is easy to adjust the viscosity of the epoxy resin composition to a viscosity suitable for impregnation into the reinforcing fiber base, and it is easy to adjust the mechanical properties of the fiber-reinforced composite material to a desired range.
- a bisphenol-type epoxy resin that is liquid at ° C is preferred.
- the bisphenol type epoxy resin a bisphenol A type epoxy resin is more preferable from the viewpoint of good heat resistance and chemical resistance of the fiber reinforced composite material.
- the bisphenol F type epoxy resin is more preferable from the viewpoint that the viscosity is lower than that of the bisphenol A type epoxy resin having the same molecular weight and the elastic modulus of the fiber reinforced composite material is high.
- a bifunctional epoxy resin is usually used.
- a trifunctional epoxy resin or a tetrafunctional epoxy resin may be used. By blending a trifunctional epoxy resin or a tetrafunctional epoxy resin, the heat resistance of the fiber reinforced composite material can be further improved without impairing other physical properties.
- JER registered trademark
- 825, 827, 828, 828EL, 828US, 828XA, 806, 806H, 807, 1750, YL6810 manufactured by Mitsubishi Chemical Corporation
- EPICLON registered trademark
- a component (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
- the content of component (A) in the epoxy resin composition of the present invention is preferably designed so that the viscosity of the epoxy resin composition at 25 ° C. is 0.1 to 10 Pa ⁇ s. Varies by When a trifunctional or higher functional epoxy resin is used in combination as the component (A), the content of the trifunctional or higher functional epoxy resin in 100 parts by mass of the component (A) is preferably 5 to 80 parts by mass. When designed within the above range, the heat resistance can be increased while the viscosity of the resin composition impregnated into the reinforcing fiber is good.
- Component (B) is an epoxy resin curing agent.
- a component (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
- Component (B) affects the mechanical properties, storage stability, curing temperature and time of the cured product of the molding material of the present invention containing the above-described epoxy resin composition. Some of the components (B) can act as thickeners.
- the component (B) is not limited as long as it can cure the epoxy resin.
- amine compounds, acid anhydride compounds, phenol complexes, mercaptans, Lewis acid and other amine complexes, boron chloride Examples include amine complexes and imidazole compounds.
- the form can employ
- the component (B) it is preferable to contain at least one of an amine compound, particularly a polyamine compound described later, or an acid anhydride compound.
- Aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis ( Hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine and the like.
- polyether amines examples include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, and polyoxypropylene triamines.
- alicyclic amines examples include isophorone diamine, metacene diamine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-aminopropyl) -2,4. , 8,10-tetraoxaspiro (5,5) undecane, norbornenediamine and the like.
- Aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4 -Toluenediamine, diethyltoluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'- Diaminodiphenylsulfone, m-aminobenzylamine, ⁇ - (m-aminophenyl) ethylamine, ⁇ - (p-aminophenyl) ethylamine, diaminodiethyldimethyldip
- a component (B) may be used individually by 1 type, and may be used combining 2 or more types by arbitrary compounding ratios.
- an alicyclic diamine is preferable because the pot life of the molding material containing the above-described epoxy resin composition can be extended and the storage stability of the B-stage can be improved.
- alicyclic diamines having one or two cyclohexane rings in the molecule are more preferred.
- Component (B) has an alicyclic skeleton in the molecule, and the amino group has an alicyclic skeleton from the point that the pot life of this molding material can be lengthened and the storage stability of B-stage formation is good.
- a compound directly bonded to is preferred.
- a primary amine having two alicyclic skeletons in the molecule is preferable because the pot life of the molding material can be extended and the storage stability of the B-stage can be improved.
- Component (B) is preferably an alicyclic diamine having a substituent other than an amino group on the ⁇ carbon of the amino group. Those having a substituent other than an amino group on the ⁇ carbon of the amino group tend to inhibit the reaction of the active hydrogen of the amino group, so that the pot life of the epoxy resin composition can be further extended.
- substituent other than the amino group an alkyl group having 1 to 4 carbon atoms, a benzyl group, and a cyclohexyl group are preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable from the viewpoint of increasing the pot life of the epoxy resin composition. , Methyl group, ethyl group, and isopropyl group are particularly preferable.
- Component (B) is preferably a compound represented by the following formula (1) from the viewpoint of having the above-described characteristics.
- R 1 is a single bond, a methylene group, —C (CH 3 ) 2 —, —O— or —SO 2 —
- R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom Or an alkyl group having 1 to 4 carbon atoms.
- the compound represented by the formula (1) include 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 3,3′-diethyl-4,4′-diaminodicyclohexylmethane, bis (4-amino-3-methyl-5-ethylcyclohexyl) methane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylmethane, etc. .
- the compound represented by Formula (1) may be used individually by 1 type, and may be used in combination of 2 or more type.
- 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane is particularly preferable from the viewpoint of rapid curability of the epoxy resin composition after the B-stage.
- a monofunctional amine as a component (B).
- the viscosity increase of the molding material of the present invention can be adjusted by using this together with the alicyclic diamine.
- monofunctional amines include aniline, benzylamine, and cyclohexylamine.
- the content of the monofunctional amine is 0.01 to 5 with respect to 100 parts by mass of the component (A) from the viewpoint of avoiding a decrease in pot life of the molding material. Part by mass is preferable, and 0.1 to 2 parts by mass is more preferable.
- imidazole compounds examples include 2,4-diamino-6- [2- (2-methyl-1-imidazolyl)] ethyl-s-triazine, 2,4-diamino-6- [2- (2′-methyl-1). '-Imidazolyl)] ethyl-s-triazine, 2-phenyl-4,5-bis (hydroxymethyl) imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5 -Hydroxymethylimidazole, 2-paratoluyl-4-methyl-5-hydroxymethylimidazole, 2-methatoruyl-4-methyl-5-hydroxymethylimidazole, 2-methatoruyl-4,5-bis (hydroxymethyl) imidazole, 2- 1H-imidazole such as p-toluyl-4,5-bis (hydroxymethyl) imidazole
- 2- 1H-imidazole such as p-toluyl-4,5-bis (
- the acid anhydride includes a cyclic acid anhydride having a structure in which one or more water molecules are removed from two or more acids in the molecule.
- Cyclic acid anhydrides include dodecenyl succinic anhydride, polyadipic anhydride, polyazelinic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, phthalic anhydride , Pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride and the like.
- the component (B) is preferably a compound that is solid in an epoxy resin at a temperature of 25 ° C. and is liquid at the time of curing, in particular, from the point that both pot life and reactivity at the time of curing can be achieved.
- Imidazole is preferred, and it is preferred to contain dicyandiamide as component (B). More preferably, dicyandiamide and imidazole solid at 25 ° C. are used in combination.
- component (B) is a solid in an epoxy resin at an ambient temperature of 25 ° C.
- the reactivity with the epoxy resin at 25 ° C. is low, and the storage stability is excellent.
- the molding material cured with dicyandiamide has high adhesion to reinforcing fibers.
- a molding material cured with imidazole has high heat resistance.
- the content of the component (B) is preferably 5 to 40 parts by mass, more preferably 7 to 30 parts by mass with respect to 100 parts by mass of the component (A).
- the content of the component (B) is preferably 5 parts by mass or more, more preferably 7 parts by mass or more with respect to 100 parts by mass of the component (A)
- a sufficient curing rate can be obtained.
- the content of the component (B) is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, with respect to 100 parts by mass of the component (A)
- the water absorption rate of the fiber-reinforced composite material is suppressed, In addition, the heat resistance of the fiber reinforced composite material is unlikely to decrease.
- this content is with respect to 100 mass parts of a component (A). 1 to 20 parts by mass is preferable, and 3 to 10 parts by mass is more preferable. If the content of this compound is not less than the lower limit of the above range, a sufficient curing rate can be obtained. If the content of this compound is less than or equal to the upper limit of the above range, the water absorption rate of the fiber reinforced composite material is suppressed, and the heat resistance of the fiber reinforced composite material is unlikely to decrease.
- component (B) When component (B) is added as a thickener, in addition to the alicyclic amines described above, phthalic anhydride or hydrogenated anhydrous, which may have a substituent, is highly effective as a thickener. Phthalic acid is preferred.
- the alicyclic which has one or two cyclohexane rings in the above-mentioned molecule
- numerator In addition to the alicyclic diamine containing diamine, tetrahydromethylphthalic anhydride is preferred.
- the pot life of the molding material of the present invention can be extended and the storage stability of the B-stage is improved, it has an alicyclic skeleton in the molecule and the amino group is directly bonded to the alicyclic skeleton.
- tetrahydromethylphthalic anhydride is preferred.
- a primary amine having two alicyclic skeletons in the molecule can be used because the pot life of the molding material of the present invention can be lengthened and the storage stability of B-stage formation is good.
- tetrahydromethyl phthalic anhydride is preferable.
- component (B) When component (B) is added particularly as a thickener, those having the above-mentioned characteristics are preferable.
- the active hydrogen content is 0.1 to 0.5 per total amount (molar amount) of the epoxy groups of component (A) contained in the epoxy resin composition.
- An equivalent amount or an acid anhydride is preferably 0.05 to 0.25 equivalent, and an active hydrogen is 0.20 to 0.45 equivalent or an acid anhydride is 0.10 to 0.23 equivalent. More preferably, the amount of active hydrogen is 0.25 to 0.4 equivalent, or the amount of acid anhydride is 0.12 to 0.2 equivalent. If content of a component (B) is more than the lower limit of the said range, B-staging (thickening) will fully advance. If the content of the component (B) is less than or equal to the upper limit of the above range, the flexibility of the molding material containing the thickened product of the epoxy resin composition will not be too hard, and the fluidity will not decrease too much during heat compression molding. .
- Component (C) in the molding material of one embodiment of the present invention is a compound having a solubility parameter of 11.2 or less and a melting point of 115 ° C. or less.
- the component (C) in the molding material according to one embodiment of the present invention which is a compound having a solubility parameter of 11.2 or less and a melting point of 115 ° C. or less, is referred to as a “first embodiment of the component (C)”. There is something to say.
- the component (C) in the molding material of another aspect of the present invention is at least one of an ester compound having an alkyl group having 5 to 40 carbon atoms or an aliphatic alcohol having an alkyl group having 5 to 40 carbon atoms. It is a certain compound.
- the component in the molding material according to another aspect of the present invention which is at least one of an ester compound having an alkyl group having 5 to 40 carbon atoms or an aliphatic alcohol having an alkyl group having 5 to 40 carbon atoms (C) may be referred to as “second aspect of component (C)”.
- Component (C) in the molding material of the present invention is a component that improves the demoldability of the fiber-reinforced composite material obtained by heat compression molding of the molding material of the present invention from the mold, and is used as an internal mold release agent. It has the function of.
- the epoxy resin contained in the molding material is cured in the mold. Since an epoxy resin has high adhesiveness to a metal, a cured product of the epoxy resin tends to adhere to a mold. By using the internal mold release agent, it is possible to suppress the adhesion at the interface between the mold and the cured epoxy resin during demolding.
- Epoxy resins have the property of once becoming a low viscosity and flowing before being cured in the process of heat compression molding, so when an external release agent is used to improve demoldability, the release of the resin due to the effect of resin flow.
- the mold may flow out of the system.
- the component (C) moves to the interface between the mold and the fiber-reinforced composite material during the heat compression molding and does not flow out of the system due to the resin flow during the heat compression molding.
- the solubility parameter of the component (C) in the first embodiment of the component (C) is 11.2 or less. Moreover, it is preferable that the solubility parameter of the component (C) in the 2nd aspect of a component (C) is 11.2 or less. Further, the solubility parameter of the component (C) in the first embodiment of the component (C) and the component (C) in the second embodiment of the component (C) is preferably 11.0 or less, more preferably 10.9 or less. It is. Moreover, 8.0 or more are preferable, 8.7 or more are more preferable, 8.8 or more are further more preferable, and 8.9 or more are especially preferable.
- the solubility parameter of component (C) is preferably 8.0 to 11.2, more preferably 8.7 to 11.2, and even more preferably 8.8 to 11.0. Particularly preferably, it is 8.0 to 9.6 or 10.3 to 10.9, and more preferably 8.9 to 9.6.
- the rate of separation from the epoxy resin composition is appropriate at the time of heat compression molding, and it tends to bleed at the interface between the mold and the fiber-reinforced composite material. Because of this tendency, the fiber-reinforced composite material is excellent in mold release from the mold.
- the melting point of the component (C) in the first embodiment of the component (C) is 115 ° C. or lower. Moreover, it is preferable that melting
- the melting point of the component (C) in the first aspect of the component (C) and the component (C) in the second aspect of the component (C) is preferably ⁇ 30 ° C. or higher.
- the melting point of component (C) is preferably ⁇ 20 to 100 ° C., more preferably ⁇ 10 to 90 ° C., further preferably ⁇ 5 to 80 ° C., and particularly preferably 40 to 70 ° C. If the melting point of component (C) is ⁇ 30 ° C.
- the component (C) is less likely to bleed on the surface of the molding material, and the component (C) is less likely to flow along with the resin flow during the heat compression molding, and the component present at the interface between the mold and the fiber reinforced composite material (C ) Is suppressed, and the fiber-reinforced composite material is excellent in mold release from the mold.
- the melting point of the component (C) is 115 ° C. or lower, preferably 100 ° C. or lower, more preferably 90 ° C. or lower, further preferably 80 ° C. or lower, particularly preferably 70 ° C. or lower, the component ( Since C) moves to the interface between the mold and the molding material, the fiber-reinforced composite material is excellent in demoldability from the mold.
- Component (C) in the first aspect of component (C) includes an ester compound of a fatty acid and an aliphatic alcohol, an ester compound of a polyvalent carboxylic acid and an aliphatic alcohol, an ester compound of a polyhydric alcohol and a fatty acid, a fat Aliphatic alcohols, fatty acid amides, fatty acid metal salts and the like.
- the fatty chain may be a saturated fatty chain or an unsaturated fatty chain.
- Component (C) in the first aspect of component (C) is carbon from the point that the alkyl chain is present at a high concentration on the surface of the fiber-reinforced composite material, and the demoldability from the mold tends to be improved.
- it is an ester compound having an alkyl group of 5 to 40 or an aliphatic alcohol having an alkyl group of 5 to 40 carbon atoms
- component (C) in the second embodiment of component (C) Is an ester compound having an alkyl group having 5 to 40 carbon atoms or a compound which is at least one of an aliphatic alcohol having an alkyl group having 5 to 40 carbon atoms.
- Component (C) in the first embodiment of component (C) and component (C) in the second embodiment of component (C) are more preferably ester compounds having an alkyl group having 10 to 30 carbon atoms, More preferred are ester compounds having 20 alkyl chains. Specifically, it is an ester compound having a long chain alkyl group represented by the following chemical formula.
- R 1 and R 2 are the same or different and each is an alkyl group, and at least one of R 1 and R 2 is an alkyl group having 5 to 40 carbon atoms.
- the release property of the fiber-reinforced composite material from the mold is good, and the mold surface tends to be hardly contaminated at the time of mold release.
- sorbitan fatty acid ester is more preferable, and sorbitan monostearate as shown in the following chemical formula is particularly preferable.
- the content of the component (C) is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, and 0.3 to 6 parts by mass with respect to 100 parts by mass of the component (A). More preferred is 0.5 to 5 parts by mass.
- the content of the component (C) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, particularly preferably 0.5 parts by mass or more with respect to 100 parts by mass of the component (A). If it exists, the mold release property from the metal mold
- the content of the component (C) is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, further preferably 6 parts by mass or less, particularly preferably 5 parts by mass with respect to 100 parts by mass of the component (A). If it is below, it is easy to make the mold release property of the fiber reinforced composite material compatible with the heat resistance of the fiber reinforced composite material.
- epoxy resin composition contained in the molding material of the present invention may contain as necessary, curing acceleration other than the above components (A), (B), and (C) is promoted.
- curing acceleration other than the above components (A), (B), and (C) is promoted.
- a curing accelerator is preferably used for the following reasons.
- the reaction start temperature can be lowered without greatly deteriorating the storage stability, and the molding material can be cured in a short time.
- the mechanical properties (bending strength, flexural modulus) and thermal properties (heat resistance) of the fiber reinforced composite material can be improved.
- a urea compound is preferable because the mechanical properties (bending strength and flexural modulus) of the fiber-reinforced composite material are increased.
- urea compounds include 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3- (3-chloro-4-methylphenyl) -1,1- Examples include dimethylurea, 2,4-bis (3,3-dimethylureido) toluene, 1,1 ′-(4-methyl-1,3-phenylene) bis (3,3-dimethylurea) and the like.
- inorganic filler examples include calcium carbonate, aluminum hydroxide, clay, barium sulfate, magnesium oxide, glass powder, hollow glass beads, and aerosil.
- the epoxy resin composition contained in the molding material of the present invention can be prepared by a conventionally known method.
- each component may be mixed and prepared at the same time, and a master batch in which component (B), component (C), etc. are appropriately dispersed in component (A) in advance is prepared and used. May be.
- a master batch in which component (B), component (C), etc. are appropriately dispersed in component (A) in advance is prepared and used. May be.
- it is preferable to devise measures not to raise the temperature during kneading such as adjusting the kneading speed or water cooling the kneading pot.
- Examples of the kneading apparatus include a raking machine, an attritor, a planetary mixer, a dissolver, a triple roll, a kneader, a universal stirrer, a homogenizer, a homodispenser, a ball mill, and a bead mill. Two or more kneading apparatuses may be used in combination.
- the epoxy resin composition contained in the molding material of the present invention is a matrix resin of a molding material which is an intermediate material used for the production of a fiber reinforced composite material, particularly a matrix resin for SMC and a bulk molding compound (hereinafter referred to as “BMC”). It is also suitable as a matrix resin. Since the epoxy resin composition contained in the molding material of the present invention has a low viscosity and good impregnation properties, it can also be used as a matrix resin composition in the molding material of a fiber reinforced composite material by the resin transfer molding method. .
- the epoxy resin composition contained in the molding material of the present invention may be a thickened product of the epoxy resin composition. That is, the molding material of the present invention may contain a thickened product of the above-described epoxy resin composition instead of the above-described epoxy resin composition.
- the thickened product of the epoxy resin composition is obtained by thickening the epoxy resin composition contained in the molding material of the present invention, that is, a B-stage.
- the thickened product of the epoxy resin composition is obtained, for example, as follows. After impregnating the above-mentioned epoxy resin composition into the reinforcing fiber base by a known method suitable for the form of the reinforcing fiber base, the temperature is about room temperature to 80 ° C. for several hours to several days, or 80 to 200. By maintaining the temperature at about 0 ° C. for several seconds to several minutes, the epoxy group of component (A) in the epoxy resin composition reacts with component (B), and the epoxy resin composition becomes B-staged.
- the reaction conditions between the epoxy group of component (A) and component (B) are preferably selected so that the viscosity at 23 ° C. of the thickened product of the epoxy resin composition obtained after the reaction falls within the range described below.
- the viscosity at 23 ° C. of the thickened product of the epoxy resin composition is preferably 3000 to 150,000 Pa ⁇ s, more preferably 5000 to 300000 Pa ⁇ s. If the viscosity of the thickened product of the epoxy resin composition at 23 ° C. is equal to or higher than the lower limit of the above range, the surface tack is reduced when the molding material is handled. If the viscosity at 23 ° C. of the thickened product of the epoxy resin composition is not more than the upper limit of the above range, the flow characteristics during heat compression molding will be good. The viscosity at 23 ° C. of the thickened product of the epoxy resin composition is measured using a B-type viscometer.
- component (A) epoxy resin
- component (B ′) compound having a partial structure represented by the following formula (3)
- component (B) epoxy resin cured It preferably contains an agent (excluding component (B ′)) and component (C): a compound having a solubility parameter of 11.2 or less and a melting point of 115 ° C. or less.
- component (A) epoxy resin
- component (B ′) a compound having a partial structure represented by the following formula (3)
- component (C) ester compound having an alkyl group having 5 to 40 carbon atoms or alkyl group having 5 to 40 carbon atoms
- component (A1) aromatic epoxy resin
- component (A2) aliphatic epoxy resin
- component (B ′) The compound having the partial structure represented by 3)
- the component (C): the solubility parameter is 11.2 or less.
- component (A1) aromatic epoxy resin
- component (A2) aliphatic epoxy resin
- component (B ′) 3) a compound having a partial structure represented by 3
- component (B) an epoxy resin curing agent (excluding component (B ′))
- component (C) an alkyl group having 5 to 40 carbon atoms.
- an ester compound having at least one of aliphatic alcohols having an alkyl group having 5 to 40 carbon atoms are preferred.
- R 1 is a single bond, a methylene group, —C (CH 3 ) 2 —, —O— or —SO 2 —
- R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom Or an alkyl group having 1 to 4 carbon atoms.
- the component (A1) in the thickened product of the preferred epoxy resin composition is 25 in that the mechanical properties (bending strength, flexural modulus) and thermal properties (heat resistance) of the fiber reinforced composite material tend to be good.
- a liquid aromatic epoxy resin having a viscosity at 0.3 ° C. of 0.3 Pa ⁇ s or more is preferred.
- the viscosity at 25 ° C. of the epoxy resin is measured using an E-type viscometer.
- reinforcing fiber Various types can be used depending on the application and purpose of the molding material, including carbon fibers (including graphite fibers; the same applies hereinafter), aramid fibers, silicon carbide fibers, alumina fibers, and boron fibers. , Tungsten carbide fiber, glass fiber and the like. From the viewpoint of mechanical properties of the fiber-reinforced composite material, carbon fibers and glass fibers are preferable, and carbon fibers are particularly preferable.
- the reinforcing fiber is usually used in the state of a reinforcing fiber bundle composed of single fibers in the range of 1000 or more and 60000 or less.
- the reinforcing fiber bundle may exist while maintaining the shape of the reinforcing fiber bundle, or may exist in a bundle of fewer fibers.
- SMC and BMC they usually exist in smaller bundles.
- a chopped reinforcing fiber bundle made of short fibers is preferable.
- the length of the short fiber is preferably 0.3 to 10 cm, and more preferably 1 to 5 cm. If the length of the short fiber is 0.3 cm or more, a fiber-reinforced composite material having good mechanical properties can be obtained. If the length of the short fiber is 10 cm or less, SMC or BMC having good flow characteristics during heat compression molding can be obtained.
- a reinforcing fiber base material in SMC a sheet-like material in which chopped reinforcing fiber bundles are stacked two-dimensionally at random is more preferable.
- the SMC which is the molding material of the present invention, is produced, for example, by sufficiently impregnating the above-mentioned epoxy resin composition into a sheet of a chopped reinforcing fiber bundle and thickening the epoxy resin composition as necessary.
- the BMC which is the molding material of the present invention, is produced, for example, by thoroughly mixing the chopped reinforcing fiber bundle and the above-described epoxy resin composition into a bulk shape and increasing the viscosity of the epoxy resin composition as necessary.
- the method of mixing the chopped reinforcing fiber bundle and the epoxy resin composition into a bulk shape various conventionally known methods can be adopted.
- the impregnation property of the epoxy resin composition into the chopped reinforcing fiber bundle, the fiber From the viewpoint of productivity, such as dispersibility, the method of mixing with a pressure kneader is preferred. You may perform mixing by a pressure kneader, heating as needed.
- the heating temperature is preferably equal to or lower than the temperature at which the epoxy resin begins to cure, and more preferably 10 to 35 ° C.
- the pressure at the time of mixing by the pressure kneader is not particularly required to be higher than the atmospheric pressure, but when the viscosity of the epoxy resin composition is high, the epoxy resin composition takes in air and is kneaded, and the epoxy into the chopped reinforcing fiber bundle When impregnation with the resin composition becomes difficult, the pressure may be higher than atmospheric pressure. After obtaining the bulk material, by thickening the epoxy resin composition, tackiness on the surface of the BMC is suppressed, and a BMC suitable for the molding operation is obtained.
- the molding material of the present invention described above contains the above-described epoxy resin composition or its thickened product and reinforcing fibers, and therefore has excellent mold release properties, mechanical properties, and heat resistance. A reinforced composite material can be obtained.
- the fiber-reinforced composite material of the present invention is a cured product of the molding material of the present invention.
- the fiber-reinforced composite material of the present invention is formed by thermoforming a molding material such as SMC or BMC and curing the epoxy resin composition contained in the molding material of the present invention, or contained in the molding material of the present invention. It is manufactured by further curing a thickened epoxy resin.
- the following method is mentioned, for example.
- One SMC or a stack of a plurality of SMCs is set between a pair of molds.
- SMC is heated and compressed at 120 to 230 ° C. for 2 to 60 minutes to cure the epoxy resin composition to obtain a fiber-reinforced composite material as a molded product.
- a honeycomb structure such as corrugated cardboard may be used as a core material, and SMC may be disposed on both sides or one side.
- Examples of a method for producing a fiber-reinforced composite material using BMC include methods by compression molding, transfer molding, injection molding, and the like. Since the epoxy resin composition contained in the molding material of the present invention often has a high viscosity around room temperature, after the BMC is press-fitted into a mold or the like having a predetermined shape, the BMC is heated and compressed to obtain an epoxy resin. By adopting a compression molding method for curing the composition, even a molded product having a complicated shape can be produced in a short time.
- the fiber-reinforced composite material of the present invention described above is a cured product of the molding material of the present invention, it is excellent in mold release from a mold, mechanical properties, and heat resistance.
- jER (registered trademark) 827 bisphenol A type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, viscosity at 25 ° C .: 10 Pa ⁇ s).
- jER (registered trademark) 828 bisphenol A type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, viscosity at 25 ° C .: 15 Pa ⁇ s).
- YED216M 1,6-hexanediol diglycidyl ether (manufactured by Mitsubishi Chemical Corporation).
- jER (registered trademark) 630 triglycidyl-p-aminophenol (manufactured by Mitsubishi Chemical Corporation, viscosity at 25 ° C .: 0.7 Pa ⁇ s).
- TETRAD-X N, N, N ′, N′-tetraglycidyl-m-xylylenediamine (Mitsubishi Gas Chemical Co., Ltd., viscosity at 25 ° C .: 2.3 Pa ⁇ s)
- Component B jER Cure (registered trademark) 113: 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane (manufactured by Mitsubishi Chemical Corporation).
- HN-2200 Tetrahydromethylphthalic anhydride (manufactured by Hitachi Chemical Co., Ltd.).
- DICYANEX 1400F Dicyandiamide (manufactured by Air Products).
- 2MZA-PW 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (manufactured by Shikoku Kasei Co., Ltd., 2MZA-PW).
- the melting points of the component (C) and other internal mold release agents were measured using a DSC apparatus (TA Instruments, Q1000).
- the test substance was weighed in a standard aluminum hermetic pan, and a sample was prepared by covering with a standard aluminum lid.
- the DSC exothermic curve was obtained by raising the temperature from 30 ° C. to 300 ° C. at 10 ° C./min.
- the melting point was defined as the temperature corresponding to the intersection of the base line on the endothermic start side and the tangent of the inflection point at the lowest temperature peak due to the melting point on the DSC exothermic curve.
- Example 1 The master batch of DICY 1400F, the master batch of 2MZA-PW and the master batch of Emanon 3201M-V, jER (registered trademark) 827, and YED216M were kneaded using a three-one motor so as to have the composition shown in Table 2. Then, a predetermined amount of jER Cure (registered trademark) 113 was added and kneaded again to obtain an epoxy resin composition.
- jER Cure registered trademark
- Examples 2 to 12 Comparative Examples 1 to 3
- An epoxy resin composition was obtained in the same manner as in Example 1 except that the respective components were blended so as to have the compositions shown in Tables 2 to 4.
- Example 13 A master batch of DICYANEX 1400F, a master batch of 2MZA-PW and a master batch of Rheodor SP-S10V, jER (registered trademark) 827, and YED216M were kneaded using a three-one motor so that the composition shown in Table 5 was obtained. Then, a predetermined amount of jER Cure (registered trademark) 113 was added and kneaded again to obtain an epoxy resin composition.
- jER Cure registered trademark
- Example 14 to 21 An epoxy resin composition was obtained in the same manner as in Example 13 except that each component was blended so as to have the composition shown in Table 5.
- BMCs were produced using the epoxy resin compositions obtained in Examples 1 to 7, 13 to 15, and Comparative Examples 1 and 2.
- BMC is a chopped carbon fiber bundle obtained by cutting a carbon fiber bundle (manufactured by Mitsubishi Chemical Co., Ltd., TR50S 15L) into a length of 25 mm from the epoxy resin composition obtained in each example or comparative example. Was sufficiently kneaded.
- the mass of the carbon fiber was about 30 parts by mass with respect to 100 parts by mass of the epoxy resin composition.
- a pair of upper and lower 30 cm square flat plate dies subjected to chrome plating were heated to 140 ° C., and an external mold release agent (Neos, Fleet 65) was wiped onto the surfaces of the upper and lower dies with a spray gun.
- BMC or SMC obtained by the above-mentioned BMC manufacturing or SMC manufacturing is stacked in 2 ply, and the mold is charged at a charge rate (ratio of SMC area to mold area) of about 60%, and mold temperature 140
- the epoxy resin composition was cured by heating and compression at 5 ° C. for 5 minutes under the conditions of 0 ° C. and a pressure of 8 MPa to obtain a flat fiber-reinforced composite material (CFRP molded plate) having a thickness of about 2 mm and a 300 mm square.
- a CFRP molded plate was cut into a length of 55 mm and a width of 12.7 mm to prepare a test piece.
- the test piece was measured using a dynamic viscoelasticity measuring device (TA Instruments, Q800) under the measurement conditions of a frequency of 1 Hz, a heating rate of 5 ° C./min, and a cantilever bending mode, and a temperature-tan ⁇ curve was obtained.
- the temperature at which the maximum value was exhibited was taken as the glass transition temperature (Tg). The higher the Tg, the better the heat resistance, and the higher the mold temperature, the better the mold release.
- Tg glass transition temperature
- the bending properties of the CFRP molding plate molded with SMC were evaluated.
- a CFRP molded plate was cut into a length of 110 mm and a width of 25 mm, and the cut surface was treated with sandpaper # 1200 to prepare a test piece.
- a universal testing machine Instron, Instron (registered trademark) 4465
- analysis software Bluehill a test piece is subjected to a bending test using a three-point bending jig in an environment of a temperature of 23 ° C. and a humidity of 50% RH.
- Strength (MPa) and flexural modulus (GPa) were calculated. Measurement was performed using a total of 12 test pieces, and the average value was adopted.
- the molding material of the present invention is superior to the conventional molding material, especially the conventional SMC, and is excellent in the demolding property of the fiber reinforced composite material using the molding material, and the mold occupation time at the time of molding the SMC is short. It is excellent in that it gives a molded product of fiber reinforced composite material. Further, it has processability, moldability and pot life equivalent to those of conventional SMC, and is excellent in storage stability after impregnating the reinforcing fiber base material.
- the SMC using the epoxy resin composition contained in the molding material of the present invention as a matrix resin is excellent in impact resistance and heat resistance unique to epoxy resins, and has high bending strength and bending elastic modulus. It is suitably used as a raw material for structural parts.
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Abstract
Description
本願は、2017年5月24日に、日本に出願された特願2017-103062号に基づき優先権を主張し、その内容をここに援用する。
また、本願は、2017年7月27日に、日本に出願された特願2017-145253号に基づき優先権を主張し、その内容をここに援用する。
(1)芳香族エポキシ樹脂、特定の式で示されるアミノ化合物、ジシアンジアミドおよびイミダゾール化合物からなる、Bステージ化が容易なエポキシ樹脂組成物(特許文献1)。
(2)エポキシ樹脂と硬化剤と無機充填材とを含有するエポキシ樹脂組成物において、界面活性剤等の相溶化剤とカルナバワックス、ステアリン酸等の離型剤(以下、内部離型剤とも記す。)との溶融混合物を配合した、連続成形後の脱型性に優れるエポキシ樹脂組成物(特許文献2)。
しかし、SMCに用いるエポキシ樹脂組成物は、接着性が高く、金型にも強固に接着する。そのため、エポキシ樹脂組成物を用いたSMCを硬化させてなる繊維強化複合材料は、金型からの脱型性が悪い。脱型性が悪い繊維強化複合材料は、金型占有時間が長くなり、生産性を低下させる。また、金型に強固に接着した繊維強化複合材料を脱型しようとすると、繊維強化複合材料に負荷がかかる。
繊維強化複合材料の金型からの脱型性を改善するために外部離型剤を用いることもできるが、脱型後の繊維強化複合材料の表面に離型剤が転写され、塗装等の後工程に悪影響を及ぼすことが懸念され、金型表面に離型剤が残留することで、他材の成形物にも悪影響を及ぼすことも珍しくない。さらに、複雑な形状の金型の場合、部分的に外部離型剤の塗布が難しい個所や塗布の斑が生じることがある。
また、脱型性の改善のために内部離型剤を用いることもできるが、従来の内部離型剤には、溶出した内部離型剤が金型に転写され後工程へ悪影響を及ぼしたり、溶出した内部離型剤が繊維強化複合材料の外観に凝集し、外観への影響を及ぼしたりといった課題がある。
(2)のエポキシ樹脂組成物は、半導体封止における連続成形後の脱型性に優れるとされている。(2)のエポキシ樹脂組成物は、離型剤として従来から用いられているカルナバワックス、金属石鹸等を用いている。しかし、(2)のエポキシ樹脂組成物をSMCに用いた場合、従来の離型剤では内部離型剤としては効果が得られず、繊維強化複合材料の金型からの脱型性は不十分である。
[1]
成分(A):エポキシ樹脂と、
成分(B):エポキシ樹脂硬化剤と、
成分(C):溶解度パラメータが11.2以下であり、融点が115℃以下である化合物と、
強化繊維とを含有する、成形材料。
[2]
成分(C)として含有される化合物の少なくとも一種が、脂肪酸と脂肪族アルコールとのエステル化合物、多価カルボン酸と脂肪族アルコールとのエステル化合物、多価アルコールと脂肪酸とのエステル化合物、脂肪族アルコール、脂肪酸アミド、および、脂肪酸の金属塩から選ばれる化合物である、[1]に記載の成形材料。
[3]
成分(C)として含有される化合物の少なくとも一種が、溶解度パラメータが8.0~9.6、または、10.3~10.9の範囲の化合物である、[1]または[2]に記載の成形材料。
[4]
成分(C)として含有される化合物の少なくとも一種が、融点が-30℃以上の化合物である、[1]~[3]のいずれかに記載の成形材料。
[5]
成分(A):エポキシ樹脂と、
成分(B):エポキシ樹脂硬化剤と、
成分(C):炭素数が5~40のアルキル基を有するエステル化合物または炭素数が5~40のアルキル基を有する脂肪族アルコールの少なくとも一方である化合物と、
強化繊維とを含有する、成形材料。
[6]
前記成分(C)として含有される化合物の少なくとも一種が、水酸基を有する脂肪族化合物である、[5]に記載の成形材料。
[7]
前記成分(C)として含有される化合物の少なくとも一種が、ソルビタン脂肪酸エステルである、[6]に記載の成形材料。
[8]
前記成分(C)として含有される化合物の少なくとも一種が、ソルビタンモノステアレートである、[7]に記載の成形材料。
[9]
前記成分(B)として含有されるエポキシ樹脂硬化剤の少なくとも一種が、ポリアミン系化合物または酸無水物系化合物の少なくとも一方である、[1]~[8]のいずれかに記載の成形材料。
[10]
前記成分(B)として含有されるエポキシ樹脂硬化剤の少なくとも一種が、脂環式ジアミンである、[1]~[9]のいずれかに記載の成形材料。
[11]
前記成分(B)として含有されるエポキシ樹脂硬化剤の少なくとも一種が、ジシアンジアミドである、[1]~[10]のいずれかに記載の成形材料。
[12]
前記強化繊維が、炭素繊維である、[1]~[11]のいずれかに記載の成形材料。
[13]
シートモールディングコンパウンドである、[1]~[12]のいずれかに記載の成形材料。
[14]
[1]~[13]のいずれかに記載の成形材料の硬化物である、繊維強化複合材料。
本発明の繊維強化複合材料は、金型からの脱型性や表面外観に優れ、成形後の金型表面の汚れが少なく、機械特性および耐熱性に優れる。
「エポキシ樹脂」は、分子中にエポキシ基を1つ以上有する化合物である。単官能エポキシ樹脂はエポキシ基が1つの化合物、二官能エポキシ樹脂はエポキシ基が2つの化合物、三官能エポキシ樹脂はエポキシ基が3つの化合物、四官能エポキシ樹脂はエポキシ基が4つの化合物である。
δ=[ΣEcoh/ΣV]1/2 (2)
ただし、δは、溶解度パラメータであり、ΣEcohは、凝集エネルギーであり、ΣVは、モル分子容である。
「アミノ基のβ炭素」は、アミノ基が結合した炭素原子(α炭素)に隣接する炭素原子である。
「ポリアミン系化合物」は、分子中にアミノ基を2つ以上有する化合物である。
数値範囲を示す「~」は、その前後に記載された数値を下限値および上限値として含むことを意味する。
本発明の一つの態様の成形材料は、
成分(A):エポキシ樹脂と、
成分(B):エポキシ樹脂硬化剤と、
成分(C):溶解度パラメータが11.2以下であり、融点が115℃以下である化合物とを含むエポキシ樹脂組成物と、強化繊維とを含有する。
また、本発明の別の態様の成形材料は、
成分(A):エポキシ樹脂と、
成分(B):エポキシ樹脂硬化剤と、
成分(C):炭素数が5~40のアルキル基を有するエステル化合物または炭素数が5~40のアルキル基を有する脂肪族アルコールの少なくとも一方の化合物とを含むエポキシ樹脂組成物と、強化繊維とを含有する。
エポキシ樹脂組成物の25℃における粘度が0.1~10Pa・sであれば、強化繊維基材への含浸が良好である。エポキシ樹脂組成物の25℃における粘度が0.5~5Pa・sであれば、強化繊維基材への含浸性に加え、SMC等の製造において、キャリアフィルム上への塗工精度が高い(目付けの振れが小さい)。
エポキシ樹脂組成物の25℃における粘度は、E型粘度計を用いて測定される。
成分(A)は、エポキシ樹脂である。
成分(A)としては、ビスフェノール類(ビスフェノールA、ビスフェノールF、ビスフェノールAD、これらのハロゲン置換体等)のグリシジルエーテル;フェノール類と芳香族カルボニル化合物との縮合反応により得られる多価フェノール類のグリシジルエーテル;多価アルコール類(ポリオキシアルキレンビスフェノールA等)のグリシジルエーテル;芳香族アミン類から誘導されるポリグリシジル化合物等が挙げられる。
ビスフェノール型エポキシ樹脂としては、繊維強化複合材料の耐熱性および耐薬品性が良好である点からは、ビスフェノールA型エポキシ樹脂がより好ましい。
また、同程度の分子量を有するビスフェノールA型エポキシ樹脂よりも粘度が低く、繊維強化複合材料の弾性率が高い点からは、ビスフェノールF型エポキシ樹脂がより好ましい。
成分(A)として、三官能のエポキシ樹脂または四官能エポキシ樹脂を用いてもよい。三官能のエポキシ樹脂や四官能のエポキシ樹脂を配合することによって、他の物性を損なうことなく、繊維強化複合材料の耐熱性をさらに向上できる。
三菱ケミカル社製のjER(登録商標)の825、827、828、828EL、828US、828XA、806、806H、807、1750、YL6810、
DIC社製のEPICLON(登録商標)の840、840-S、850、850-S、EXA-850CRP、850-LC、830、830-S、835、EXA-830CRP、EXA-830LVP、EXA-835LV、
新日鉄住金化学社製のエポトート(登録商標)のYD-127、YD-128、YD-128G、YD-128S、YD-128CA、YDF-170、
日本化薬社製のRE-303S-L、RE-310S、GAN、GOT等。
三菱ケミカル社製のjER(登録商標)の152、604、630、630LSD、
新日鉄住金化学社製のYH-434、YH434L、
住友化学工業社製のスミエポキシ(登録商標)のELM434、ELM100、ELM120、
三菱ガス化学社製のTETRAD-X等。
成分(A)は、1種を単独で用いてもよく、2種以上を組み合せて用いてもよい。
成分(A)として三官能以上のエポキシ樹脂を併用する場合、成分(A)の100質量部中の三官能以上のエポキシ樹脂の含有量は5~80質量部が好ましい。
前記範囲内に設計すると、強化繊維への樹脂組成物の含浸が良好な粘度のまま耐熱性を高くすることができる。
成分(B)は、エポキシ樹脂硬化剤である。
成分(B)は、1種を単独で用いてもよく、2種以上を組み合せて用いてもよい。
成分(B)は、上述のエポキシ樹脂組成物を含有する本発明の成形材料の硬化物の機械的特性、貯蔵安定性、硬化の温度や時間に影響を与える。また、成分(B)の中には、増粘剤として作用できるものがある。
成分(B)として、アミン系化合物、特に後述するポリアミン系化合物、または酸無水物系化合物の少なくとも一方を含有することが好ましい。
成分(B)としては、増粘剤としての効果が高い点から、脂環式アミン類が好ましい。
アミノ基以外の置換基としては、エポキシ樹脂組成物のポットライフが長くなる点から、炭素数1~4のアルキル基、ベンジル基、シクロヘキシル基が好ましく、炭素数1~4のアルキル基がより好ましく、メチル基、エチル基、イソプロピル基が特に好ましい。
式(1)で表される化合物としては、Bステージ化後のエポキシ樹脂組成物の速硬化性の点から、3,3’-ジメチル-4,4’-ジアミノジシクロヘキシルメタンが特に好ましい。
成分(B)として単官能アミンを併用する場合、単官能アミンの含有量は、成形材料のポットライフの低下を避ける点から、成分(A)の100質量部に対して、0.01~5質量部が好ましく、0.1~2質量部がより好ましい。
環状酸無水物としては、ドデセニル無水コハク酸、ポリアジピン酸無水物、ポリアゼライン酸無水物、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水メチルハイミック酸、ヘキサヒドロ無水フタル酸、無水フタル酸、無水ピロメリット酸、無水トリメリット酸、ベンゾフェノンテトラカルボン酸無水物等が挙げられる。
成分(B)が25℃の雰囲気温度で、エポキシ樹脂中で固体である場合、25℃におけるエポキシ樹脂との反応性が低く、貯蔵安定性に優れる。特に、ジシアンジアミドで硬化した成形材料は強化繊維への接着性も高い。また、イミダゾールで硬化した成形材料は耐熱性が高い。
成分(B)の含有量が、成分(A)の100質量部に対して、好ましくは5質量部以上、より好ましくは7質量部以上であれば、十分な硬化速度が得られる。成分(B)の含有量が、成分(A)の100質量部に対して、好ましくは40質量部以下、より好ましくは30質量部以下であれば、繊維強化複合材料の吸水率が抑えられ、また、繊維強化複合材料の耐熱性が低下しにくい。
この化合物の含有量が前記範囲の下限値以上であれば、十分な硬化速度が得られる。この化合物の含有量が前記範囲の上限値以下であれば、繊維強化複合材料の吸水率が抑えられ、また、繊維強化複合材料の耐熱性が低下しにくい。
これらは1種を単独で用いてもよく、2種以上を組み合せて用いてもよい。
成分(B)の含有量が前記範囲の下限値以上であれば、Bステージ化(増粘)が十分に進行する。成分(B)の含有量が前記範囲の上限値以下であれば、エポキシ樹脂組成物の増粘物を含む成形材料の柔軟性が硬くなり過ぎず、加熱圧縮成形時に流動性が低下しすぎない。
本発明の一つの態様の成形材料における成分(C)は、溶解度パラメータが11.2以下であり、融点が115℃以下である化合物である。以下、溶解度パラメータが11.2以下であり、融点が115℃以下である化合物である、本発明の一つの態様の成形材料における成分(C)を、「成分(C)の第1態様」と言うことがある。
また、本発明の別の態様の成形材料における成分(C)は、炭素数が5~40のアルキル基を有するエステル化合物または炭素数が5~40のアルキル基を有する脂肪族アルコールの少なくとも一方である化合物である。以下、炭素数が5~40のアルキル基を有するエステル化合物または炭素数が5~40のアルキル基を有する脂肪族アルコールの少なくとも一方である化合物である、本発明の別の態様の成形材料における成分(C)を、「成分(C)の第2態様」と言うことがある。
本発明の成形材料における成分(C)は、本発明の成形材料を加熱圧縮成形することで得られる繊維強化複合材料の金型からの脱型性を向上する成分であり、内部離型剤としての機能を有するものである。
成分(C)は、加熱圧縮成形の際に金型と繊維強化複合材料との界面へと移行し、かつ加熱圧縮成形の際の樹脂流動によって系外へ流出しない。
具体的には、成分(C)の溶解度パラメータは、8.0~11.2が好ましく、8.7~11.2がより好ましく、8.8~11.0がさらに好ましい。特に好ましくは、8.0~9.6または10.3~10.9であり、8.9~9.6がさらに好ましい。
成分(C)の溶解度パラメータが前記範囲内であれば、加熱圧縮成形の際に、エポキシ樹脂組成物から分離する速度が適切であり、金型と繊維強化複合材料との界面にブリードしやすくなる傾向にあるため、繊維強化複合材料の金型からの脱型性に優れる。
また、成分(C)の融点は、-20~100℃が好ましく、-10~90℃がより好ましく、-5~80℃がさらに好ましく、40~70℃が特に好ましい。成分(C)の融点が-30℃以上、好ましくは-20℃以上、より好ましくは-10℃以上、さらに好ましくは-5℃以上、特に好ましくは40℃以上であれば、加熱圧縮成形する前に成分(C)が成形材料の表面にブリードしにくく、加熱圧縮成形の際の樹脂流動とともに成分(C)が流されにくくなり、金型と繊維強化複合材料との界面に存在する成分(C)の濃度の低下が抑えられ、繊維強化複合材料の金型からの脱型性に優れる。成分(C)の融点が115℃以下、好ましくは100℃以下、より好ましくは90℃以下、さらに好ましくは80℃以下、特に好ましくは70℃以下であれば、エポキシ樹脂が硬化する前に成分(C)が金型と成形材料との界面に移行するため、繊維強化複合材料の金型からの脱型性に優れる。
具体的には、エチレングリコールジステアレート、クエン酸ステアリル、ステアリン酸メチル、ミリスチン酸ミリスチル、ベヘニルアルコール、ステアリルアルコール、ビスフェノールAエチレングリコールエーテルジラウレート、エチレンビスオレイン酸アミド、ラウリン酸アミド、ソルビタンモノステアレート等が挙げられる。
成分(C)の第1態様における成分(C)および成分(C)の第2態様における成分(C)としては、炭素数10~30のアルキル基を有するエステル化合物がより好ましく、炭素数12~20のアルキル鎖を有するエステル化合物がさらに好ましい。
具体的には、下記化学式で示されるような長鎖アルキル基を有するエステル化合物である。
成分(C)の含有量が、成分(A)の100質量部に対して、好ましくは0.1質量部以上、さらに好ましくは0.3質量部以上、特に好ましくは0.5質量部以上であれば、繊維強化複合材料の金型からの脱型性がさらに優れる。成分(C)の含有量が、成分(A)の100質量部に対して、好ましくは10質量部以下、より好ましくは7質量部以下、さらに好ましくは6質量部以下、特に好ましくは5質量部以下であれば、繊維強化複合材料の金型からの脱型性と繊維強化複合材料の耐熱性を両立しやすい。
本発明の成形材料に含有されるエポキシ樹脂組成物が必要に応じて含有していてもよい他の成分としては、上記成分(A)、成分(B)、成分(C)以外の、硬化促進剤、無機質充填材、有機顔料、無機顔料等が挙げられる。
成分(B)と適切な硬化促進剤とを併用することによって、貯蔵安定性を大きく損なうことなく反応開始温度を低下させることができ、成形材料の短時間硬化が可能となる。また、繊維強化複合材料の機械特性(曲げ強度、曲げ弾性率)および熱特性(耐熱性)も向上させることができる。
尿素化合物としては、3-フェニル-1,1-ジメチル尿素、3-(3,4-ジクロロフェニル)-1,1-ジメチル尿素、3-(3-クロロ-4-メチルフェニル)-1,1-ジメチル尿素、2,4-ビス(3,3-ジメチルウレイド)トルエン、1,1’-(4-メチル-1,3-フェニレン)ビス(3,3-ジメチル尿素)等が挙げられる。
本発明の成形材料に含有されるエポキシ樹脂組成物は、従来公知の方法で調製できる。例えば、各成分を同時に混合して調製してもよく、あらかじめ成分(A)に、成分(B)、成分(C)等を各々適宜分散させたマスターバッチを調製し、これを用いて調製してもよい。また、混練による剪断発熱等で、系内の温度が上がる場合には、混練速度を調整したり、混練釜を水冷したりする等、混練中に温度を上げない工夫をすることが好ましい。
混練装置としては、らいかい機、アトライタ、プラネタリミキサー、ディゾルバー、三本ロール、ニーダ、万能撹拌機、ホモジナイザー、ホモディスペンサー、ボールミル、ビーズミルが挙げられる。混練装置は、2種以上を併用してもよい。
本発明の成形材料に含有されるエポキシ樹脂組成物は、繊維強化複合材料の製造に用いられる中間材料である成形材料のマトリックス樹脂、特にSMC用のマトリックス樹脂およびバルクモールディングコンパウンド(以下、「BMC」とも記す。)用のマトリックス樹脂として好適である。
本発明の成形材料に含有されるエポキシ樹脂組成物は、粘度が低く含浸性が良好であることから、レジントランスファーモールディング製法の繊維強化複合材料の成形材料におけるマトリックス樹脂組成物としても用いることができる。
以上説明した、本発明の成形材料に含有されるエポキシ樹脂組成物にあっては、金型との接着性が高いエポキシ樹脂を含有しているにもかかわらず、繊維強化複合材料の金型からの脱型が容易であり、繊維強化複合材料の表面外観を損なわず、金型汚れが非常に少ない。
また、このエポキシ樹脂組成物を用いることによって、Bステージ化が容易であり、ポットライフが長く、Bステージ化後には加工性および貯蔵安定性が良好であり、かつ機械的特性および耐熱性にも優れる、成形材料を得ることができる。
本発明の成形材料に含有されるエポキシ樹脂組成物は、当該エポキシ樹脂組成物の増粘物であってもよい。すなわち、本発明の成形材料は、上述のエポキシ樹脂組成物に代えて、上述のエポキシ樹脂組成物の増粘物を含んでいてもよい。
エポキシ樹脂組成物の増粘物は、本発明の成形材料に含有されるエポキシ樹脂組成物を増粘させたもの、すなわちBステージ化したものである。
上述のエポキシ樹脂組成物を、強化繊維基材の形態に合った周知の方法によって強化繊維基材に含浸させた後、室温~80℃程度の温度に数時間~数日間、または、80~200℃程度の温度に数秒~数分保持することによって、エポキシ樹脂組成物中の成分(A)が有するエポキシ基と、成分(B)とが反応し、エポキシ樹脂組成物がBステージ化する。
成分(A)が有するエポキシ基と成分(B)との反応条件は、反応後に得られるエポキシ樹脂組成物の増粘物の23℃における粘度が後述する範囲になるよう選択することが好ましい。
エポキシ樹脂組成物の増粘物の23℃における粘度が前記範囲の下限値以上であれば、成形材料の取扱い時に表面のタックが少なくなる。エポキシ樹脂組成物の増粘物の23℃における粘度が前記範囲の上限値以下であれば、加熱圧縮成形時の流動特性が良好となる。
エポキシ樹脂組成物の増粘物の23℃における粘度は、B型粘度計を用いて測定する。
また、別の態様として、エポキシ樹脂組成物の増粘物としては、成分(A):エポキシ樹脂と、成分(B’):下記式(3)で表される部分構造を有する化合物と、成分(B):エポキシ樹脂硬化剤(ただし、成分(B’)を除く。)と、成分(C):炭素数が5~40のアルキル基を有するエステル化合物または炭素数が5~40のアルキル基を有する脂肪族アルコールの少なくとも一方である化合物とを含有するものが好ましい。
また、さらに別の態様として、エポキシ樹脂組成物の増粘物としては、成分(A1):芳香族エポキシ樹脂と、成分(A2):脂肪族エポキシ樹脂と、成分(B’):下記式(3)で表される部分構造を有する化合物と、成分(B):エポキシ樹脂硬化剤(ただし、成分(B’)を除く。)と、成分(C):炭素数が5~40のアルキル基を有するエステル化合物または炭素数が5~40のアルキル基を有する脂肪族アルコールの少なくとも一方である化合物とを含有するものが好ましい。
エポキシ樹脂の25℃における粘度は、E型粘度計を用いて測定する。
強化繊維としては、成形材料の用途や使用目的に応じて様々なものを採用することができ、炭素繊維(黒鉛繊維を含む。以下同様。)、アラミド繊維、炭化ケイ素繊維、アルミナ繊維、ボロン繊維、タングステンカーバイド繊維、ガラス繊維等が挙げられる。繊維強化複合材料の機械特性の点から、炭素繊維、ガラス繊維が好ましく、炭素繊維が特に好ましい。
成形材料中では強化繊維束の形状を保ったまま存在している場合もあれば、より少ない繊維からなる束に分かれて存在する場合もある。SMCやBMC中では、通常、より少ない束に分かれて存在する。
短繊維の長さは、0.3~10cmが好ましく、1~5cmがより好ましい。
短繊維の長さが0.3cm以上であれば、機械特性が良好な繊維強化複合材料が得られる。短繊維の長さが10cm以下であれば、加熱圧縮成形時の流動特性が良好なSMCやBMCが得られる。
SMCにおける強化繊維基材としては、チョップド強化繊維束が二次元ランダムに積み重なったシート状物がより好ましい。
本発明の成形材料であるSMCは、例えば、チョップド強化繊維束のシート状物に、上述のエポキシ樹脂組成物を十分に含浸させ、必要に応じてエポキシ樹脂組成物を増粘させることによって製造される。
例えば、下記の方法が挙げられる。
本発明の成形材料であるBMCは、例えば、チョップド強化繊維束と上述のエポキシ樹脂組成物とを十分に混合してバルク状にし、必要に応じてエポキシ樹脂組成物を増粘させることにより製造される。
加圧ニーダによる混合は、必要に応じて加熱しながら行ってもよい。加熱温度は、エポキシ樹脂が硬化を始める温度以下が好ましく、10~35℃がより好ましい。加圧ニーダによって混合する際の圧力は、大気圧以上にする必要は特にないが、エポキシ樹脂組成物の粘度が高い場合、エポキシ樹脂組成物が空気を取り込み混練され、チョップド強化繊維束へのエポキシ樹脂組成物の含浸が困難になる場合は、大気圧以上の圧力にしてもよい。
バルク状物を得た後、エポキシ樹脂組成物を増粘させることによって、BMCの表面のタックが抑制され、成形作業に適したBMCが得られる。
以上説明した本発明の成形材料にあっては、上述のエポキシ樹脂組成物またはその増粘物と、強化繊維とを含有するため、金型からの脱型性、機械特性および耐熱性に優れる繊維強化複合材料を得ることができる。
本発明の繊維強化複合材料は、本発明の成形材料の硬化物である。
本発明の繊維強化複合材料は、SMC、BMC等の成形材料を加熱成形して、本発明の成形材料に含有されるエポキシ樹脂組成物を硬化させることによって、または、本発明の成形材料に含有されるエポキシ樹脂の増粘物をさらに硬化させることによって製造される。
1枚のSMCまたは複数枚のSMCを重ねたものを、1対の金型の間にセットする。SMCを120~230℃で2~60分間加熱圧縮して、エポキシ樹脂組成物を硬化させ、成形品である繊維強化複合材料を得る。
ダンボール等のハニカム構造体を芯材とし、その両面または片面にSMCを配してもよい。
本発明の成形材料に含有されるエポキシ樹脂組成物は、室温付近の粘度が高い場合が多いことから、所定の形状の金型等にBMCを圧入した後、BMCを加熱圧縮して、エポキシ樹脂組成物を硬化させる、圧縮成形による方法を採用することによって、複雑な形状の成形品であっても短時間で製造することができる。
以上説明した本発明の繊維強化複合材料にあっては、本発明の成形材料の硬化物であるため、金型からの脱型性、機械特性および耐熱性に優れる。
本発明は、上述した各実施形態に限定されるものではなく、請求の範囲に記載された事項の範囲内で種々の変更が可能である。異なる実施形態に、上述した各実施形態に示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。
(成分(A))
jER(登録商標)827:ビスフェノールA型液状エポキシ樹脂(三菱ケミカル社製、25℃における粘度:10Pa・s)。
jER(登録商標)828:ビスフェノールA型液状エポキシ樹脂(三菱ケミカル社製、25℃における粘度:15Pa・s)。
YED216M:1,6-ヘキサンジオールジグリシジルエーテル(三菱ケミカル社製)。
jER(登録商標)630:トリグリシジル-p-アミノフェノール(三菱ケミカル社製、25℃における粘度:0.7Pa・s)。
TETRAD-X:N,N,N',N'-テトラグリシジル-m-キシリレンジアミン(三菱ガス化学社製、25℃における粘度:2.3Pa・s)
jERキュア(登録商標)113:3,3’-ジメチル-4,4’-ジアミノジシクロヘキシルメタン(三菱ケミカル社製)。
HN―2200:テトラヒドロメチル無水フタル酸(日立化成社製)。
DICYANEX1400F:ジシアンジアミド(エアープロダクツ社製)。
2MZA-PW:2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]-エチル-s-トリアジン(四国化成社製、2MZA-PW)。
成分(C)および他の内部離型剤としては、下記のものを用意した。
被験物質を装置標準のアルミニウムハーメチックパンに秤量し、装置標準のアルミニウムリッドで蓋をして試料を作製した。30℃から300℃まで10℃/分で昇温してDSC発熱曲線を得た。DSC発熱曲線上の融点に起因する最も低温側のピークにおいて、吸熱開始側におけるベースラインと変曲点の接線との交点に対応する温度を融点とした。
DICYANEX1400Fおよび2MZA-PW、ならびに成分(C)、他の内部離型剤のうちの室温で固体のものについて、それぞれjER(登録商標)827(またはjER828)と質量比1:1で混合し、三本ロールで混練し、各成分のマスターバッチを得た。
(実施例1)
表2に示す組成となるように、DICY1400Fのマスターバッチ、2MZA-PWのマスターバッチおよびエマノーン3201M-Vのマスターバッチと、jER(登録商標)827と、YED216Mとをスリーワンモーターを用いて混練してから、jERキュア(登録商標)113を所定量添加し、再度混練し、エポキシ樹脂組成物を得た。
表2~表4に示す組成となるように各成分を配合した以外は実施例1と同様にして、エポキシ樹脂組成物を得た。
表5に示す組成となるように、DICYANEX1400Fのマスターバッチ、2MZA-PWのマスターバッチおよびレオドールSP-S10Vのマスターバッチと、jER(登録商標)827と、YED216Mとをスリーワンモーターを用いて混練してから、jERキュア(登録商標)113を所定量添加し、再度混練し、エポキシ樹脂組成物を得た。
表5に示す組成となるように各成分を配合した以外は実施例13と同様にして、エポキシ樹脂組成物を得た。
表6に示す組成となるように、DICYANEX1400Fのマスターバッチ、2MZA-PWのマスターバッチおよびレオドールSP-S10Vのマスターバッチと、jER(登録商標)828と、TETRAD-Xとをスリーワンモーターを用いて混練してから、HN-2200を所定量添加し、再度混練し、エポキシ樹脂組成物を得た。
実施例1~7、13~15および比較例1~2にて得られたエポキシ樹脂組成物を用い、BMCを作製した。
BMCは、それぞれの実施例または比較例にて得られたエポキシ樹脂組成物に、フィラメント数が15000本の炭素繊維束(三菱ケミカル社製、TR50S 15L)を長さ25mmに切断したチョップド炭素繊維束を十分に混練して得た。炭素繊維の質量は、エポキシ樹脂組成物の100質量部に対して、約30質量部とした。
実施例8~12、16~23および比較例3にて得られたエポキシ樹脂組成物を、ドクターブレードを用いてポリエチレン製キャリアフィルム上に600g/m2になるように塗布した。
2枚のキャリアフィルムで、エポキシ樹脂組成物側が内側となるように、BMCの製造で用いたものと同じチョップド炭素繊維束を挟み込んだ。これをロールの間に通して押圧して、エポキシ樹脂組成物をチョップド炭素繊維束に含浸させ、SMC前駆体を得た。SMC前駆体を室温(23℃)にて168時間静置することによって、SMC前駆体中のエポキシ樹脂組成物を十分に増粘させて、チョップド炭素繊維束にエポキシ樹脂組成物が良好に含浸したSMCを得た。SMCにおける炭素繊維量は1200g/m2(SMCの100質量%中の炭素繊維の含有率は約50質量%となる。)とした。
クロムメッキ処理を施した上下一対の30cm角の平板金型を140℃まで加温し、外部離型剤(ネオス社製、フリリース65)をスプレーガンで上下金型の表面にふきつけた。前述のBMCの製造またはSMCの製造にて得られたBMCまたはSMCを2ply積層し、金型にチャージ率(金型面積に対するSMCの面積の割合)約60%でチャージして、金型温度140℃、圧力8MPaの条件で5分間加熱圧縮し、エポキシ樹脂組成物を硬化させ、厚さ約2mm、300mm角の平板状の繊維強化複合材料(CFRP成形板)を得た。
CFRP成形板を金型から取り出す際、CFRP成形板の表面に吸盤(ヤマオカエンタープライズ社製、吸盤2フィンガー)を密着させ、垂直方向に人力で引き上げて脱型した。吸盤で脱型できない場合は油圧エジェクターピンで押し上げて脱型した。下記基準にて脱型性を評価した。
結果を表2~表6に示す。
A:吸盤で容易に脱型できた。
B:吸盤で比較的容易に脱型できた。
C:吸盤で脱型できなかった。油圧エジェクターピンで脱型した。
CFRP成形板を長さ55mm、幅12.7mmに切り出し、試験片を作製した。試験片について、動的粘弾性測定装置(TAインストルメンツ社製、Q800)を用い、周波数1Hz、昇温速度5℃/分、両持ち曲げモードの測定条件で測定を行い、温度-tanδ曲線が極大値を示すときの温度をガラス転移温度(Tg)とした。Tgが高いほど耐熱性に優れ、型温における剛性が高いほど脱型性にも優れる。
結果を表2~表6に示す。
SMCで成形したCFRP成形版について、曲げ特性の評価を行った。
CFRP成形板を長さ110mm、幅25mmに切り出し、切り出した面をサンドペーパー#1200で処理し、試験片を作製した。試験片について、万能試験機(Instron社製、Instron(登録商標)4465)および解析ソフトBluehillを用い、温度23℃、湿度50%RHの環境下、3点曲げ治具で曲げ試験を行い、曲げ強度(MPa)および曲げ弾性率(GPa)を算出した。
計12本の試験片を用いて測定を行い、その平均値を採用した。
測定条件を以下に示す。
Dは試験片の厚さ、Lはサポート間距離である。
結果を表3~表6に示す。
測定条件:圧子R=3.2、サポートR=1.6、サポート間距離L[mm]=40×D、クロスヘッド速度[mm/分]=0.01×L×L/6/D。
実施例13~23のCFRP成形版について、CFRP成形板の外観を下記基準にて評価した。
結果を表5~表6に示す。
A:成形板の外観に内部離形剤などのブリードが全く見られず、外観が優れていた。
B:成形板の外観に内部離型剤が少量ブリードし、外観不良が生じた。
C:成形板の外観に内部離型剤が多量にブリードし、外観不良が生じた。
実施例13~23のCFRP成形版について、CFRP成形板を金型から取り出した後の金型表面の汚れを下記基準にて評価した。
結果を表5~表6に示す。
A:連続で成形しても金型に汚れがほとんど転写されていなかった。
B:金型に汚れが若干転写され、連続で成形すると金型汚れが増加した。
C:一度の成形で金型が汚れた。
本発明の成形材料に含有されるエポキシ樹脂組成物をマトリックス樹脂とするSMCは、エポキシ樹脂特有の耐衝撃性、耐熱性に優れ、かつ高い曲げ強度および曲げ弾性率を有するため、工業用、自動車用の構造部品の原料として好適に使用される。
Claims (14)
- 成分(A):エポキシ樹脂と、
成分(B):エポキシ樹脂硬化剤と、
成分(C):溶解度パラメータが11.2以下であり、融点が115℃以下である化合物と、
強化繊維とを含有する、成形材料。 - 成分(C)として含有される化合物の少なくとも一種が、脂肪酸と脂肪族アルコールとのエステル化合物、多価カルボン酸と脂肪族アルコールとのエステル化合物、多価アルコールと脂肪酸とのエステル化合物、脂肪族アルコール、脂肪酸アミド、および、脂肪酸の金属塩から選ばれる化合物である、請求項1に記載の成形材料。
- 成分(C)として含有される化合物の少なくとも一種が、溶解度パラメータが8.0~9.6、または、10.3~10.9の範囲の化合物である、請求項1または2に記載の成形材料。
- 成分(C)として含有される化合物の少なくとも一種が、融点が-30℃以上の化合物である、請求項1~3のいずれか一項に記載の成形材料。
- 成分(A):エポキシ樹脂と、
成分(B):エポキシ樹脂硬化剤と、
成分(C):炭素数が5~40のアルキル基を有するエステル化合物または炭素数が5~40のアルキル基を有する脂肪族アルコールの少なくとも一方である化合物と、
強化繊維とを含有する、成形材料。 - 前記成分(C)として含有される化合物の少なくとも一種が、水酸基を有する脂肪族化合物である、請求項5に記載の成形材料。
- 前記成分(C)として含有される化合物の少なくとも一種が、ソルビタン脂肪酸エステルである、請求項6に記載の成形材料。
- 前記成分(C)として含有される化合物の少なくとも一種が、ソルビタンモノステアレートである、請求項7に記載の成形材料。
- 前記成分(B)として含有されるエポキシ樹脂硬化剤の少なくとも一種が、ポリアミン系化合物または酸無水物系化合物の少なくとも一方である、請求項1~8のいずれか一項に記載の成形材料。
- 前記成分(B)として含有されるエポキシ樹脂硬化剤の少なくとも一種が、脂環式ジアミンである、請求項1~9のいずれか一項に記載の成形材料。
- 前記成分(B)として含有されるエポキシ樹脂硬化剤の少なくとも一種が、ジシアンジアミドである、請求項1~10のいずれか一項に記載の成形材料。
- 前記強化繊維が、炭素繊維である、請求項1~11のいずれか一項に記載の成形材料。
- シートモールディングコンパウンドである、請求項1~12のいずれか一項に記載の成形材料。
- 請求項1~13のいずれか一項に記載の成形材料の硬化物である、繊維強化複合材料。
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020066746A1 (ja) * | 2018-09-25 | 2020-04-02 | 日鉄ケミカル&マテリアル株式会社 | 繊維強化複合材料用樹脂組成物及びそれを用いた繊維強化複合材料 |
WO2020071170A1 (ja) * | 2018-10-01 | 2020-04-09 | 三菱ケミカル株式会社 | 成形材料、繊維強化複合材料、及び繊維強化複合材料の製造方法 |
JPWO2019176568A1 (ja) * | 2018-03-16 | 2020-04-16 | 三菱ケミカル株式会社 | シートモールディングコンパウンド及び炭素繊維複合材料成形品 |
WO2020196600A1 (ja) * | 2019-03-28 | 2020-10-01 | 東レ株式会社 | 炭素繊維強化複合材料の成形品およびその製造方法 |
WO2020250957A1 (ja) * | 2019-06-14 | 2020-12-17 | Dic株式会社 | エポキシ樹脂組成物、硬化物、繊維強化複合材料、プリプレグ及びトウプリプレグ |
WO2022054747A1 (ja) | 2020-09-11 | 2022-03-17 | 東レ株式会社 | エポキシ樹脂組成物、成形材料および繊維強化複合材料 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2971016T3 (es) * | 2018-09-05 | 2024-06-03 | Mitsubishi Chem Corp | Compuesto para el moldeo de láminas y material compuesto reforzado con fibra |
WO2022085707A1 (ja) * | 2020-10-22 | 2022-04-28 | 三菱ケミカル株式会社 | 電着塗装品の製造方法、プリプレグおよびエポキシ樹脂組成物 |
Citations (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59149923A (ja) * | 1983-02-16 | 1984-08-28 | Hitachi Ltd | 耐熱性成形組成物 |
JPS6143619A (ja) * | 1984-08-07 | 1986-03-03 | Mitsubishi Rayon Co Ltd | エポキシ樹脂組成物 |
JPH02133947A (ja) * | 1988-11-14 | 1990-05-23 | Nitto Denko Corp | 半導体装置 |
JPH0338330A (ja) * | 1989-07-05 | 1991-02-19 | Hitachi Chem Co Ltd | エポキシ樹脂積層板の製造方法 |
JPH03157449A (ja) * | 1989-11-16 | 1991-07-05 | Sumitomo Bakelite Co Ltd | 樹脂組成物 |
JPH05329976A (ja) * | 1992-05-27 | 1993-12-14 | Nippon Oil Co Ltd | 複合材料およびその製造方法 |
JPH06166742A (ja) | 1992-12-02 | 1994-06-14 | Sumitomo Chem Co Ltd | エポキシ樹脂組成物 |
JPH08157695A (ja) | 1994-12-02 | 1996-06-18 | Shin Etsu Chem Co Ltd | 半導体封止用エポキシ樹脂組成物及び半導体装置 |
JP2001072783A (ja) * | 1999-09-08 | 2001-03-21 | Toray Ind Inc | プリプレグの製造方法 |
JP2003026904A (ja) * | 2001-07-11 | 2003-01-29 | Polyplastics Co | 難燃性樹脂組成物およびその成形品 |
JP2003073528A (ja) * | 2001-09-03 | 2003-03-12 | Sumitomo Bakelite Co Ltd | エポキシ樹脂組成物及び半導体装置 |
JP2003192747A (ja) * | 2001-12-26 | 2003-07-09 | Dainippon Ink & Chem Inc | 樹脂組成物、それを用いた成形材料および成形品 |
JP2005015693A (ja) * | 2003-06-27 | 2005-01-20 | Shin Etsu Chem Co Ltd | エポキシ樹脂組成物および半導体装置 |
JP2006016446A (ja) * | 2004-06-30 | 2006-01-19 | Toray Ind Inc | 樹脂組成物ならびにそれからなる成形品 |
US7169462B1 (en) * | 2004-03-01 | 2007-01-30 | Laticrete International, Inc. | Waterproofing membrane |
JP2008189833A (ja) * | 2007-02-06 | 2008-08-21 | Shin Etsu Chem Co Ltd | 熱硬化性エポキシ樹脂組成物及び半導体装置 |
JP2009019099A (ja) * | 2007-07-11 | 2009-01-29 | Showa Highpolymer Co Ltd | 繊維強化複合材料用樹脂組成物、それを用いた成形材料及び繊維強化複合材料 |
JP2011006508A (ja) * | 2009-06-23 | 2011-01-13 | Tosoh Corp | 重合体の製造方法 |
JP2012092168A (ja) * | 2010-10-25 | 2012-05-17 | Panasonic Corp | 絶縁樹脂組成物、樹脂ワニス、プリプレグ、金属張積層板、及びプリント配線板 |
JP2012167225A (ja) * | 2011-02-16 | 2012-09-06 | Shin-Etsu Chemical Co Ltd | 熱硬化性エポキシ樹脂組成物、光半導体装置用反射部材及び光半導体装置 |
JP2013127132A (ja) * | 2011-12-19 | 2013-06-27 | Toray Ind Inc | サイジング剤塗布炭素繊維 |
WO2014189101A1 (ja) * | 2013-05-24 | 2014-11-27 | 株式会社ダイセル | 繊維強化複合材料用組成物、プリプレグ、及び繊維強化複合材料 |
JP2015151457A (ja) * | 2014-02-14 | 2015-08-24 | 住友ベークライト株式会社 | 液状エポキシ樹脂組成物及び液状エポキシ樹脂成形材料 |
JP2015166457A (ja) * | 2015-03-13 | 2015-09-24 | セイコーエプソン株式会社 | 成膜用インク、成膜方法、液滴吐出装置、膜付きデバイスおよび電子機器 |
JP2016180071A (ja) * | 2015-03-25 | 2016-10-13 | 信越化学工業株式会社 | Ledリフレクター用白色熱硬化性エポキシ樹脂組成物 |
WO2016182077A1 (ja) * | 2015-05-13 | 2016-11-17 | 三菱レイヨン株式会社 | シートモールディングコンパウンド及び繊維強化複合材料 |
JP2017071708A (ja) * | 2015-10-08 | 2017-04-13 | 信越化学工業株式会社 | 熱硬化性エポキシ樹脂組成物及び光半導体装置 |
JP2017103062A (ja) | 2015-11-30 | 2017-06-08 | 東芝ライテック株式会社 | 照明制御スイッチ |
JP2017145253A (ja) | 2012-12-28 | 2017-08-24 | ベーリンガー インゲルハイム フェトメディカ ゲーエムベーハーBoehringer Ingelheim Vetmedica GmbH | マイコプラズマワクチン作製方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3587776T2 (de) | 1984-08-07 | 1994-07-21 | Mitsubishi Rayon Co | Zwischenprodukt für Verbundstoffe. |
WO2001081445A1 (fr) * | 2000-04-21 | 2001-11-01 | Mitsubishi Rayon Co., Ltd. | Composition de resine epoxy et preimpregne fabrique avec cette composition de resine epoxy |
JP2002088229A (ja) * | 2000-09-18 | 2002-03-27 | Asahi Denka Kogyo Kk | 水性樹脂組成物 |
US20080255283A1 (en) | 2007-02-06 | 2008-10-16 | Takayuki Aoki | Thermosetting epoxy resin composition and semiconductor device |
EP2085426B1 (de) * | 2008-01-30 | 2010-10-13 | Sika Technology AG | Auswaschbeständige hitzehärtende Epoxidharzklebstoffe |
WO2011048765A1 (ja) * | 2009-10-20 | 2011-04-28 | 住友ベークライト株式会社 | 半導体封止用エポキシ樹脂組成物、半導体装置及び離型剤 |
JP5976269B2 (ja) * | 2010-08-26 | 2016-08-23 | セイコーエプソン株式会社 | 成膜用インク、成膜方法 |
US9234312B2 (en) * | 2012-03-29 | 2016-01-12 | Matsumoto Yushi-Seiyaku Co., Ltd. | Sizing agent for reinforcement fibers, and application thereof |
JP2014106491A (ja) * | 2012-11-29 | 2014-06-09 | Kyocera Document Solutions Inc | 静電荷像現像用トナー |
JP6396128B2 (ja) * | 2014-09-04 | 2018-09-26 | 旭化成株式会社 | 繊維強化用樹脂組成物、硬化物、プリプレグ、及び繊維強化プラスチック |
CN105419246A (zh) * | 2016-01-18 | 2016-03-23 | 苏州法斯特信息科技有限公司 | 一种陶瓷成型用高耐磨塑质模具材料的制备方法 |
JP2017203107A (ja) * | 2016-05-11 | 2017-11-16 | 三菱ケミカル株式会社 | 成形材料および繊維強化複合材料 |
CN106398119B (zh) * | 2016-08-31 | 2018-11-09 | 四川国能高科生物树脂有限公司 | 一种纤维增强的生物树脂胶复合材料及其制备方法 |
-
2018
- 2018-05-14 CN CN201880033455.XA patent/CN110650989B/zh active Active
- 2018-05-14 EP EP18806851.4A patent/EP3632982A1/en active Pending
- 2018-05-14 WO PCT/JP2018/018491 patent/WO2018216524A1/ja active Application Filing
- 2018-05-14 JP JP2018528074A patent/JP6828745B2/ja active Active
-
2019
- 2019-11-19 US US16/688,716 patent/US11104793B2/en active Active
Patent Citations (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59149923A (ja) * | 1983-02-16 | 1984-08-28 | Hitachi Ltd | 耐熱性成形組成物 |
JPS6143619A (ja) * | 1984-08-07 | 1986-03-03 | Mitsubishi Rayon Co Ltd | エポキシ樹脂組成物 |
JPH02133947A (ja) * | 1988-11-14 | 1990-05-23 | Nitto Denko Corp | 半導体装置 |
JPH0338330A (ja) * | 1989-07-05 | 1991-02-19 | Hitachi Chem Co Ltd | エポキシ樹脂積層板の製造方法 |
JPH03157449A (ja) * | 1989-11-16 | 1991-07-05 | Sumitomo Bakelite Co Ltd | 樹脂組成物 |
JPH05329976A (ja) * | 1992-05-27 | 1993-12-14 | Nippon Oil Co Ltd | 複合材料およびその製造方法 |
JPH06166742A (ja) | 1992-12-02 | 1994-06-14 | Sumitomo Chem Co Ltd | エポキシ樹脂組成物 |
JPH08157695A (ja) | 1994-12-02 | 1996-06-18 | Shin Etsu Chem Co Ltd | 半導体封止用エポキシ樹脂組成物及び半導体装置 |
JP2001072783A (ja) * | 1999-09-08 | 2001-03-21 | Toray Ind Inc | プリプレグの製造方法 |
JP2003026904A (ja) * | 2001-07-11 | 2003-01-29 | Polyplastics Co | 難燃性樹脂組成物およびその成形品 |
JP2003073528A (ja) * | 2001-09-03 | 2003-03-12 | Sumitomo Bakelite Co Ltd | エポキシ樹脂組成物及び半導体装置 |
JP2003192747A (ja) * | 2001-12-26 | 2003-07-09 | Dainippon Ink & Chem Inc | 樹脂組成物、それを用いた成形材料および成形品 |
JP2005015693A (ja) * | 2003-06-27 | 2005-01-20 | Shin Etsu Chem Co Ltd | エポキシ樹脂組成物および半導体装置 |
US7169462B1 (en) * | 2004-03-01 | 2007-01-30 | Laticrete International, Inc. | Waterproofing membrane |
JP2006016446A (ja) * | 2004-06-30 | 2006-01-19 | Toray Ind Inc | 樹脂組成物ならびにそれからなる成形品 |
JP2008189833A (ja) * | 2007-02-06 | 2008-08-21 | Shin Etsu Chem Co Ltd | 熱硬化性エポキシ樹脂組成物及び半導体装置 |
JP2009019099A (ja) * | 2007-07-11 | 2009-01-29 | Showa Highpolymer Co Ltd | 繊維強化複合材料用樹脂組成物、それを用いた成形材料及び繊維強化複合材料 |
JP2011006508A (ja) * | 2009-06-23 | 2011-01-13 | Tosoh Corp | 重合体の製造方法 |
JP2012092168A (ja) * | 2010-10-25 | 2012-05-17 | Panasonic Corp | 絶縁樹脂組成物、樹脂ワニス、プリプレグ、金属張積層板、及びプリント配線板 |
JP2012167225A (ja) * | 2011-02-16 | 2012-09-06 | Shin-Etsu Chemical Co Ltd | 熱硬化性エポキシ樹脂組成物、光半導体装置用反射部材及び光半導体装置 |
JP2013127132A (ja) * | 2011-12-19 | 2013-06-27 | Toray Ind Inc | サイジング剤塗布炭素繊維 |
JP2017145253A (ja) | 2012-12-28 | 2017-08-24 | ベーリンガー インゲルハイム フェトメディカ ゲーエムベーハーBoehringer Ingelheim Vetmedica GmbH | マイコプラズマワクチン作製方法 |
WO2014189101A1 (ja) * | 2013-05-24 | 2014-11-27 | 株式会社ダイセル | 繊維強化複合材料用組成物、プリプレグ、及び繊維強化複合材料 |
JP2015151457A (ja) * | 2014-02-14 | 2015-08-24 | 住友ベークライト株式会社 | 液状エポキシ樹脂組成物及び液状エポキシ樹脂成形材料 |
JP2015166457A (ja) * | 2015-03-13 | 2015-09-24 | セイコーエプソン株式会社 | 成膜用インク、成膜方法、液滴吐出装置、膜付きデバイスおよび電子機器 |
JP2016180071A (ja) * | 2015-03-25 | 2016-10-13 | 信越化学工業株式会社 | Ledリフレクター用白色熱硬化性エポキシ樹脂組成物 |
WO2016182077A1 (ja) * | 2015-05-13 | 2016-11-17 | 三菱レイヨン株式会社 | シートモールディングコンパウンド及び繊維強化複合材料 |
JP2017071708A (ja) * | 2015-10-08 | 2017-04-13 | 信越化学工業株式会社 | 熱硬化性エポキシ樹脂組成物及び光半導体装置 |
JP2017103062A (ja) | 2015-11-30 | 2017-06-08 | 東芝ライテック株式会社 | 照明制御スイッチ |
Non-Patent Citations (2)
Title |
---|
R. F. FEDORS, POLYM. ENG. SCI., vol. 14, no. 2, 1974, pages 147 - 154 |
See also references of EP3632982A4 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2019176568A1 (ja) * | 2018-03-16 | 2020-04-16 | 三菱ケミカル株式会社 | シートモールディングコンパウンド及び炭素繊維複合材料成形品 |
WO2020066746A1 (ja) * | 2018-09-25 | 2020-04-02 | 日鉄ケミカル&マテリアル株式会社 | 繊維強化複合材料用樹脂組成物及びそれを用いた繊維強化複合材料 |
WO2020071170A1 (ja) * | 2018-10-01 | 2020-04-09 | 三菱ケミカル株式会社 | 成形材料、繊維強化複合材料、及び繊維強化複合材料の製造方法 |
WO2020196600A1 (ja) * | 2019-03-28 | 2020-10-01 | 東レ株式会社 | 炭素繊維強化複合材料の成形品およびその製造方法 |
US11993688B2 (en) | 2019-03-28 | 2024-05-28 | Toray Industries, Inc. | Molded article of carbon fiber composite material and production method for molded article of carbon fiber composite material |
WO2020250957A1 (ja) * | 2019-06-14 | 2020-12-17 | Dic株式会社 | エポキシ樹脂組成物、硬化物、繊維強化複合材料、プリプレグ及びトウプリプレグ |
JP6825757B1 (ja) * | 2019-06-14 | 2021-02-03 | Dic株式会社 | エポキシ樹脂組成物、硬化物、繊維強化複合材料、プリプレグ及びトウプリプレグ |
CN113874441A (zh) * | 2019-06-14 | 2021-12-31 | Dic株式会社 | 环氧树脂组合物、固化物、纤维增强复合材料、预浸料及丝束预浸料 |
WO2022054747A1 (ja) | 2020-09-11 | 2022-03-17 | 東レ株式会社 | エポキシ樹脂組成物、成形材料および繊維強化複合材料 |
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