WO2010109957A1 - エポキシ樹脂組成物、プリプレグ、炭素繊維強化複合材料および電子電気部品筐体 - Google Patents
エポキシ樹脂組成物、プリプレグ、炭素繊維強化複合材料および電子電気部品筐体 Download PDFInfo
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- WO2010109957A1 WO2010109957A1 PCT/JP2010/051589 JP2010051589W WO2010109957A1 WO 2010109957 A1 WO2010109957 A1 WO 2010109957A1 JP 2010051589 W JP2010051589 W JP 2010051589W WO 2010109957 A1 WO2010109957 A1 WO 2010109957A1
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- Prior art keywords
- epoxy resin
- composite material
- carbon fiber
- fiber reinforced
- reinforced composite
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- LTURHSAEWJPFAA-UHFFFAOYSA-N sulfuric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OS(O)(=O)=O.NC1=NC(N)=NC(N)=N1 LTURHSAEWJPFAA-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- QEEHNBQLHFJCOV-UHFFFAOYSA-N tris(2-phenylphenyl) phosphate Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1OP(OC=1C(=CC=CC=1)C=1C=CC=CC=1)(=O)OC1=CC=CC=C1C1=CC=CC=C1 QEEHNBQLHFJCOV-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 238000002137 ultrasound extraction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- BHTBHKFULNTCHQ-UHFFFAOYSA-H zinc;tin(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Sn+4] BHTBHKFULNTCHQ-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J5/24—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/04—Epoxynovolacs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
Definitions
- the present invention relates to an epoxy resin composition suitable as a matrix resin for a carbon fiber reinforced composite material. More specifically, an epoxy resin composition capable of providing a carbon fiber reinforced composite material excellent in flame retardancy, curability and mechanical properties, a prepreg composed of the epoxy resin composition and carbon fiber, and obtained by curing the prepreg.
- the present invention relates to a carbon fiber reinforced composite material, and an electronic / electrical component casing using the carbon fiber reinforced composite material.
- Fiber reinforced composite materials using epoxy resins and other thermosetting resins as matrix resins are used for golf clubs, tennis rackets, fishing rods, etc. due to their light weight and excellent mechanical properties. It is used in a wide range of fields, including sports fields, structural materials such as aircraft and vehicles, and reinforcement of concrete structures. In recent years, not only excellent mechanical properties, but also carbon fibers have electrical conductivity, and the composite material has excellent electromagnetic wave shielding properties, so it can also be used in the case of electronic and electrical equipment such as laptop computers and video cameras. Used for thinning the housing and reducing the mass of equipment.
- Such a carbon fiber reinforced composite material is often obtained by laminating a prepreg obtained by impregnating a carbon fiber with a thermosetting resin, followed by heating and pressing.
- the materials are required to have flame resistance so that the materials do not ignite and burn due to fire.
- the materials are required to have flame resistance so that the materials do not ignite and burn due to fire.
- it is required to make the material flame-retardant.
- a compound having a halogen represented by bromine in the molecule has been widely used for flame retardancy of carbon fiber reinforced composite materials.
- a flame retardant epoxy resin composition using antimony trioxide as a flame retardant in addition to brominated epoxy resin or brominated epoxy resin can be mentioned.
- the resin composition containing halogen as described above and its cured product may generate harmful substances such as hydrogen halide during combustion, and may adversely affect the human body and natural environment. Development of an epoxy resin composition exhibiting excellent flame retardancy even without containing is underway.
- Patent Document 1 As a flame-retarding technique for an epoxy resin composition that does not contain a halogen, a technique of a matrix resin for a carbon fiber reinforced composite material composed of red phosphorus and a phosphate ester is disclosed (for example, Patent Document 1). This technique does not generate halogen gas and can provide flame retardancy. However, since red phosphorus has a red coloration due to the compounding of red phosphorus, it takes more time to clean the equipment and equipment in the manufacturing process than the resin without red coloration in the epoxy resin preparation and prepreg process. In housing applications, there is a problem that the color tone of the product surface of the carbon fiber reinforced composite material is limited.
- Phosphoric acid esters have a low phosphorus content in the compound as compared to red phosphorus, and a large amount of blending is required to ensure sufficient flame retardancy, resulting in a problem of reduced curability and heat resistance.
- a flame-retarding technique using a phenol novolac type epoxy resin and a phosphoric acid ester is disclosed for use as a laminate (for example, Patent Document 2).
- Patent Document 2 a flame-retarding technique using a phenol novolac type epoxy resin and a phosphoric acid ester is disclosed for use as a laminate.
- this technique has a problem that not only the heat resistance and flexibility of the epoxy resin are lowered, but also the productivity is poor because the curing speed is delayed and a long time is required for curing.
- Patent Document 3 a technique for maintaining a balance between flame retardancy and moisture resistance by using a phosphate ester and a phosphazene compound in combination as a sealing material is disclosed (for example, Patent Document 3).
- Patent Document 3 a technique for maintaining a balance between flame retardancy and moisture resistance by using a phosphate ester and a phosphazene compound in combination as a sealing material.
- An object of the present invention is to provide a carbon fiber reinforced composite material that solves the problems in the prior art described above, has high flame retardancy, and is excellent in fast curability, heat resistance, and mechanical properties.
- An object of the present invention is to provide an epoxy resin composition, a prepreg, and a carbon fiber reinforced composite material suitable for manufacturing a fiber reinforced composite material, and an electronic / electrical component casing.
- the epoxy resin composition of the present invention has the following configuration in order to achieve the above object. That is, the following component [A] an epoxy resin containing 50% by mass or more of a compound represented by the following formula (I), [B] an organic nitrogen compound curing agent, [C] a phosphate ester, and [D] a phosphazene compound. It is an epoxy resin composition characterized by including.
- the epoxy resin composition includes a phenoxy resin.
- a preferred embodiment of the prepreg of the present invention is obtained by impregnating carbon fiber with the epoxy resin composition of the present invention.
- a preferred embodiment of the carbon fiber reinforced composite material of the present invention is obtained by curing the epoxy resin composition constituting the prepreg of the present invention.
- a preferred embodiment of the carbon fiber reinforced composite material of the present invention uses a prepreg made of an epoxy resin composition having a phosphorus atom content of 1.2 to 4% by mass contained in the entire epoxy resin composition, and has a thickness of 2 mm.
- the flame retardancy in the UL94 test is V-1 or higher.
- a preferred method for producing the carbon fiber reinforced composite material of the present invention is obtained by curing the prepreg of the present invention by a press molding method.
- the electronic / electrical component casing of the present invention is made of the carbon fiber reinforced composite material.
- the epoxy resin composition of the present invention has excellent rapid curability, heat resistance and mechanical properties, and is obtained by curing a prepreg containing the epoxy resin composition and carbon fibers. Since the fiber reinforced composite material has excellent flame retardancy, heat resistance and mechanical properties, the fiber reinforced composite material can be suitably used for materials that are required to have flame retardancy, particularly for electronic and electronic component housings.
- the epoxy resin composition of the present invention includes a component [A] that is an epoxy resin containing 50% by mass or more of a compound having a structure represented by the formula (I), and a component [B] that is an organic nitrogen compound curing agent. And component [C] which is a phosphate ester and component [D] which is a phosphazene compound.
- Component [A] in the present invention is an epoxy resin containing 50 mass% or more of an epoxy resin represented by the following formula (I) in all epoxy resins.
- the carbon fiber reinforced composite material which imparts excellent rapid curability and heat resistance to the epoxy resin composition and is heat cured by combining the epoxy resin composition with carbon fiber, has high flame retardancy, and Heat resistance can be imparted.
- the compound represented by the formula (I) in the present invention include a phenol novolac type epoxy resin and a cresol novolac type epoxy resin, and include cases where these epoxy resins are used alone or in combination of two or more.
- phenol novolac type epoxy resins include “jER (registered trademark)” 152, “jER (registered trademark)” 154 (manufactured by Japan Epoxy Resin Co., Ltd.), and “Epicron (registered trademark)” N-740.
- cresol novolac type epoxy resin Commercial products of cresol novolac type epoxy resin include “jER (registered trademark)” 180S (manufactured by Japan Epoxy Resin Co., Ltd.), “Epicron (registered trademark)” N-660, and “Epicron (registered trademark)” N-665.
- the compound represented by the formula (I) contained in the component [A] in the present invention among the above epoxy resins, the methyl group contained in the cresol novolac type epoxy resin is easy to burn, so that the flame retardancy point Thus, a phenol novolac type epoxy resin is preferable.
- the content of the compound represented by the formula (I) is 50% by mass or more in the component [A], more preferably 55% by mass or more, and further preferably 60% by mass or more.
- the resulting epoxy resin composition is excellent in fast curability and heat resistance, and the obtained carbon fiber reinforced composite material is described later.
- the content of the compound represented by the formula (I) is preferably high from the viewpoints of flame retardancy, fast curability and heat resistance, but generally used epoxy resins have a molecular weight distribution, so the upper limit is usually 95 mass. %.
- n in the formula (I) is not specified as long as it is an integer of 1 or more, but high flame retardancy, fast curability and heat resistance are obtained as the compounding amount of a compound having a larger n is increased.
- the content of the compound having n of 2 or more is preferably 80% by mass or more, more preferably 90% by mass or more in the compound represented by the formula (I).
- the component [A] in the present invention contains 50% by mass or more of the compound having a structure represented by the formula (I), and from the viewpoint of tackiness and draping properties of the prepreg, the following formula (II) It is preferable that the epoxy resin represented by these is included.
- R 4, R 5, R 6, R 7 represents a hydrogen atom or a methyl group.
- the content of the compound represented by formula (I) is high, and among them, the content of the compound having n of 2 or more is preferably high.
- the value of n increases, the molecular weight of the compound increases, and when n is 2 or more, it is often solid at room temperature, so that suitable tackiness and draping properties can be obtained when used as a prepreg. It may not be possible.
- the epoxy resin represented by the formula (II) by adding a predetermined amount of the epoxy resin represented by the formula (II), it is possible to impart tackiness and draping properties suitable for the prepreg in addition to flame retardancy, fast curability and heat resistance.
- the epoxy resin containing the epoxy resin represented by the formula (II) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolac type epoxy resin.
- bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferably used because of the high content of the epoxy resin represented by the formula (II).
- a liquid epoxy resin is preferably used at a temperature of 25 ° C. because it provides suitable prepreg handling properties.
- being liquid at a temperature of 25 ° C. means an epoxy resin having a glass transition temperature or a melting point of 25 ° C. or lower and exhibiting fluidity at a temperature of 25 ° C.
- the glass transition temperature is the midpoint temperature determined based on JIS K7121 (1987) using a differential scanning calorimeter (DSC), and the melting point of the crystalline thermosetting resin is determined according to JIS K7121 (1987). It is the melting peak temperature obtained based on this.
- component [A] in the present invention when used for applications such as housings, among bisphenol A type epoxy resins and bisphenol F type epoxy resins, the rigidity of the carbon fiber reinforced composite material is improved due to its high elastic modulus. Therefore, a bisphenol F type epoxy resin is preferable.
- the content of the compound represented by the formula (II) is preferably 15 to 40% by mass, more preferably 15 to 35% by mass in the component [A].
- the epoxy resin [A] in the present invention may contain an epoxy resin other than the above epoxy resin.
- Epoxy resins made from phenols include bisphenol S type epoxy resin, bisphenol AD type epoxy resin, epoxy resin having biphenyl skeleton, resorcinol type epoxy resin, epoxy resin having naphthalene skeleton, trisphenylmethane type epoxy resin, phenol Examples thereof include glycidyl ether type epoxy resins such as aralkyl type epoxy resins, dicyclopentadiene type epoxy resins and diphenylfluorene type epoxy resins, and various isomers and alkyl-substituted products thereof.
- epoxy resins such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, Also included in this type are epoxy resins obtained by modifying epoxy resins made from phenols with urethane or isocyanate.
- epoxy resins made from amines include N, N, O-triglycidyl-m-aminophenol, N, N, O-triglycidyl-p-aminophenol, N, N, O-triglycidyl-4- Amino-3-methylphenol, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, N, N, N ′, N′-tetraglycidyl-4,4′-methylenedianiline, N, N , N ′, N′-tetraglycidyl-2,2′-diethyl-4,4′-methylenedianiline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis Examples thereof include glycidylamine type epoxy resins such as (diglycidylaminomethyl) cyclohexane.
- Examples of the epoxy resin using carboxylic acid as a raw material include glycidyl ester type epoxy resins such as phthalic acid diglycidyl ester and terephthalic acid diglycidyl ester.
- Examples of the epoxy resin made from a compound having an intramolecular unsaturated carbon bond include vinylcyclohexene diepoxide, 3,4-epoxycyclohexanecarboxylic acid-3,4-epoxycyclohexylmethyl, and bis-3,4-epoxycyclohexyl adipate.
- Examples include alicyclic epoxy resins such as methyl.
- Component [B] in the present invention is an organic nitrogen compound curing agent.
- the organic nitrogen compound curing agent contains a nitrogen atom in the molecule as at least one functional group selected from the group consisting of an amino group, an amide group, an imidazole group, a urea group, and a hydrazide group, and cures an epoxy resin.
- a compound that can examples include aromatic amines, aliphatic amines, tertiary amines, secondary amines, imidazoles, urea derivatives, carboxylic acid hydrazides, Lewis acid complexes of the above nitrogen compounds, dicyandiamide, tetramethylguanidine.
- aromatic amines examples include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, and the like.
- aliphatic amines include diethylenetriamine, triethylenetetramine, isophoronediamine, bis (aminomethyl) norbornane, bis (4-aminocyclohexyl) methane, dimer acid ester of polyethyleneimine, and the like.
- Modified amines obtained by reacting an amine having active hydrogen such as a group amine with a compound such as an epoxy compound, acrylonitrile, phenol and formaldehyde, thiourea are also included.
- Tertiary amines include N, N-dimethylpiperazine, N, N-dimethylaniline, triethylenediamine, N, N-dimethylbenzylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylamino). And methyl) phenol.
- Examples of secondary amines include piperidine.
- Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl.
- carboxylic acid hydrazide examples include adipic acid hydrazide and naphthalenecarboxylic acid hydrazide.
- urea derivative examples include 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), 3- (3-chloro-4-methylphenyl) -1 1,4-dimethylurea, 4,4′-methylenebis (diphenyldimethylurea), 2,4-toluenebis (3,3-dimethylurea) and the like.
- Lewis acid complexes of nitrogen compounds include boron trifluoride / piperidine complex, boron trifluoride / monoethylamine complex, boron trifluoride / triethanolamine complex, boron trichloride / octylamine complex, and the like.
- the organic nitrogen compound curing agent [B] in the present invention is for stability in the resin preparation process, storage stability at room temperature, or stability against thermal history received in the process of impregnating the carbon fiber with the epoxy resin composition. It is preferable to have a thermal activation type latency.
- the thermal activation type potential means a property in which it is in a state of low activity as it is, but undergoes a phase change or chemical change by receiving a certain thermal history and changes to a state of high activity. .
- dicyandiamide is preferably used as the organic nitrogen compound curing agent [B] in the present invention.
- Dicyandiamide is a solid curing agent at room temperature and hardly dissolves in an epoxy resin at 25 ° C., but dissolves when heated to 100 ° C. or more and reacts with an epoxy group. That is, it is a latent curing agent having the characteristics of being insoluble at low temperatures and soluble at high temperatures.
- the latent curing agent an amine duct type latent curing agent and a microcapsule type latent curing agent are also preferably used.
- the amine duct type latent curing agent is obtained by reacting an active ingredient such as a compound having a primary, secondary or tertiary amino group, or various imidazole compounds with a compound capable of reacting with those compounds. This refers to a polymer having a high molecular weight and insolubilized at the storage temperature.
- the microcapsule type latent curing agent has a curing agent as a core, and this is coated with a polymer substance such as epoxy resin, polyurethane resin, polystyrene, polyimide, or cyclodextrin as a shell to form an epoxy resin and a curing agent. This is one that reduces contact.
- a polymer substance such as epoxy resin, polyurethane resin, polystyrene, polyimide, or cyclodextrin as a shell to form an epoxy resin and a curing agent. This is one that reduces contact.
- amine duct type latent curing agents include “Amicure (registered trademark)” PN-23, PN-H, PN-31, PN-40, PN-50, PN-F, MY-24, MY- H (above, manufactured by Ajinomoto Fine Techno Co., Ltd.), “ADEKA HARDNER (registered trademark)” EH-3293S, EH-3615S, EH-4070S (above, manufactured by ADEKA Corporation), and the like.
- the blending amount of the component [B] in the present invention is 0.6 to 1.4 equivalents based on the active hydrogen equivalents of all epoxy groups in the epoxy resin composition from the viewpoint of heat resistance and mechanical properties. preferable.
- the blending amount depends on the type of organic nitrogen compound curing agent to be used. For example, when dicyandiamide is used, it is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the total epoxy resin. More preferably, it is 1 to 10 parts by mass.
- the component [B] in the present invention may be used alone or in combination, and in addition to the component [B], an appropriate curing accelerator can be combined in order to enhance the curing activity.
- an appropriate curing accelerator can be combined in order to enhance the curing activity.
- dicyandiamide can be suitably used in combination with a urea derivative or an imidazole.
- Dicyandiamide alone requires about 170 to 180 ° C. for curing, whereas an epoxy resin composition using such a combination can be cured at 80 to 150 ° C.
- aromatic amines such as 4,4′-diaminodiphenylsulfone and 3,3′-diaminodiphenylsulfone include boron trifluoride / monoethylamine complex, boron trichloride / A Lewis acid such as an octylamine complex can be suitably used in combination.
- an amine duct type latent curing agent such as “Amicure (registered trademark)” PN-23 can be suitably used in combination with a carboxylic acid dihydrazide such as adipic acid dihydrazide for the purpose of promoting curing.
- a combination of dicyandiamide and a compound having two or more urea bonds in one molecule or a combination of dicyandiamide and imidazoles is preferable from the viewpoint of curability and stability.
- a compound having two or more urea bonds in one molecule 4,4′-methylenebis (diphenyldimethylurea) or 2,4-toluenebis (3,3-dimethylurea) is preferable.
- -Phenyl-4,5-dihydroxymethylimidazole or 2-phenyl-4-methyl-5-hydroxymethylimidazole is preferred.
- Component [C] in the present invention is a phosphate ester.
- Phosphate ester refers to an ester compound of phosphoric acid and an alcohol compound or a phenol compound.
- a flame retardance can be provided to a carbon fiber reinforced composite material by mix
- phosphate ester examples include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropyl).
- Phenyl) phosphate tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyl Oxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, Phenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenylmethanephosphonate, diethyl phenylphosphonate, Mention may
- the condensed phosphate ester examples include resorcinol bis (di2,6-xylyl) phosphate, resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like.
- resorcinol bis (di2,6-xylyl) phosphate examples include resorcinol bis (di2,6-xylyl) phosphate, resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like.
- PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.
- a commercially available product of resorcinol bis (diphenyl phosphate) is CR-733S (manufactured by Daihachi Chemical Industry Co., Ltd.).
- Examples of commercially available bisphenol A bis (diphenyl phosphate) include CR-741 (manufactured by Daihachi Chemical Industry Co., Ltd.). Of these, resorcinol bis (di2,6-xylyl) phosphate is preferably used from the viewpoint of excellent curability and heat resistance.
- Component [D] in the present invention is a phosphazene compound.
- the phosphazene compound can impart flame retardancy to the carbon fiber reinforced composite material by containing a phosphorus atom and a nitrogen atom in the molecule.
- the phosphazene compound is not particularly limited as long as it does not contain a halogen atom and has a phosphazene structure in the molecule.
- the phosphazene structure represents a structure represented by the formula: —P (R 2 ) ⁇ N— [wherein R is an organic group].
- the phosphazene compound is generally represented by the following formulas (III) and (IV).
- X 1 , X 2 , X 3 and X 4 represent hydrogen, a hydroxyl group, an amino group or an organic group containing no halogen atom.
- N represents an integer of 3 to 10.
- examples of the organic group not containing a halogen atom represented by X 1 , X 2 , X 3 , and X 4 include an alkoxy group, a phenyl group, an amino group, and an allyl group. Is mentioned.
- phosphazene compounds include SPR-100, SA-100, SPB-100, SPB-100L (above, Otsuka Chemical Co., Ltd.), FP-100, FP-110 (above, Fushimi Pharmaceutical). Can be mentioned.
- the flame retardancy, curability, heat resistance and mechanical properties are superior to using each component alone.
- Phosphoric ester [C] tends to become brittle due to a decrease in the amount of deflection of the cured resin, in addition to a significant decrease in curability and heat resistance due to the blending.
- the elastic modulus of the phosphazene compound [D] is reduced by blending, in addition to the improvement of the deflection amount, the content of phosphorus atoms contained in the structure is generally higher than that of the phosphate ester [C].
- the total amount of the phosphate ester [C] and the phosphazene compound [D] used in combination in the epoxy resin composition used in the present invention is preferably 5 to 60 parts by mass with respect to 100 parts by mass of the epoxy resin. More preferably, it is 10 to 50 parts by mass.
- the blending amount is 5 parts by mass or more, the effect of flame retardancy can be easily obtained, and when it is within 60 parts by mass, the heat resistance and carbon fiber of a cured product obtained by heating and curing the epoxy resin composition The mechanical properties of the reinforced composite material can be maintained at a high level.
- the flame-retardant effect of phosphorus atoms is considered to be due to the effect of promoting the formation of carbides of phosphorus atoms, and is greatly affected by the phosphorus atom content in the epoxy resin composition.
- the phosphorus atom content in the total epoxy resin composition is preferably 1.2 to 4% by mass, and more preferably 1.4 to 4% by mass.
- the phosphorus atom content is 1.2% by mass or more, the effect of flame retardancy is easily obtained, and when the content is within 4% by mass, the heat resistance of the cured product and the mechanical properties of the carbon fiber reinforced composite material are obtained.
- the rigidity and Charpy impact value can be prevented from being lowered and maintained at a high level.
- the phosphorus atom content (mass%) referred to here is determined by the mass of phosphorus atoms (g) / the mass of all epoxy resin compositions (g) ⁇ 100.
- the phosphorus atom content in the epoxy resin composition can be obtained by the above calculation method, or by organic element analysis of the epoxy resin composition or cured resin, ICP-MS (inductively coupled plasma mass spectrometry), or the like. You can also.
- each of the phosphate ester [C] and the phosphazene compound [D] may be used alone, or any one or both may be used in combination of two or more.
- the phosphate ester [C] and the phosphazene compound [D] in the present invention may be incorporated into the epoxy skeleton during the curing reaction, or may be dispersed or compatible with the epoxy resin composition.
- the epoxy resin composition of the present invention may contain one or more other flame retardants in order to improve flame retardancy.
- flame retardants include compounds containing nitrogen atoms such as melamine cyanurate, melamine sulfate, guanidine sulfamate, metal hydrates such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, tin hydroxide, zinc borate , Metal oxides such as zinc hydroxystannate and magnesium oxide, silicone resins and silicone oils.
- the epoxy resin composition of this invention can mix
- thermoplastic resin at least two kinds selected from polymethyl methacrylate, polyvinyl formal, polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone, aromatic vinyl monomer / vinyl cyanide monomer / rubber polymer are used as constituent components
- polymers such as polyamide, polyester, polycarbonate, polyarylene oxide, polysulfone, polyethersulfone, polyimide, and phenoxy resin.
- polyvinyl formal and phenoxy resin are preferably used because they have good compatibility with the epoxy resin and have a large effect of controlling the fluidity of the epoxy resin composition, and among them, represented by the following formula (I)
- a phenoxy resin is particularly preferably used because of its good compatibility with the above compound and high flame retardancy.
- phenoxy resin used here in addition to phenoxy resin which has bisphenol skeletons, such as bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A type and F type mixed phenoxy resin, naphthalene skeleton And a phenoxy resin having a biphenyl skeleton.
- phenoxy resin which has bisphenol skeletons such as bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A type and F type mixed phenoxy resin, naphthalene skeleton And a phenoxy resin having a biphenyl skeleton.
- Examples of commercially available bisphenol A type phenoxy resins include YP-50, YP-50S, and YP-55U (above, manufactured by Tohto Kasei Co., Ltd.).
- As a commercial product of bisphenol F type phenoxy resin FX-316 (manufactured by Toto Kasei Co., Ltd.) can be mentioned.
- bisphenol A / F mixed phenoxy resins include YP-70 and ZX-1356-2 (above, manufactured by Tohto Kasei Co., Ltd.). Among these, bisphenol F type phenoxy resin and bisphenol A type / F type mixed phenoxy resin are preferred because they exhibit better compatibility and flame retardancy.
- the blending amount when the thermoplastic resin is blended is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin.
- the molecular weight of the thermoplastic resin component is not particularly limited because the preferred molecular weight varies depending on the type of the thermoplastic resin used, but usually the one having a mass average molecular weight of 10,000 or more is used. Is preferred. More preferably, it is 30000-80000. Thereby, the said characteristic can be expressed effectively.
- the mass average molecular weight here refers to a polystyrene-reduced mass average molecular weight obtained by GPC (gel permeation chromatography).
- the structure and compounding ratio of the compound contained in the epoxy resin composition of the present invention can be specified by the following method. That is, each component was extracted from the epoxy resin composition by ultrasonic extraction using chloroform and then methanol, and the obtained extract was analyzed by IR, 1 H-NMR, 13 C-NMR spectrum, and the formula ( The structure of the compound represented by I), the organic nitrogen compound curing agent, the phosphate ester, and the phosphazene can be specified. Further, the mobile phase was chloroform / acetonitrile using the chloroform extract thus obtained. Normal phase HPLC is measured, and the peak intensity ratio of the obtained chromatograph is compared with the peak intensity ratio of a known epoxy resin commercial product. By repeating sample preparation and normal phase HPLC measurement while changing the ratio of each compound, the compounding ratio of each compound can be specified.
- the viscosity at 50 ° C. is preferably 50 to 30000 Pa ⁇ s for the purpose of imparting processability such as tack and drape, More preferably, it is 50 to 20000 Pa ⁇ s.
- the viscosity at 50 ° C. is preferably 50 to 30000 Pa ⁇ s for the purpose of imparting processability such as tack and drape, More preferably, it is 50 to 20000 Pa ⁇ s.
- the viscosity at 50 ° C. here is determined by the following method. That is, using a dynamic viscoelasticity measuring device ARES (manufactured by TA Instruments Japan), after setting the epoxy resin composition on a parallel plate having a diameter of 40 mm so that the distance between the parallel plates is 1 mm, the torsion mode (frequency 0.5 Hz) to obtain the complex viscosity ⁇ *.
- ARES dynamic viscoelasticity measuring device
- the glass transition temperature of the cured product obtained by curing the epoxy resin composition of the present invention is preferably 90 to 250 ° C, more preferably 90 to 220 ° C, and still more preferably 95 to 200 ° C.
- the glass transition temperature is preferably 90 to 250 ° C, more preferably 90 to 220 ° C, and still more preferably 95 to 200 ° C.
- the glass transition temperature here is a torsional mode using a dynamic viscoelasticity measuring device ARES (manufactured by TA Instruments Japan) using a resin cured product having a width of 12.7 mm, a length of 45 mm, and a thickness of 2 mm as a test piece.
- the glass transition temperature is measured by raising the temperature at a rate of 5 ° C./min at a frequency of 1 Hz), and the glass transition temperature is lower than the staircase change portion due to the glass transition of G ′, and the gradient of the staircase change portion. Means the point of intersection with the tangent drawn at the point where the maximum is, that is, the extrapolated glass transition start temperature.
- the flexural modulus measured according to JIS K7171 (1999) of the cured product obtained by curing the epoxy resin composition of the present invention is preferably in the range of 2.5 to 5 GPa, more preferably 2.8 to 5 GPa. is there.
- Such a cured product is obtained by curing the epoxy resin composition from 25 ° C. at a rate of temperature increase of 1.5 ° C./min and then curing at 150 ° C. for 3 minutes.
- the amount of deflection measured according to JIS K7171 (1999) of a cured product obtained by curing the epoxy resin composition of the present invention is preferably 2 mm or more, and more preferably 2.5 mm or more.
- the carbon fiber reinforced composite material obtained by curing the prepreg can easily obtain suitable strength in the non-fiber direction and interlayer shear strength.
- the upper limit of the obtained deflection amount is about 6 mm.
- the epoxy resin composition of the present invention is preferably cured in a short time in industrial material applications where it is desired to be able to be produced in large quantities in a short time, in particular, in applications such as electronic / electrical component housings. It is preferable that the gelation time in is 3 minutes or less. Further, for the purpose of improving productivity, it is desirable to gel in a shorter time.
- the gelation time of an epoxy resin composition here can be measured as follows. That is, an epoxy resin composition was sampled as a 2 cm 3 sample, and the sample was put into a die heated to 150 ° C.
- the prepreg of the present invention uses carbon fibers as reinforcing fibers. By using carbon fiber, it is possible to develop excellent flame retardancy, strength, and impact resistance in the fiber-reinforced composite material.
- any type of carbon fiber can be used depending on the application, and such carbon fiber is preferably used with a tensile strength in the range of 2 GPa to 12 GPa.
- the tensile strength is preferably as high as possible from the viewpoint of high tensile strength inherent to carbon fiber and high impact resistance when a composite material is used, and a more preferable tensile strength is 3 GPa to 10 GPa.
- Such carbon fibers usually have a tensile modulus of 150 GPa to 1000 GPa, and the use of carbon fibers having a high tensile modulus leads to obtaining a high modulus when used as a fiber-reinforced composite material.
- the tensile elastic modulus is required to have high rigidity, and more preferably 200 GPa to 1000 GPa when importance is attached to the reduction in thickness and weight, such as an electronic / electrical component casing.
- the tensile strength and elastic modulus of carbon fiber here mean the strand tensile strength and the strand tensile elastic modulus measured according to JIS R7601 (1986).
- the carbon fibers used in the present invention are classified into polyacrylonitrile-based, rayon-based and pitch-based carbon fibers. Among these, polyacrylonitrile-based carbon fibers having high tensile strength are preferably used.
- the polyacrylonitrile-based carbon fiber can be produced, for example, through the following steps. A spinning dope containing polyacrylonitrile obtained from a monomer containing acrylonitrile as a main component is spun by a wet spinning method, a dry wet spinning method, a dry spinning method, or a melt spinning method. The spun coagulated yarn can be made into a precursor through a spinning process, and then carbon fiber can be obtained through processes such as flame resistance and carbonization.
- Examples of commercially available carbon fibers used in the present invention include “Torayca (registered trademark)” T700SC-12000 (tensile strength: 4.9 GPa, tensile elastic modulus: 230 GPa, manufactured by Toray Industries, Inc.), “Torayca (registered trademark)” “T800HB-12000 (tensile strength: 5.5 GPa, tensile elastic modulus: 294 GPa, manufactured by Toray Industries, Inc.)” And TORAYCA (registered trademark) M40JB-12000 (tensile strength: 4.4 GPa, tensile modulus: 377 GPa, manufactured by Toray Industries, Inc.).
- the prepreg of the present invention is a sheet-like intermediate material in which carbon fiber is impregnated with the above epoxy resin composition.
- the epoxy resin composition is dissolved in an organic solvent such as methyl ethyl ketone or methanol to lower the viscosity, impregnated while immersing the sheet-like fiber made of carbon fiber, and then an oven or the like.
- a method such as a hot melt method in which the film is superimposed from both sides or one side of the fiber and impregnated by heating and pressurization can be used.
- the hot melt method is used. Can be preferably used.
- the maximum temperature reached by the epoxy resin composition is preferably Is in the range of 60 ° C to 150 ° C, more preferably in the range of 80 ° C to 130 ° C.
- the epoxy resin composition does not necessarily need to be impregnated to the inside of the fiber bundle, and the epoxy resin composition is localized near the surface of fibers or fiber fabrics arranged in one direction in a sheet shape. It may be an embodiment.
- Examples of the form of carbon fiber in the prepreg of the present invention include long fibers aligned in one direction, bi-directional woven fabric, multiaxial woven fabric, non-woven fabric, mat, knit, braided string, etc., but are not limited thereto. Absent.
- the long fiber here means a single fiber or a fiber bundle substantially continuous for 10 mm or more.
- a so-called unidirectional prepreg using long fibers aligned in one direction has a high fiber strength direction and a high strength utilization rate in the fiber direction because the fibers are less bent. Further, when the unidirectional prepreg is formed after a plurality of prepregs are laminated in an appropriate laminated configuration, the elastic modulus and strength of each surface of the carbon fiber reinforced composite material can be freely controlled.
- a fabric prepreg using various fabrics is also a preferred embodiment because a material with low strength and elastic anisotropy can be obtained, and a fiber fabric pattern is floated on the surface and the design is excellent. It is also possible to form a carbon fiber reinforced composite material using multiple types of prepregs, for example, both unidirectional prepregs and woven prepregs.
- the prepreg of the present invention preferably has a carbon fiber mass content (hereinafter referred to as Wf) of 50 to 90% by mass with respect to the total mass of the prepreg. More preferred is 60 to 85% by mass, and particularly preferred is 65 to 85% by mass.
- Wf carbon fiber mass content
- the content of the matrix resin can be within a suitable range, and various properties required for a carbon fiber reinforced composite material having high flame retardancy, and excellent specific modulus and specific strength. Characteristics are easily obtained.
- Wf means the fiber mass content measured according to JIS K7071 (1988).
- the epoxy resin composition in order to form a carbon fiber reinforced composite material using a prepreg, is heated and cured while applying pressure to a laminate in which a predetermined number of layers are laminated after cutting the prepreg into a predetermined dimension.
- a method or the like can be preferably used.
- Examples of methods for heat-curing the epoxy resin composition while applying heat and pressure include a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, and an internal pressure molding method.
- the temperature at which the carbon fiber reinforced composite material is molded depends on the type of curing agent contained in the epoxy resin composition, but is usually adjusted in the temperature range of 80 to 220 ° C. By setting the molding temperature in an appropriate range, sufficient fast curability can be easily obtained, and an effect of suppressing the occurrence of warpage due to overheating can be easily obtained.
- the pressure for molding the carbon fiber reinforced composite material varies depending on the thickness of the prepreg, Wf, etc., but is usually adjusted within a pressure range of 0.1 to 1 MPa.
- the pressure for molding the carbon fiber reinforced composite material varies depending on the thickness of the prepreg, Wf, etc., but is usually adjusted within a pressure range of 0.1 to 1 MPa.
- the carbon fiber reinforced composite material of the present invention has a high flame retardancy measured at a thickness of 2 mm or less, preferably as high as V-1 or more, more preferably as V-0, as measured by the UL94 standard. It is a thing.
- the thickness is 1.5 mm or less, preferably V-1 or more, assuming that there is a possibility that the carbon fiber reinforced composite material may be used with a thinner thickness.
- V-0 has a high flame retardancy of 1 or more, more preferably V-0.
- the flame retardancy of V-0 and V-1 refers to the combustion time and its state, the presence or absence of fire spread, the presence or absence of dripping (drip) in the UL94 standard (American Combustion Test Method devised by Underwriters Laboratories Inc.) And flame retardancy satisfying the conditions of V-0 and V-1 defined by the flammability of the droplets and the drops.
- the tensile strength in the fiber direction is preferably 1000 MPa or more.
- the tensile strength is measured in accordance with the method described in ASTM D3039.
- the carbon fiber reinforced composite material of the present invention is preferably used as an electronic / electrical component casing.
- the electronic / electrical component housing obtained by the present invention is suitable for those requiring strength, lightness and flame retardancy.
- the mode is not particularly limited because it varies depending on the application, but the laminate of the carbon fiber reinforced composite material of the present invention may be used alone or may be used by being joined to another member.
- carbon fiber reinforced composite materials may be used, for example, may be made of a metal material, may be made of a thermoplastic resin, and is reinforced with reinforcing fibers such as carbon fiber and glass fiber. It may be made of a resin composition.
- the metal material to be joined as another member include aluminum, iron, magnesium, titanium, and alloys thereof.
- thermoplastic resin to be bonded as another member examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PENP), polyesters such as liquid crystal polyester, and polyethylene ( PE), polypropylene (PP), polybutylene and other polyolefins and styrene resins, polyoxymethylene (POM), polyamide (PA), polycarbonate (PC), polymethylene methacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene Sulfide (PPS), polyphenylene ether (PPE), modified PPE, polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone (PSU), PSU, polyethersulfone, polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyarylate (PAR), polyether
- thermoplastic resin reinforced with reinforcing fibers as a thermoplastic resin to be joined as another member, since a light weight that cannot be realized when a metal material to be joined as another member is joined is obtained.
- an adhesive may be used or it may be welded via a thermoplastic resin composition layer. Also, fitting or fitting, mechanical joining such as bolts and screws may be performed.
- the carbon fiber reinforced composite material of the present invention When the carbon fiber reinforced composite material of the present invention is used as an electronic / electrical component casing, it is desired that the carbon fiber reinforced composite material is not easily deformed by a load from the outer surface such as the upper and lower surfaces and the side surface.
- the rigidity is obtained by the following method. For example, using a material testing machine such as an Instron universal testing machine (Instron), a test piece size of 100 mm ⁇ 70 mm, an indenter diameter of 20 mm, a crosshead speed of 5 mm / min was measured, and a load of 50 N was applied. The amount of deflection at the time is obtained, and if the amount of deflection is low, it can be evaluated that the rigidity is high.
- the carbon fiber reinforced composite material of the present invention desirably has a deflection amount of 1.5 mm or less when a load of 50 N is applied.
- the material absorbs a large amount of impact when dropped, and a material having a high Charpy impact value is preferably used.
- the Charpy impact value is desirably 100 J / m 2 or more. More preferably, it is 150 J / m 2 or more, and more preferably 200 J / m 2 or more.
- the Charpy impact value is measured according to the method described in JIS K7077 (1991). The upper limit of the Charpy impact value is not limited, and the higher the Charpy impact value, the greater the impact absorbing ability of the material when dropped, which is preferable because the durability of the applied product is improved.
- the epoxy resin composition, the prepreg, the carbon fiber reinforced composite material, and the electronic / electrical component casing of the present invention will be described more specifically with reference to examples.
- the preparation method of each component and epoxy resin composition used in the examples is as shown in (1) and (2) below, and the preparation method of the prepreg is as shown in (6) below.
- various properties (physical properties) were measured by the following methods (3) to (5) and (7) to (12). These physical properties were measured in an environment of a temperature of 23 ° C. and a relative humidity of 50% unless otherwise specified.
- Organic nitrogen compound curing agent (component [B]) Dicy7 (Dicyandiamide, manufactured by Japan Epoxy Resin Co., Ltd.) “OMICURE®” 24 (2,4′-toluenebis (3,3-dimethylurea), manufactured by PTI Japan) “Omicure (registered trademark)” 52 (4,4′-methylenebis (diphenyldimethylurea), manufactured by PTI Japan) DCMU-99 (3,4-dichlorophenyl-1,1-dimethylurea, manufactured by Hodogaya Chemical Co., Ltd.) 2P4MHZ (2-phenyl-4-methyl-5-hydroxymethylimidazole, manufactured by Shikoku Chemicals Co., Ltd.) Phosphate ester (component [C]) PX-200 (resorcinol bis (di2,6-xylyl) phosphate, phosphorus content 9.0%, manufactured by Daihachi Chemical Industry Co., Ltd.) CR-733S (resorcinol bis
- a test piece having a width of 12.7 mm and a length of 45 mm was cut out from the cured resin, and a dynamic viscoelasticity measuring device ARES (manufactured by TA Instruments Japan) was used, with a frequency of 1 Hz, a temperature of 25 to 250 ° C., and 5 ° C./min. The temperature was measured by raising the temperature.
- the glass transition temperature is the intersection of the base line on the lower temperature side of the step change portion due to the glass transition of G ′ and the tangent drawn at the point where the gradient of the step change portion is maximum, that is, the extrapolated glass transition start temperature The transition temperature was used.
- the prepreg was produced as follows. Using the reverse roll coater, the epoxy resin composition obtained in the above (2) was applied onto the release paper to prepare a resin film having a basis weight of 25 g / m 2 . Next, the above resin film is laminated on both sides of the carbon fiber aligned in one direction in a sheet shape so that the fiber mass per unit area becomes 100 g / m 2 , under conditions of a temperature of 95 ° C. and a pressure of 0.2 MPa. Heating and pressing were impregnated with the epoxy resin composition to prepare a unidirectional prepreg with a Wf of 67%.
- Tack value is 0.1 kg or more, less than 0.3 kg, or more than 2.0 kg and 3.0 kg or less, and adhesiveness is a little too strong or is a little weak.
- X Tack value is 0.0 kg or more and less than 0.1 kg, or larger than 3.0 kg, the tackiness is too strong, or there is no tackiness.
- Flame retardance was evaluated by a vertical combustion test based on the UL94 standard. Five test pieces having a width of 12.7 ⁇ 0.1 mm and a length of 127 ⁇ 1 mm were cut out from the molded carbon fiber reinforced composite material. The height of the flame of the burner was adjusted to 19 mm, and the lower end of the center of the test piece held vertically was exposed to the flame for 10 seconds, then separated from the flame and the burning time was recorded. Immediately after extinguishing the flame, the burner flame was further applied for 10 seconds to separate it from the flame, and the combustion time was measured.
- V It was determined to be ⁇ 0, and V ⁇ 1 was determined if the burning time was within 30 seconds and the total burning time after contacting 5 test pieces 10 times was within 250 seconds. Further, when there was a flammable drop even at the same combustion time as V-1, it was determined as V-2, and when the combustion time was longer than that, or when it burned up to the specimen holder, it was determined as V-out.
- Prepregs are laminated in the fiber direction, and formed by heating press at a temperature of 150 ° C for 3 minutes under a pressure of 0.6 MPa, with a thickness of 1 ⁇ 0.05 mm in one direction
- a carbon fiber reinforced composite material plate was obtained.
- a glass tab having a length of 56 mm and a thickness of 1.5 mm was bonded to both surfaces of the obtained carbon fiber reinforced composite material, and then a width of 12.7 ⁇ 0.1 mm and a length of 250 so that the 0 ° direction became the length direction.
- Rigidity test prepregs are laminated in a configuration of (0/90/45) s, and molding by heating press is performed at a temperature of 150 ° C. for 3 minutes under a pressure of 0.6 MPa, and a thickness of 0.6 ⁇ 0
- a carbon fiber reinforced composite plate with a thickness of 0.05 mm was obtained.
- a test piece is cut out from the obtained carbon fiber reinforced composite material so that the 45 ° direction is the length direction and fixed to the frame shape, and the size of the test piece excluding the fixed portion is 70 mm wide and 100 mm long. I made it.
- Instron universal testing machine manufactured by Instron
- measurement was performed with an indenter diameter of 20 mm and a crosshead speed of 5 mm / min, and the amount of deflection when a load of 50 N was applied was determined.
- Charpy impact test A prepreg is laminated in the fiber direction, and molding by autoclave is performed at a temperature of 150 ° C for 3 minutes under a pressure of 0.6 MPa, and a unidirectional carbon having a thickness of 3 ⁇ 0.05 mm.
- a fiber reinforced composite plate was obtained.
- a shock was applied to the center of the test piece at a distance of 60 mm between the tables, a moment around the rotation axis of the hammer of 295 N ⁇ m, and a lifting angle of 134.5 °, and the Charpy impact value was obtained from the swing angle of the hammer after the test piece was broken.
- a Charpy impact tester manufactured by Yonekura Seisakusho was used for the test.
- the epoxy resin composition had a gelation time of 87 seconds and could be cured in 3 minutes.
- the cured resin had a good Tg of 160 ° C.
- the cured resin had a good balance of elastic modulus of 3.8 GPa and deflection amount of 3.3 mm. Further, the flame retardancy of the composite material was V-1 at a thickness of 0.6-0.7 mm, and V-0 at a thickness of 0.19-0.21 mm, and sufficient flame retardancy was obtained.
- the Tg of the composite material after curing at 150 ° C. for 3 minutes was sufficiently high at 153 ° C., and the mechanical properties such as 0 ° tensile strength, rigidity of the molded product, and Charpy impact value were also good.
- Example 2 Using “Omicure®” 52 in place of “Omicure®” 24 of component [B] and increasing the amount of SPB-100 of component [D] from 5 parts to 10 parts to obtain a phosphorus content of 1.
- a cured resin, a prepreg, and a composite material were prepared in the same manner as in Example 1 except that YP-70 was used instead of YP-50 as the thermoplastic resin.
- V-0 was achieved at both thicknesses of 0.6-0.7 mm and 0.19-0.21 mm. Resin cured product characteristics, composite material characteristics, and molded product characteristics were also good.
- Example 3 The total amount of component [C] and component [D] is increased to 30 parts by mass, and a cured resin is obtained in the same manner as in Example 1 except that YP-70 is used as the thermoplastic resin as in Example 2.
- a prepreg and a composite material were produced. When the characteristics were evaluated, the flame retardancy of the composite material achieved V-0 at thicknesses of 0.6-0.7 mm and 0.19-0.21 mm. In Example 3 in which 20 parts by mass of phosphoric acid ester was blended, although the Tg of the composite material was slightly lowered, it was at a satisfactory level, and other characteristics were good.
- Example 5 Increase the amount of “Omicure (registered trademark)” 24 of component [B] to 6 parts by mass, and increase the total amount of component [C] and component [D] to 50 parts to increase the phosphorus content.
- a cured resin, a prepreg, and a composite material were prepared in the same manner as in Example 1 except that YP-70 was used as the thermoplastic resin in the same manner as in Example 2 except that the amount was adjusted to 3%.
- the gelation time was slightly late as 130 seconds, Tg of the cured resin, Tg of the composite material, and Charpy impact value of the molded product were slightly low, but were satisfactory and other characteristics were good.
- Example 6 Using “Epiclon (registered trademark)” N-770 and “jER (registered trademark)” 152 as component [A], Dicy7 and “Omicure (registered trademark)” 24 as component [B], A cured resin, a prepreg, and a composite material were produced in the same manner as in Example 2 except that the content of the compound represented by the formula (I) was 82%. When the characteristics were evaluated, the cured resin characteristics, composite material characteristics, and molded product characteristics were good. The tackiness of the prepreg was also high and suitable as compared with Examples 1 to 5.
- Example 8 N-770, “jER (registered trademark)” 828 is used as component [A], and the content of the compound represented by formula (I) in component [A] is 55%.
- the flame retardancy of the composite material was V-1 at a thickness of 0.6-0.7 mm and a thickness of 0.19-0.21 mm.
- Example 6 and Example 7 in which the blending of the component [C] is the same, the gelation time was slowed down to 136 seconds and the Tg of the composite material was reduced, but it was at a level without problems. Other characteristics were similarly good.
- Example 9 A cured resin, prepreg, and composite material were produced in the same manner as in Example 3 except that CR-733S was used instead of PX-200 as component [C]. Compared to Example 3, the gelation time was as slow as 147 seconds, and the amount of deflection of the cured resin, the Tg of the composite material, and the Charpy impact value were slightly low, but were at a level without any problems. The flame retardancy of the composite material achieved V-0 for both the thickness of 0.6-0.7 mm and the thickness of 0.19-0.21 mm.
- Example 10 A resin cured product, prepreg, and composite material were prepared using DCMU-99 as component [B]. Compared with Examples 2 and 3 using "Omicure (registered trademark)" 52 and “Omicure (registered trademark)” 24, the gelation time was as slow as 141 seconds, and the Tg of the composite material was low, but at a satisfactory level. In addition, the flame retardancy of the composite material achieved V-0 at a thickness of 0.6-0.7 mm and a thickness of 0.19-0.21 mm, and other properties were also good.
- Example 11 In the same manner as in Example 10, a cured resin, a prepreg, and a composite material were produced using DCMU-99 as the component [B]. Although the gelation time is a little slow as 131 seconds and the Tg of the composite material is low, it is a level that is not problematic, and the flame retardancy of the composite material is 0.6-0.7 mm in thickness and 0.19-0.21 mm in thickness. V-0 was achieved and the other characteristics were also good.
- Example 12 A resin cured product, a prepreg, and a composite material were prepared using 2P4MHZ as the component [B]. When the properties were evaluated, the flame retardancy of the composite material achieved V-0 at thicknesses of 0.6-0.7 mm and 0.19-0.21 mm, and the cured resin properties, composite material properties, molded product properties was also good.
- Example 13 A cured resin, a prepreg, and a composite material were prepared using “Vinylec (registered trademark)” K as a thermoplastic resin. When the characteristics were evaluated, the 0 ° tensile strength and Charpy impact value of the molded product were slightly low, but they were at a level that was not a problem, and the other characteristics showed good results.
- Example 16 Resin cured product in the same manner as in Examples 14 and 15, using “Epiclon (registered trademark)” N-770, “jER (registered trademark)” 154 and “jER (registered trademark)” 828 as the component [A].
- a prepreg and a composite material were prepared. When the characteristics were evaluated, the flame retardancy of the composite material achieved V-0 at thicknesses of 0.6-0.7 mm and 0.19-0.21 mm, and the tackiness of the prepreg was also appropriate. The resin cured product characteristics, composite material characteristics, and molded product characteristics were also good.
- Example 17 Resin cured products, prepregs, and composite materials were prepared using “Epiclon (registered trademark)” N-770 alone as component [A]. Although the cured resin properties, composite material properties and molded product properties were good, the prepreg was not tacky and was difficult to handle.
- Example 18 A cured resin, a prepreg, and a composite material were produced using “jER (registered trademark)” 154 alone as the component [A]. When the properties were evaluated, the flame retardancy of the composite material achieved V-1 at a thickness of 0.6-0.7 mm, V-0 at a thickness of 0.19-0.21 mm, and other properties were also good. there were.
- the carbon fiber reinforced composite material using the epoxy resin composition of the present invention is preferably used for structural materials such as blades of aircrafts, vehicles, windmills, building materials, etc., as well as electronic / electrical component cases such as notebook personal computers.
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Abstract
Description
このような炭素繊維強化複合材料は、熱硬化性樹脂を炭素繊維に含浸して得られるプリプレグを積層し、加熱加圧して得られることが多い。
炭素繊維強化複合材料の様々な用途の中で、特に航空機や車両などの構造材料や建築材料などにおいては、火災によって材料が着火燃焼しないように材料に難燃性を有することが求められている。また、電子電気機器においても、装置内部からの発熱や外部の高温にさらされることにより、筐体や部品などが発火し燃焼する事故を防ぐために、材料の難燃化が求められている。
しかしながら上記の様なハロゲンを含む樹脂組成物やその硬化物は、燃焼時にハロゲン化水素等の有害物質を発生する可能性があり、人体や自然環境に悪影響を及ぼす可能性があることから、ハロゲンを含有せずとも優れた難燃性を示すエポキシ樹脂組成物の開発が進められている。
ハロゲンを含有しないエポキシ樹脂組成物の難燃化技術として、赤リンおよびリン酸エステルからなる炭素繊維強化複合材料用マトリックス樹脂の技術が開示されている(例えば特許文献1)。この技術はハロゲンガスを発生せず、難燃性を得ることができる。しかしながら赤リンは配合により樹脂に赤色の着色があるため、エポキシ樹脂の調整およびプリプレグ化工程において、赤色の着色がない樹脂と比べて製造における装置や器具の洗浄に手間がかかり、さらに電子電気部品筐体用途においては炭素繊維強化複合材料の製品表面の色調が限定されるといった問題がある。リン酸エステルは化合物中に含まれるリン含有率が赤リン対比低く、十分な難燃性を確保するために多量の配合が必要となり、硬化性および耐熱性が低下するといった問題がある。また、積層板用途などで、フェノールノボラック型エポキシ樹脂とリン酸エステルを使用する難燃化技術が開示されている(例えば特許文献2)。しかしながらこの技術では、エポキシ樹脂の耐熱性および柔軟性が低下してしまうだけでなく、硬化速度が遅延し硬化に長時間を要するため生産性が悪いという問題点がある。また、封止材用途などで、リン酸エステルとホスファゼン化合物を併用し、難燃性および耐湿性のバランスを保つ技術が開示されているが(例えば特許文献3)、炭素繊維強化複合材料としたときに良好なプロセス性や力学特性が得られないといった問題がある。
すなわち、次の構成成分[A]下記式(I)で表される化合物を50質量%以上含むエポキシ樹脂、[B]有機窒素化合物硬化剤、[C]リン酸エステル、[D]ホスファゼン化合物を含むことを特徴とするエポキシ樹脂組成物である。
本発明のエポキシ樹脂組成物の好ましい様態によれば、熱可塑性樹脂としてフェノキシ樹脂を含むものである。
本発明のエポキシ樹脂組成物は、前記式(I)で表される構造を有する化合物を50質量%以上含むエポキシ樹脂である成分[A]と、有機窒素化合物硬化剤である成分[B]と、リン酸エステルである成分[C]と、ホスファゼン化合物である成分[D]を含んでなる。
本発明における成分[A]は、下記式(I)で表されるエポキシ樹脂を全エポキシ樹脂中に50質量%以上含むエポキシ樹脂である。
これにより、エポキシ樹脂組成物に優れた速硬化性、および耐熱性を付与し、かつ該エポキシ樹脂組成物を炭素繊維と組み合わせて加熱硬化させた炭素繊維強化複合材料に、高い難燃性、および耐熱性を付与することができる。
本発明における式(I)で表される化合物は、例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂が挙げられ、これらのエポキシ樹脂を単独、または2種以上組み合わせた場合を含むものである。
フェノールノボラック型エポキシ樹脂の市販品としては、“jER(登録商標)”152、“jER(登録商標)”154(以上、ジャパンエポキシレジン(株)製)、“エピクロン(登録商標)”N-740、“エピクロン(登録商標)”N-770、“エピクロン(登録商標)”N-775(以上、DIC(株)製)、PY307、EPN1179、EPN1180(以上、ハンツマン・アドバンスト・マテリアル社製)、YDPN638、YDPN638P(以上、東都化成(株)製)、DEN431、DEN438、DEN439(以上、ダウケミカル社製)、EPR600(Bakelite社製)、EPPN-201(日本化薬(株)製)などが挙げられる。
クレゾールノボラック型エポキシ樹脂の市販品としては、“jER(登録商標)”180S(ジャパンエポキシレジン(株)製)、“エピクロン(登録商標)”N-660、“エピクロン(登録商標)”N-665、“エピクロン(登録商標)”N-670、“エピクロン(登録商標)”N-673、“エピクロン(登録商標)”N-680、“エピクロン(登録商標)”N-695、“エピクロン(登録商標)”N-665-EXP、“エピクロン(登録商標)”N-672-EXP、“エピクロン(登録商標)”N-655-EXP-S、“エピクロン(登録商標)”N-662-EXP-S、“エピクロン(登録商標)”N-665-EXP-S、“エピクロン(登録商標)”N-670-EXP-S、“エピクロン(登録商標)”N-685-EXP-S(以上、DIC(株)製)、ECN9511、ECN1273、ECN1280、ECN1285、ECN1299(以上、ハンツマン・アドバンスト・マテリアル社製)、YDCN-701、YDCN-702、YDCN-703、YDCN-704(以上、東都化成(株)製)、CER-1020、EOCN-1020-62、EOCN-1020、EOCN-102S、EOCN-103S、EOCN-104S(以上、日本化薬(株)製)、ESCN200L、ESCN220L、ESCN220F、ESCN220HH(以上、住友化学(株)製)、EPR650(Bakelite社製)などが挙げられる。
本発明における成分[A]に含まれる式(I)で表される化合物としては、上記エポキシ樹脂の中でも、クレゾールノボラック型エポキシ樹脂に含まれるメチル基が燃焼しやすいことから、難燃性の点で、フェノールノボラック型エポキシ樹脂が好ましい。
本発明において式(I)で表される化合物の含有率は、成分[A]中50質量%以上であり、より好ましくは55質量%以上、さらに好ましくは60質量%以上である。式(I)で表される化合物の含有率が50質量%以上配合することにより、得られるエポキシ樹脂組成物は、速硬化性および耐熱性に優れ、さらに得られる炭素繊維強化複合材料は、後述のとおりUL94燃焼試験でV-1以上といった高い難燃性を得られるようになる。式(I)で表される化合物の含有率は難燃性、速硬化性および耐熱性の観点から高いほうが好ましいが、一般的に用いられるエポキシ樹脂は分子量分布をもっているため、上限は通常95質量%程度である。
さらに、本発明における成分[A]は、式(I)で表される構造を有する化合物を50質量%以上含むことに加えて、プリプレグのタック性、ドレープ性の観点から、下記式(II)で表されるエポキシ樹脂を含むことが好ましい。
上記のとおり、難燃性、速硬化性および耐熱性の観点から、式(I)で表される化合物の含有率が高く、かつその中でも、nが2以上の化合物の含有率が高いほうが好ましいものの、一方で、nの値が大きくなるにつれ化合物の分子量が大きくなり、nが2以上となると室温で固形である場合が多いことから、プリプレグとしたときに好適なタック性、ドレープ性が得られない場合がある。よって、式(II)で表されるエポキシ樹脂を所定量配合することで、難燃性、速硬化性および耐熱性に加え、プリプレグに好適なタック性、ドレープ性を付与することができる。
式(II)で表されるエポキシ樹脂を含むエポキシ樹脂としては、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、フェノールノボラック型エポキシ樹脂が挙げられる。
また、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂の市販品のうち、好適なプリプレグ取扱性を与えることから、25℃の温度で液状のエポキシ樹脂が好ましく用いられる。ここで25℃の温度で液状であるとは、ガラス転移温度または融点が25℃以下であり、25℃の温度で流動性を示すエポキシ樹脂をいう。ガラス転移温度は、示差走査熱量計(DSC)を用いてJIS K7121(1987)に基づいて求めた中間点温度であり、また、結晶性の熱硬化性樹脂の融点は、JIS K7121(1987)に基づいて求めた融解ピーク温度である。
本発明において、式(II)で表される化合物の含有率は、成分[A]中15~40質量%であることが好ましく、より好ましくは15~35質量%である。配合量を15質量%以上とすることにより、好適なタック性およびドレープ性を付与できるようになり、さらに40質量%以内とすることにより、タックが過多となることを防ぎ、優れた難燃性を維持できるようになる。
フェノール類を原料とするエポキシ樹脂としては、ビスフェノールS型エポキシ樹脂、ビスフェノールAD型エポキシ樹脂、ビフェニル骨格を有するエポキシ樹脂、レゾルシノール型エポキシ樹脂、ナフタレン骨格を有するエポキシ樹脂、トリスフェニルメタン型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ジフェニルフルオレン型エポキシ樹脂などグリシジルエーテル型エポキシ樹脂やそれぞれの各種異性体やアルキル置換体などが挙げられる。また、エチレングリコールジグリジジルエーテル、プロピレングリコールジグリシジルエーテル、ヘキサメチレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテルなどの脂肪族エポキシ樹脂や、フェノール類を原料とするエポキシ樹脂をウレタンやイソシアネートで変性したエポキシ樹脂などもこのタイプに含まれる。
アミン類を原料とするエポキシ樹脂としては、N,N,O-トリグリシジル-m-アミノフェノール、N,N,O-トリグリシジル-p-アミノフェノール、N,N,O-トリグリシジル-4-アミノ-3-メチルフェノール、N,N-ジグリシジルアニリン、N,N-ジグリシジル-o-トルイジン、N,N,N’,N’-テトラグリシジル-4,4’-メチレンジアニリン、N,N,N’,N’-テトラグリシジル-2,2’-ジエチル-4,4’-メチレンジアニリン、N,N,N’,N’-テトラグリシジル-m-キシリレンジアミン、1,3-ビス(ジグリシジルアミノメチル)シクロヘキサンなどグリシジルアミン型エポキシ樹脂が挙げられる。
分子内不飽和炭素結合を有する化合物を原料とするエポキシ樹脂としては、ビニルシクロヘキセンジエポキシド、3,4-エポキシシクロヘキサンカルボン酸-3,4-エポキシシクロヘキシルメチル、アジピン酸ビス-3,4-エポキシシクロヘキシルメチルなどの脂環式エポキシ樹脂が挙げられる。
本発明における成分[B]の配合量は、エポキシ樹脂組成物の中の全エポキシ基の活性水素当量に対して0.6~1.4当量配合することが、耐熱性や機械物性の点から好ましい。その配合量は、用いる有機窒素化合物硬化剤の種類によるが、例えばジシアンジアミドを用いた場合、全エポキシ樹脂100質量部に対して1~15質量部であることが好ましい。より好ましくは1~10質量部である。
上記式(III)、(IV)中、X1、X2、X3、X4で表されるハロゲン原子を含まない有機基としては、例えば、アルコキシ基、フェニル基、アミノ基、アリル基等が挙げられる。
また、リン原子の難燃効果は、リン原子の炭化物形成の促進効果によるものと考えられており、エポキシ樹脂組成物中のリン原子含有率に大きく影響を受ける。本発明において、全エポキシ樹脂組成物中のリン原子含有率が1.2~4質量%であることが好ましく、さらに好ましくは、1.4~4質量%である。リン原子含有率が1.2質量%以上とすることにより、難燃の効果が得られやすくなり、さらに4質量%以内とすることにより、硬化物の耐熱性や炭素繊維強化複合材料の力学特性、特に剛性やシャルピー衝撃値の低下を防ぎ、高いレベルで維持できるようになる。ここでいうリン原子含有率(質量%)は、リン原子の質量(g)/全エポキシ樹脂組成物の質量(g)×100で求められる。なお、エポキシ樹脂組成物中のリン原子含有率は、上述の計算方法により求めることも、エポキシ樹脂組成物や樹脂硬化物の有機元素分析やICP-MS(誘導結合プラズマ質量分析)などにより求めることもできる。
本発明におけるリン酸エステル[C]およびホスファゼン化合物[D]は、硬化反応中にエポキシ骨格に取り込まれても、エポキシ樹脂組成物に分散または相溶していてもよい。
また、本発明のエポキシ樹脂組成物には、難燃性向上のために他の難燃剤の1種もしくは2種以上を含有してもよい。
熱可塑性樹脂としては、ポリメタクリル酸メチル、ポリビニルホルマール、ポリビニルブチラール、ポリビニルアセタール、ポリビニルピロリドン、芳香族ビニル単量体・シアン化ビニル単量体・ゴム質重合体から選ばれる少なくとも2種類を構成成分とする重合体、ポリアミド、ポリエステル、ポリカーボネート、ポリアリーレンオキシド、ポリスルホン、ポリエーテルスルホン、ポリイミド、フェノキシ樹脂などが挙げられる。これらの中でも、エポキシ樹脂と良好な相溶性を有し、エポキシ樹脂組成物の流動性制御の効果が大きい点から、ポリビニルホルマールおよびフェノキシ樹脂が好ましく用いられ、この中でも下記式(I)で表される化合物との相溶性が良く、難燃性が高い点から、フェノキシ樹脂が特に好ましく用いられる。
ビスフェノールA型フェノキシ樹脂の市販品としては、YP-50、YP-50S、YP-55U(以上、東都化成(株)製)が挙げられる。ビスフェノールF型フェノキシ樹脂の市販品としては、FX-316(東都化成(株)製)が挙げられる。ビスフェノールA型・F型混合型フェノキシ樹脂の市販品としては、YP-70、ZX-1356-2(以上、東都化成(株)製)が挙げられる。この中でも、より優れた相溶性、難燃性を示すことから、ビスフェノールF型フェノキシ樹脂やビスフェノールA型・F型混合型フェノキシ樹脂が好ましい。
本発明のエポキシ樹脂組成物を硬化してなる硬化物のガラス転移温度は、90~250℃であることが好ましく、より好ましくは90~220℃であり、更に好ましくは95~200℃である。ガラス転移温度を90℃以上とすることにより、樹脂硬化物に高い耐熱性を与え、高温環境下で使用の際に炭素繊維強化複合材料が変形するのを防ぐ効果が得られやすくなる。ガラス転移温度を250℃以下とすることにより、樹脂硬化物の脆化を防ぎ、炭素繊維強化複合材料の引張強度や耐衝撃性を高いレベルで維持できるようになる。ここでいうガラス転移温度は、幅12.7mm、長さ45mm、厚み2mmの樹脂硬化物を試験片として用いて、動的粘弾性測定装置ARES(TA Instruments Japan社製)を用い、ねじりモード(周波数1Hz)にて5℃/minの昇温速度で昇温することにより測定し、ガラス転移温度はG’のガラス転移による階段状変化部分より低温側のベースラインと、階段状変化部分の勾配が最大となる点で引いた接線との交点、すなわち補外ガラス転移開始温度を意味する。
本発明のエポキシ樹脂組成物を硬化してなる硬化物のJIS K7171(1999)に従って測定されるたわみ量は、2mm以上であることが好ましく、さらに好ましくは2.5mm以上である。上記硬化物のたわみ量を2mm以上とすることにより、該プリプレグを硬化させてなる炭素繊維強化複合材料には、好適な非繊維方向の強度や層間剪断強度が得られやすくなる。たわみ量は大きければ大きいほど好ましいが、本発明において、得られるたわみ量の上限は6mm程度である。
本発明のエポキシ樹脂組成物は、短時間で大量に生産できることが望まれる産業材料用途、特に電子電気部品筐体などの用途では、短時間で硬化することが好ましく、具体的には、成形温度におけるゲル化時間が3分以下であることが好ましい。また、生産性を向上する目的においては、より短時間でゲル化することが望ましい。ここでいうエポキシ樹脂組成物のゲル化時間は次のようにして測定することができる。すなわち、エポキシ樹脂組成物を2cm3サンプルとして採取し、加硫/硬化測定試験機キュラストメータV型(JSRトレーディング(株)製)を用いて150℃に加熱したダイスにサンプルを入れ、ねじり応力をかけてサンプルの硬化の進行にともなう粘度上昇をダイスに伝わるトルクとして測定する。測定開始後、トルクが0.005N・mに達するまでの時間をゲル化時間とする。
本発明のプリプレクは、強化繊維として炭素繊維を用いる。炭素繊維を用いることにより、繊維強化複合材料に優れた難燃性、強度、耐衝撃性を発現させることができる。
本発明の炭素繊維強化複合材料は、電子電気部品筐体として好ましく用いられる。特に、本発明で得られる電子電気部品筐体は、強度、軽量性および難燃性が要求されるものに好適である。
別の部材として接合させる金属材料としては、例えば、アルミニウム、鉄、マグネシウム、チタンおよびこれらの合金などが挙げられる。
特に、別の部材として接合させる熱可塑性樹脂として強化繊維で強化された熱可塑性樹脂を用いると、別の部材として接合させる金属材料を接合させた場合には実現できない軽量性が得られるので好ましい。
本発明の炭素繊維強化複合材料と別の部材を接合させる目的で、接着剤を用いたり、熱可塑性樹脂組成物層を介して溶着させたりしても良い。また、嵌合や嵌め込み、ボルト、ネジなどの機械接合などを行っても良い。
(1)樹脂組成物の各成分と炭素繊維
エポキシ樹脂
“エピクロン(登録商標)”N-770(固形フェノールノボラック型エポキシ樹脂、式(I)中のR=H、式(I)で表される化合物の含有率91%、DIC(株)製)
“jER(登録商標)”154(半固形フェノールノボラック型エポキシ樹脂、式(I)中のR=H、式(I)で表される化合物(の含有率83%、ジャパンエポキシレジン(株)製)
“jER(登録商標)”152(半固形フェノールノボラック型エポキシ樹脂、式(I)中のR=H、式(I)で表される化合物の含有率62%、ジャパンエポキシレジン(株)製)
“jER(登録商標)”806(液状ビスフェノールF型エポキシ樹脂、式(I)で表される化合物の含有率0%、ジャパンエポキシレジン(株)製)
“jER(登録商標)”828(液状ビスフェニールA型エポキシ樹脂、式(I)で表される化合物の含有率0%、ジャパンエポキシレジン(株)製)
“jER(登録商標)”834(液状ビスフェニールA型エポキシ樹脂、式(I)で表される化合物の含有率0%、ジャパンエポキシレジン(株)製)
“jER(登録商標)”1001(固形ビスフェニールA型エポキシ樹脂、式(I)で表される化合物の含有率0%、ジャパンエポキシレジン(株)製)
ここでいう「式(I)で表される化合物の含有率」とは、上記エポキシ樹脂市販品中に含まれる、式(I)で表される化合物(nが1以上の化合物)の含有率を表す。
Dicy7(ジシアンジアミド、ジャパンエポキシレジン(株)製)
“オミキュア(登録商標)”24(2,4’-トルエンビス(3,3-ジメチルウレア)、ピイ・ティ・アイ・ジャパン(株)製)
“オミキュア(登録商標)”52(4,4’-メチレンビス(ジフェニルジメチルウレア)、ピイ・ティ・アイ・ジャパン(株)製)
DCMU-99(3,4-ジクロロフェニル-1,1-ジメチルウレア、保土谷化学工業(株)製)
2P4MHZ(2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール、四国化成工業(株)製)
リン酸エステル(成分[C])
PX-200(レゾルシノールビス(ジ2,6-キシリル)ホスフェート、リン含有率9.0%、大八化学工業(株)製)
CR-733S(レゾルシノールビス(ジホスフェート)、リン含有率10.9%、大八化学工業(株)製)
ホスファゼン化合物(成分[D])
SPB-100(ホスホニトリル酸フェニルエステル、リン含有率13.4%、大塚化学(株)製)
FP-110(ホスホニトリル酸フェニルエステル、リン含有率13.4%、伏見製薬所製)
熱可塑性樹脂
YP-50(ビスフェノールA型フェノキシ樹脂、東都化成(株)製)
YP-70(ビスフェノールA型・F型共重合フェノキシ樹脂、東都化成(株)製)
FX-316(ビスフェノールF型フェノキシ樹脂、東都化成(株)製)
“ビニレック(登録商標)”K(ポリビニルホルマール、チッソ(株)製)
炭素繊維
“トレカ(登録商標)”T700SC-12000(引張強度4.9GPa、引張弾性率230GPa、東レ(株)製)。
(2)エポキシ樹脂組成物の調合
ニーダー中に、エポキシ樹脂、熱可塑性樹脂、リン酸エステル、ホスファゼン化合物を所定量加え、混錬しつつ、160℃の温度まで昇温させ、固形成分を完全に溶解させることにより透明な粘調液を得た。混錬を続けたまま50~60℃の温度まで降温させ、有機窒素化合物硬化剤を所定量加えて均一に分散するように30分撹拌し、エポキシ樹脂組成物を得た。
エポキシ樹脂組成物から2cm3をサンプルとして準備し、樹脂の硬化を追跡するためにキュラストメータV型(JSRトレーディング(株)製)を用いて、150℃の温度でゲル化時間を測定した。測定開始後、トルクが0.005N・mに達した時間をゲル化時間とした。
未硬化のエポキシ樹脂組成物を真空中で脱泡した後、2mm厚の“テフロン(登録商標)”製スペーサーにより厚み2mmになるように設定したモールド中で、25℃から1.5℃/分の昇温速度で昇温後、150℃の温度で3分、その後130℃の温度で2時間硬化させ厚さ2mmの樹脂硬化物を得た。この樹脂硬化物から、幅12.7mm、長さ45mmの試験片を切り出し、動的粘弾性測定装置ARES(TA Instruments Japan社製)を用い、周波数1Hz、温度25~250℃、5℃/minで昇温することにより測定した。ガラス転移温度はG’のガラス転移による階段状変化部分より低温側のベースラインと、階段状変化部分の勾配が最大となる点で引いた接線との交点、すなわち補外ガラス転移開始温度をガラス転移温度とした。
上記(4)で得られた樹脂硬化物から幅10mm、長さ60mmの試験片を切り出し、インストロン万能試験機(インストロン社製)を用い、スパン32mm、クロスヘッド速度2.5mm/分とし、JIS K7171(1999)にしたがって3点曲げを実施し、弾性率およびたわみ量を得た。サンプル数をn=5とし、その平均値で比較した。
本発明において、プリプレグは、下記のようにして作製した。リバースロールコーターを用いて、離型紙上に、上記(2)で得られたエポキシ樹脂組成物を塗布して25g/m2目付の樹脂フィルムを作製した。次に、単位面積当たりの繊維質量が100g/m2となるようにシート状に一方向に整列させた炭素繊維に上記の樹脂フィルムを両面から重ね、温度95℃、圧力0.2MPaの条件で加熱加圧してエポキシ樹脂組成物を含浸させ、Wfが67%の一方向プリプレグを作製した。
プリプレグのタック値をタックテスタ(PICMAタックテスタII:東洋精機(株)製)を用い、18×18mmのカバーガラスを0.4kgfの力で5秒間プリプレグに圧着し、30mm/分の速度にて引張り、剥がれる際の抵抗力にて測定した。ここで、タック性は、以下の3段階で評価した。測定数はn=7とし、最上下の2点を外した5点の平均値で評価した。
○:タック値が0.3kg以上、2.0kg以下であり、程良い粘着性を示す。
△:タック値が0.1kg以上、0.3kg未満、または2.0kgより大きく3.0kg以下であり、粘着性がやや強すぎる、もしくはやや弱い。
×:タック値が0.0kg以上0.1kg未満、または3.0kgより大きく、粘着性が強すぎる、もしくは粘着性がない。
プリプレグを、繊維方向に揃えて積層し、加熱プレスによる成形を150℃の温度で3分、0.6MPaの圧力下で行い、炭素繊維強化複合材料を得た。得られた炭素繊維強化複合材料から質量10mgの試験片をカットしてサンプルを準備し、JIS K7121(1987)にしたがって、示差走査熱量計(DSC)を用いてガラス転移温度を測定した。測定条件は、窒素雰囲気下で、昇温速度は40℃/minとし、DSC曲線が階段状変化を示す部分の中間点ガラス転移温度を求めた。示差走査熱量計として、Pyris DSC(パーキンエルマー・インスツルメント社製)を用いた。
プリプレグを、繊維方向に揃えて積層し、加熱プレスによる成形を150℃の温度で3分、0.6MPaの圧力下で行い、それぞれ厚さ0.6-0.7mm、および0.19-0.21mmの炭素繊維強化複合材料板を得て、それぞれの難燃性を測定した。
プリプレグを、繊維方向に揃えて積層し、加熱プレスによる成形を150℃の温度で3分、0.6MPaの圧力下で行い、厚さ1±0.05mmの一方向の炭素繊維強化複合材料板を得た。得られた炭素繊維強化複合材料の両面に長さ56mm、厚さ1.5mmのガラスタブを接着した後、0°方向が長さ方向になるように幅12.7±0.1mm、長さ250±5mmの試験片を切り出し、ASTM D3039記載の方法に準じて引張速度2.0mm/分で試験し、0°引張強度を測定した。試験数はn=6とし、平均値を0°引張強度とした。
プリプレグを(0/90/45)sの構成で積層し、加熱プレスによる成形を150℃の温度で3分、0.6MPaの圧力下で行い、厚さ0.6±0.05mm厚の炭素繊維強化複合材料板を得た。得られた炭素繊維強化複合材料から45°方向が長さ方向になるように試験片を切り出して枠型に固定し、固定部分を除く試験片の大きさが幅70mm、長さ100mmとなるようにした。インストロン万能試験機(インストロン社製)を用い、圧子直径20mm、クロスヘッド速度5mm/分にて測定を行い、50Nの荷重をかけたときのたわみ量を求めた。試験数はn=5とし、平均値をたわみ量とした。
プリプレグを、繊維方向に揃えて積層し、オートクレーブによる成形を150℃の温度で3分、0.6MPaの圧力下で行い、厚さ3±0.05mmの一方向の炭素繊維強化複合材料板を得た。得られた炭素繊維強化複合材料から、0°方向が長さ方向になるように幅10±0.2mm、長さ80±1mmの試験片を切り出し、JIS K7077記載の方法に準じて試験片支持台間の距離60mm、ハンマーの回転軸まわりのモーメント295N・m、持上角度134.5°として試験片中央に衝撃を与え、試験片破談後のハンマーの振り上がり角度からシャルピー衝撃値を求めた。なお、試験には米倉製作所(株)製シャルピー衝撃試験機を用いた。
表1に示す通り、成分[A]として“エピクロン(登録商標)”N-770および“jER(登録商標)”154、成分[B]としてDicy7および“オミキュア(登録商標)”24、成分[C]としてPX-200、成分[D]としてSPB-100、熱可塑性樹脂としてYP-50を用いて、成分[A]中の式(I)で表される化合物の含有率=87%、リン含有率1.2%となるように調整したところ、エポキシ樹脂組成物のゲル化時間は87秒となり3分で硬化可能であり、樹脂硬化物のTgは160℃と良好な結果を示した。樹脂硬化物の弾性率は3.8GPa、たわみ量は3.3mmとバランスが良い特性を示した。また、複合材料の難燃性は、厚み0.6-0.7mmでV-1、厚み0.19-0.21mmでV-0を達成し十分な難燃性を得た。複合材料の150℃、3分硬化後のTgは153℃で十分に高く、0°引張強度、成型品の剛性、シャルピー衝撃値等の力学特性も良好であった。
成分[B]の“オミキュア(登録商標)”24に代えて“オミキュア(登録商標)”52を用い、成分[D]のSPB-100を5部から10部に増量してリン含有率1.7%となるように調整し、熱可塑性樹脂をYP-50に代えてYP-70を用いた以外は実施例1と同様にして樹脂硬化物、プリプレグ、複合材料を作製した。複合材料の難燃性を評価したところ、厚み0.6-0.7mmおよび0.19-0.21mmでともにV-0を達成した。樹脂硬化物特性、複合材料特性、成型品特性も良好であった。
成分[C]と成分[D]の合計配合量を30質量部に増量し、実施例2と同様に熱可塑性樹脂をとしてYP-70を用いた以外は実施例1と同様にして樹脂硬化物、プリプレグ、複合材料を作製した。特性を評価したところ、複合材料の難燃性は、厚み0.6-0.7mmおよび0.19-0.21mmでV-0を達成した。リン酸エステルを20質量部配合した実施例3では複合材料のTgがやや低くなったものの問題のないレベルであり、その他の特性は良好であった。
成分[B]の“オミキュア(登録商標)”24の配合量を6質量部に増量し、また成分[C]と成分[D]の合計配合量を50部に増量してリン含有率3.3%となるように調整し、実施例2同様に熱可塑性樹脂としてYP-70を用いた以外は、実施例1と同様にして樹脂硬化物、プリプレグ、複合材料を作製した。ゲル化時間は130秒とやや遅く、樹脂硬化物のTg、複合材料のTg、成型品のシャルピー衝撃値がやや低いものの問題のないレベルであり、その他の特性は良好であった。
成分[A]として“エピクロン(登録商標)”N-770、“jER(登録商標)”152、成分[B]としてDicy7、“オミキュア(登録商標)”24を用いて、成分[A]中の式(I)で表される化合物の含有率=82%とした以外は、実施例2と同様にして樹脂硬化物、プリプレグ、複合材料を作製した。特性を評価したところ、樹脂硬化物特性、複合材料特性、成型品特性は良好であった。プリプレグのタック性も実施例1~5と比べて高く、適性であった。
成分[A]として“jER(登録商標)”154、“jER(登録商標)”152、jER(登録商標)”806を用い、熱可塑性樹脂のYP-70を5質量部に増量し、成分[A]中の式(I)で表される化合物の含有率=63%として樹脂硬化物、プリプレグ、複合材料を作製した。複合材料の難燃性は、厚み0.6-0.7mmでV-1、厚み0.19-0.21mmでV-0であった。また、成分[A]中の式(I)で表される化合物の含有率がより高い実施例6と比較すると、ゲル化時間がやや遅くなったものの問題のないレベルであり、その他の特性については良好であった。
成分[A]としてN-770、“jER(登録商標)”828を用い、成分[A]中の式(I)で表される化合物の含有率=55%として樹脂硬化物、プリプレグ、複合材料を作製した。複合材料の難燃性は厚み0.6-0.7mmおよび厚み0.19-0.21mmでともにV-1であった。成分[C]の配合が同様である実施例2、実施例6および実施例7と比較すると、ゲル化時間は136秒と遅くなり複合材料のTgは低下したものの、問題のないレベルであり、その他の特性については同様に良好であった。
成分[C]としてPX-200に代えてCR-733Sを用いた以外は実施例3と同様にして樹脂硬化物、プリプレグ、複合材料を作製した。実施例3と比較すると、ゲル化時間が147秒と遅く、樹脂硬化物のたわみ量、複合材料のTgおよびシャルピー衝撃値がやや低い値を示したものの、問題のないレベルであった。複合材料の難燃性は、厚み0.6-0.7mmおよび厚み0.19-0.21mmでともにV-0を達成した。
成分[B]としてDCMU-99を用いて樹脂硬化物、プリプレグ、複合材料を作製した。“オミキュア(登録商標)”52および“オミキュア(登録商標)”24を用いた実施例2、3と比較すると、ゲル化時間が141秒と遅く、複合材料のTgが低いものの問題のないレベルであり、複合材料の難燃性は、厚み0.6-0.7mmおよび厚み0.19-0.21mmでV-0を達成し、その他の特性についても良好であった。
実施例10同様に成分[B]としてDCMU-99を用いて樹脂硬化物、プリプレグ、複合材料を作製した。ゲル化時間が131秒とやや遅く、複合材料のTgが低いものの問題のないレベルであり、複合材料の難燃性は、厚み0.6-0.7mmおよび厚み0.19-0.21mmでV-0を達成し、その他の特性についても良好であった。
成分[B]として2P4MHZを用いて樹脂硬化物、プリプレグ、複合材料を作製した。特性を評価したところ、複合材料の難燃性は、厚み0.6-0.7mmおよび0.19-0.21mmでV-0を達成し、樹脂硬化物特性、複合材料特性、成型品特性も良好であった。
熱可塑性樹脂として“ビニレック(登録商標)”Kを用いて樹脂硬化物、プリプレグ、複合材料を作製した。特性を評価したところ、成型品の0°引張強度とシャルピー衝撃値がやや低い値となったものの、問題のないレベルであり、その他の特性は良好な結果を示した。
成分[A]として“エピクロン(登録商標)”N-770、“jER(登録商標)”806および“jER(登録商標)”828を用い、式(I)で表される化合物中のnが2以上の化合物の含有率を92%と高め、かつ式(II)で表される化合物の含有率が32%となるように調整して樹脂硬化物、プリプレグ、複合材料を作製した。特性を評価したところ、複合材料の難燃性は、厚み0.6-0.7mmおよび0.19-0.21mmでV-0を達成し、プリプレグのタック性も適性であった。樹脂硬化物特性、複合材料特性、成型品特性についても良好であった。
成分[A]として“エピクロン(登録商標)”N-770、“jER(登録商標)”154および“jER(登録商標)”828を用いて、実施例14、15と同様にして樹脂硬化物、プリプレグ、複合材料を作製した。特性を評価したところ、複合材料の難燃性は、厚み0.6-0.7mmおよび0.19-0.21mmでV-0を達成し、プリプレグのタック性も適性であった。樹脂硬化物特性、複合材料特性、成型品特性についても良好であった。
成分[A]として“エピクロン(登録商標)”N-770を単独で用いて樹脂硬化物、プリプレグ、複合材料を作製した。樹脂硬化物特性、複合材料特性、成型品特性については良好であったが、プリプレグのタック性がなく、取り扱いが困難であった。
成分[A]として“jER(登録商標)”154を単独で用いて樹脂硬化物、プリプレグ、複合材料を作製した。特性を評価したところ、複合材料の難燃性は、厚み0.6-0.7mmでV-1、厚み0.19-0.21mmでV-0を達成し、その他の特性についても良好であった。
成分[D]を含まず、成分[C]としてPX-200を単独で15質量部用いて、リン含有率1.1%となるように調整して樹脂硬化物、炭素繊維強化複合材料を作製した。特性を評価したところ、複合材料の難燃性は、厚み0.6-0.7mmおよび0.19-0.21mmでV-outとなり不合格であった。
成分[D]を含まず、成分[C]としてCR-733Sを単独で30質量部用いて、リン含有率2.3%となるように調整して樹脂硬化物、プリプレグ、複合材料を作製した。特性を評価したところ、複合材料の難燃性は、厚み0.6-0.7mmおよび0.19-0.21mmでV-0を達成したが、樹脂硬化物の弾性率が4.1GPaと高い反面、たわみ量が1.9mmと低く、複合材料の0°引張強度、成型品のシャルピー衝撃値も低い値となった。
成分[C]を含まず、成分[D]としてSPB-100を単独で30質量部用いて、リン含有率2.8%となるように調整して樹脂硬化物、プリプレグ、複合材料を作製した。特性を評価したところ、樹脂硬化物の弾性率が2.3GPaと低くなり、成型品のたわみ量が大きく剛性が低い結果となった。
エポキシ樹脂として“jER(登録商標)”154を50質量部、“jER(登録商標)”828を50質量部、成分[C]としてPX-200、成分[D]としてSPB-100をそれぞれ10質量部用いて、成分[A]中の式(I)で表される化合物の含有率=42%、リン含有率1.7%となるように調整して、樹脂硬化物、プリプレグ、複合材料を作製した。特性を評価したところ、複合材料の難燃性は、厚み0.6-0.7mmおよび0.19-0.21mmでともにV-outとなり不合格であった。
エポキシ樹脂として“jER(登録商標)”154、“jER(登録商標)”828、“jER(登録商標)”834、“jER(登録商標)”1001、成分[C]としてCR-733を25質量部用いエポキシ樹脂中の式(I)で表される化合物/[A]=26%、リン含有率2.0%となるようにとし、熱可塑性樹脂として“ビニレック(登録商標)”Kを5質量部用いて調整し、樹脂硬化物、プリプレグ、複合材料を作製した。特性を評価したところ、ゲル化時間が195秒と遅くなり、複合材料のTgも69℃と低い値を示した。成型品の0°引張強度、シャルピー衝撃値も低い値を示した。
Claims (7)
- さらにエポキシ樹脂組成物が熱可塑性樹脂を含み、該熱可塑性樹脂がフェノキシ樹脂である請求項1に記載のエポキシ樹脂組成物。
- 請求項1または2に記載のエポキシ樹脂組成物を炭素繊維に含浸させてなるプリプレグ。
- 請求項3に記載のプリプレグを、加熱硬化せしめてなる炭素繊維強化複合材料。
- リン含有率が1.2~4質量%である請求項1または2に記載のエポキシ樹脂組成物、および炭素繊維を有してなるプリプレグを用いて得られる炭素繊維強化複合材料であって、厚さ2mm以下で、UL94燃焼試験における難燃性がV-1以上であることを特徴とする炭素繊維強化複合材料。
- 請求項3に記載のプリプレグを成形する炭素繊維強化複合材料の製造方法であって、成形がプレス成型である炭素繊維強化複合材料の製造方法。
- 請求項4または5のいずれかに記載の炭素繊維強化複合材料、または請求項6に記載の方法で得られる炭素繊維強化複合材料を用いた電子電気部品筐体。
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- 2010-02-04 WO PCT/JP2010/051589 patent/WO2010109957A1/ja active Application Filing
- 2010-02-04 JP JP2010507166A patent/JP5614280B2/ja active Active
- 2010-02-04 CN CN201080010992.6A patent/CN102341429B/zh active Active
- 2010-02-04 KR KR1020117022253A patent/KR101530754B1/ko active IP Right Grant
- 2010-02-04 US US13/255,223 patent/US20110319525A1/en not_active Abandoned
- 2010-03-24 TW TW099108628A patent/TW201041929A/zh unknown
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JP2011068772A (ja) * | 2009-09-25 | 2011-04-07 | Namics Corp | エポキシ樹脂組成物、および、それによる接着フィルム |
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JP5648685B2 (ja) * | 2011-03-22 | 2015-01-07 | 三菱レイヨン株式会社 | エポキシ樹脂組成物、プリプレグ、繊維強化複合材料、電子・電気機器用筐体 |
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JP2016148020A (ja) * | 2015-02-09 | 2016-08-18 | 東レ株式会社 | エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料 |
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JP2016148021A (ja) * | 2015-02-09 | 2016-08-18 | 東レ株式会社 | エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料 |
WO2017047439A1 (ja) * | 2015-09-18 | 2017-03-23 | 東レ株式会社 | 筐体 |
US10571963B2 (en) | 2015-09-18 | 2020-02-25 | Toray Industries, Inc. | Housing |
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Also Published As
Publication number | Publication date |
---|---|
EP2412741A1 (en) | 2012-02-01 |
EP2412741A4 (en) | 2015-12-09 |
KR101530754B1 (ko) | 2015-06-22 |
JPWO2010109957A1 (ja) | 2012-09-27 |
EP2412741B1 (en) | 2019-10-23 |
CN102341429B (zh) | 2015-04-01 |
US20110319525A1 (en) | 2011-12-29 |
CN102341429A (zh) | 2012-02-01 |
TW201041929A (en) | 2010-12-01 |
KR20120000063A (ko) | 2012-01-03 |
JP5614280B2 (ja) | 2014-10-29 |
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