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
• • 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
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/06—Elements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
  • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
• • 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
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/28—Shaping operations therefor
  • B29C70/40—Shaping or impregnating by compression not applied
  • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
  • B29K2029/14—Polyvinylacetals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0094—Condition, form or state of moulded material or of the material to be shaped having particular viscosity
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
  • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
  • B29K2105/0872—Prepregs
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2307/00—Use of elements other than metals as reinforcement
  • B29K2307/04—Carbon
• • 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
• • 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
  • C08J2363/02—Polyglycidyl ethers of bis-phenols
• • 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
  • C08J2400/00—Characterised by the use of unspecified polymers
• • 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
  • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
  • C08J2429/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols

Definitions

• the present invention relates to a carbon fiber reinforced composite material and a method for producing the carbon fiber reinforced composite material.
• Fiber-reinforced plastic one of fiber-reinforced composite materials, is lightweight, high-strength, and high-rigidity. It is used for a wide range of purposes.
• a method for producing fiber-reinforced plastics there is a method of using an intermediate material, that is, a prepreg, in which a reinforcing material made of long fibers (continuous fibers) such as reinforcing fibers is impregnated with a matrix resin. This method has the advantage that it is easy to control the content of the reinforcing fibers in the fiber-reinforced plastic and that the content can be designed to be high.
• Epoxy resins are preferably used as matrix resins for such fiber-reinforced composite materials because of their excellent moldability. Epoxy resins are used in a wide range of industrial fields because fiber-reinforced composite materials with excellent mechanical properties and heat resistance can be obtained even after curing.
• Patent Document 1 describes a prepreg containing predetermined amounts of reinforcing fiber, epoxy resin, carboxyl group-containing polyvinyl formal resin, and amine curing agent.
• Patent Document 2 describes a prepreg for a fiber-reinforced composite material containing predetermined amounts of an epoxy resin, a thermoplastic resin soluble in the epoxy resin, and a latent curing agent.
• Patent Document 3 describes a prepreg obtained by impregnating reinforcing fibers with an epoxy resin composition containing an epoxy compound, a curing agent, and a polyvinyl acetal resin.
• the present invention provides a carbon fiber reinforced composite material and a method for producing a carbon fiber reinforced composite material that can reduce resin exudation, shorten the curing time, and achieve high mechanical strength. intended to provide
• the present disclosure (1) is a carbon fiber reinforced composite material containing carbon fiber, an epoxy resin, a curing agent, and a thermoplastic resin, wherein the mixture of the epoxy resin and the thermoplastic resin has a viscosity at 30° C. and The carbon fiber reinforced composite material has a viscosity ratio at 90°C (viscosity at 30°C/viscosity at 90°C) of less than 100.
• the present disclosure (2) is the carbon fiber reinforced composite material according to the present disclosure (1), wherein the thermoplastic resin has a glass transition temperature of 60° C. or higher.
• the present disclosure (3) is the carbon fiber reinforced composite material according to the present disclosure (1) or (2), wherein the thermoplastic resin is a polyvinyl acetal resin.
• the present disclosure (4) is the carbon fiber reinforced composite material according to the present disclosure (3), wherein the polyvinyl acetal resin contains a structural unit represented by the following formula (1).
• R 1 represents an alkyl group having 1 or more carbon atoms. Also, R 1 may be the same or different.
• the present disclosure (5) is the carbon fiber reinforced composite according to any one of the present disclosure (1) to (4), wherein the polyvinyl acetal resin has a hydroxyl group content of 16.0 mol% or more and 45.0 mol% or less. material.
• the present disclosure (6) is the carbon fiber reinforced composite material according to any one of the present disclosures (1) to (5), which is used as a prepreg.
• the present disclosure (7) is the carbon fiber reinforced composite material according to any one of the present disclosure (1) to (6), wherein the epoxy resin contains a bisphenol A type epoxy resin.
• the present disclosure (8) is the carbon fiber according to any one of the present disclosure (1) to (7), which contains 0.01 parts by weight or more and 40 parts by weight or less of a thermoplastic resin with respect to 100 parts by weight of the epoxy resin. It is a reinforced composite material.
• the present disclosure (9) is the carbon fiber reinforced according to any one of the present disclosure (1) to (8), which contains 0.5 parts by weight or more and 300 parts by weight or less of an epoxy resin with respect to 100 parts by weight of the carbon fiber. Composite material.
• the present disclosure includes at least a step of producing a resin composition containing an epoxy resin, a curing agent, and a thermoplastic resin, and a step of compounding the resin composition with carbon fibers,
• the present invention will be described in detail below.
• the present inventors have found a carbon fiber reinforced composite material containing carbon fiber, an epoxy resin, a curing agent, and a thermoplastic resin, wherein the mixture of the epoxy resin and the thermoplastic resin has a predetermined viscosity characteristic. have found that it is possible to shorten the curing time and achieve high mechanical strength while reducing resin exudation, and have completed the present invention.
• the present invention contains carbon fiber, an epoxy resin, a curing agent, and a thermoplastic resin, and the mixture of the epoxy resin and the thermoplastic resin (hereinafter also simply referred to as the mixture) has a viscosity at 30 °
• the viscosity ratio (viscosity at 30° C./viscosity at 90° C.) is less than 100.
• the mixture contains the epoxy resin and the thermoplastic resin at a mixing weight ratio of 9:1. When the viscosity ratio of the mixture is less than 100, it is possible to shorten the curing time while reducing resin exudation, and achieve high mechanical strength.
• a preferable lower limit of the viscosity ratio of the mixture is 1, and a more preferable lower limit is 3.
• a preferable upper limit of the viscosity ratio is 95, and a more preferable upper limit is 50.
• the above viscosity is a sample ( mixture) can be obtained by measuring with a rheometer. For example, it means the viscosity at 30° C. and 90° C. measured under the conditions of using a 20 mm parallel plate, cooling rate: 5° C./min, number of revolutions: 100 rpm, and gap: 500 ⁇ m.
• the epoxy resin and thermoplastic resin used in the above viscosity measurement mean the epoxy resin and thermoplastic resin contained in the carbon fiber reinforced composite material.
• the mixing ratio of the epoxy resin and the thermoplastic resin when measuring the viscosity can be measured in the range of 100:43 to 100:0.1 for the epoxy resin:thermoplastic resin. More preferably, the above range is 100:30 to 100:0.1.
• the viscosity ratio of the mixture can be adjusted according to the type of thermoplastic resin, average degree of polymerization, glass transition temperature, type of epoxy resin, and the like. Moreover, when using a polyvinyl acetal resin as a thermoplastic resin, it can also be adjusted by the degree of acetalization, the amount of hydroxyl groups, the amount of acetyl groups, and the like. When a polyvinyl acetal resin is used as the thermoplastic resin, reducing the number of carbon atoms in the acetal group (the number of carbon atoms in the starting aldehyde) increases the viscosity at 30° C., increasing the viscosity ratio.
• the preferred lower limit of the viscosity of the mixture at 30° C. is 10 Pa ⁇ s, and the preferred upper limit is 1500 Pa ⁇ s.
• a more preferable lower limit of the viscosity at 30° C. is 30 Pa ⁇ s, and a more preferable upper limit is 1000 Pa ⁇ s.
• the above mixture has a preferable lower limit of viscosity at 90° C. of 0.01 Pa ⁇ s and a preferable upper limit of 10 Pa ⁇ s.
• a more preferable lower limit of the viscosity at 90° C. is 0.1 Pa ⁇ s, and a more preferable upper limit is 5 Pa ⁇ s.
• the carbon fiber reinforced composite material of the present invention contains a thermoplastic resin.
• the thermoplastic resin include polyolefin, polyester, (meth)acrylic resin, polyamide, polyurethane, ABS resin, AES resin, AAS resin, MBS resin, anion/styrene copolymer, styrene/methyl (meth)acrylate copolymer, Polymer, polystyrene, polycarbonate, polyphenylene oxide, phenoxy resin, polyphenylene sulfide, polyimide, polyetheretherketone, polyethersulfone, polysulfone, polyarylate, polyetherketones, polyethernitrile, polythioethersulfone, polybenzimidazole, poly Examples include carbodiimide, polyvinyl alcohol resin, polyvinyl acetal resin, and the like.
• thermoplastic resin it is preferable to use a resin having a Tg (glass transition temperature) of 60° C. or higher, which will be described later.
• the polyolefin include polyethylene, polypropylene, ethylene/vinyl acetate copolymer, ethylene/(meth)acrylic acid copolymer, ethylene/methyl(meth)acrylate copolymer, ethylene/ethyl(meth)acrylate. copolymers, ethylene/vinyl alcohol copolymers, ethylene/ethyl (meth)acrylate/maleic anhydride copolymers, and the like.
• the (meth)acrylic resin include polymethyl (meth)acrylate.
• Polyvinyl acetal resin is particularly preferable as the thermoplastic resin. The above thermoplastic resins may be used alone, or two or more of them may be used in combination.
• the polyvinyl acetal resin preferably contains a structural unit represented by the following formula (1).
• R 1 represents an alkyl group having 1 or more carbon atoms. Also, R 1 may be the same or different.
• R 1 is preferably an alkyl group having 1 or more carbon atoms.
• the number of carbon atoms is preferably 1 or more, and preferably 6 or less.
• R 1 in formula (1) is preferably an alkyl group having 1 or more carbon atoms and/or an alkyl group having 3 or more carbon atoms.
• the above R 1 may be the same or may be a combination of different ones.
• the above R 1 is a combination of different ones, it is preferably a combination of an alkyl group having 1 or more carbon atoms and an alkyl group having 3 or more carbon atoms.
• the alkyl group is not particularly limited as long as it is an alkyl group having 1 or more carbon atoms. Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group and sec-butyl group. group, tert-butyl group, and the like.
• pentyl group hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group and the like.
• a methyl group and an n-propyl group are preferred.
• the preferable lower limit of the content of the structural unit having an acetal group represented by the general formula (1) is 30 mol%, and the preferable upper limit thereof is 85 mol%.
• the acetal group content is 30 mol % or more, a polyvinyl acetal resin having excellent toughness can be obtained.
• the amount of acetal groups is 85 mol % or less, the compatibility with epoxy resins can be improved.
• a more preferable lower limit of the acetal group content is 60 mol %, and a more preferable upper limit thereof is 80 mol %.
• the acetal group of the polyvinyl acetal resin is obtained by acetalizing the structural unit having two hydroxyl groups of the polyvinyl alcohol resin.
• the amount of acetal groups is calculated by employing a method of counting structural units having two hydroxyl groups.
• the preferred lower limit of the content of the structural unit (hereinafter also referred to as “degree of acetoacetalization”) is 5 mol%, which is preferred.
• the upper limit is 85 mol%.
• the compatibility with the epoxy resin can be maintained and excellent viscosity characteristics can be obtained.
• the preferred lower limit of the content of the structural unit (hereinafter also referred to as "butyralization degree”) is 0.5. 1 mol %, the preferred upper limit is 80 mol %.
• the compatibility with the epoxy resin can be maintained and excellent viscosity characteristics can be obtained.
• the ratio of the degree of acetoacetalization to the degree of butyralization is preferably 0.06 or more and 850 or less. Moreover, it is more preferable that the ratio is 0.1 or more and 375 or less.
• the preferable lower limit of the content of the structural unit having a hydroxyl group represented by the general formula (2) (hereinafter also referred to as "hydroxyl group content”) is 15.0 mol%, and the preferable upper limit is 45.0. in mol %.
• the amount of hydroxyl groups is 15.0 mol % or more, a polyvinyl acetal resin having excellent adhesiveness can be obtained. Compatibility with an epoxy resin can fully be improved as the said amount of hydroxyl groups is 45.0 mol% or less.
• the hydroxyl group amount has a more preferable lower limit of 16.0 mol%, a more preferable lower limit of 18.0 mol%, a still more preferable lower limit of 20.0 mol%, a more preferable upper limit of 40.0 mol%, and a further preferable upper limit of 38.0 mol %.
• the content of the structural unit having an acetyl group represented by the general formula (3) (hereinafter also referred to as "acetyl group content”) preferably has a lower limit of 0.1 mol% and a preferred upper limit of 25. in mol %.
• acetyl group content preferably has a lower limit of 0.1 mol% and a preferred upper limit of 25. in mol %.
• the amount of acetyl groups is 0.1 mol % or more, it is possible to suppress an increase in viscosity due to intramolecular and intermolecular hydrogen bonding of hydroxyl groups in the polyvinyl acetal resin.
• the amount of acetyl groups is 25 mol % or less, handleability can be improved without excessively lowering the heat resistance of the polyvinyl acetal resin.
• a more preferred lower limit to the amount of acetyl groups is 0.5 mol%, a more preferred upper limit is 15 mol%, a still more preferred lower limit is 0.8 mol%, and a still more preferred upper limit is 14 mol%.
• the total amount of the acetal group content, the hydroxyl group content and the acetyl group content is preferably more than 95 mol %. More preferably, it is 96 mol % or more.
• the polyvinyl acetal resin preferably has an average degree of polymerization of 2500 or less.
• the average degree of polymerization is 2500 or less, sufficient mechanical strength can be imparted. Further, when the average degree of polymerization is 1000 or less, the solubility in organic solvents can be sufficiently improved, and the coatability and dispersibility can be further improved.
• a more preferable lower limit of the average degree of polymerization is 150, and a more preferable upper limit is 1,000.
• the average degree of polymerization is the same as the average degree of polymerization of the raw material polyvinyl alcohol resin.
• the average degree of polymerization of the starting polyvinyl alcohol resin can be measured according to JIS K6726-1994.
• the thermoplastic resin preferably has a glass transition temperature (Tg) of 60° C. or higher.
• Tg glass transition temperature
• the heat resistance can be improved and the amount of seepage during impregnation can be reduced.
• a more preferable lower limit of the glass transition temperature is 63°C.
• the upper limit of the glass transition temperature is not particularly limited, it is 120°C.
• the glass transition temperature can be measured using a differential scanning calorimeter (DSC).
• the polyvinyl acetal resin can usually be produced by acetalizing a polyvinyl alcohol resin.
• the method of acetalization is not particularly limited, and conventionally known methods can be used. Examples include a method of adding various aldehydes to the solution.
• aldehyde examples include linear, branched, cyclic saturated, cyclic unsaturated or aromatic aldehydes having 1 to 19 carbon atoms. Specific examples include formaldehyde, acetaldehyde, propionylaldehyde, n-butyraldehyde, isobutyraldehyde, tert-butyraldehyde, benzaldehyde, cyclohexylaldehyde and the like.
• the above aldehydes may be used alone, or two or more of them may be used in combination.
• aldehydes other than formaldehyde, cyclic saturated, cyclic unsaturated or aromatic aldehydes are preferred, and acetaldehyde and n-butyraldehyde are particularly preferred.
• the amount of the aldehyde to be added can be appropriately set according to the amount of acetal groups in the desired polyvinyl acetal resin.
• the acetalization reaction is efficiently performed, and unreacted aldehyde It is also preferable because it is easy to remove.
• polyvinyl alcohol resin conventionally known polyvinyl alcohol resins such as resins produced by saponifying polyvinyl acetate with an alkali, an acid, aqueous ammonia or the like can be used.
• the above polyvinyl alcohol resin may be completely saponified, but it is not necessary to be completely saponified if at least one unit having two consecutive hydroxyl groups with respect to the meso- and racemo-positions is present in at least one of the main chains.
• a partially saponified polyvinyl alcohol-based resin is not necessary to be completely saponified if at least one unit having two consecutive hydroxyl groups with respect to the meso- and racemo-positions is present in at least one of the main chains.
• polyvinyl alcohol resin copolymers of vinyl alcohol and monomers copolymerizable with vinyl alcohol, such as ethylene-vinyl alcohol copolymer resins and partially saponified ethylene-vinyl alcohol copolymer resins, can also be used.
• examples of the polyvinyl acetate-based resin include ethylene-vinyl acetate copolymers.
• the polyvinyl acetal resin is preferably an acetalized polyvinyl alcohol resin having a degree of saponification of 75 mol % or more. Moreover, the degree of saponification is more preferably 85 mol % or more and 99.5 mol % or less.
• the holding time after the reaction is preferably 1.5 hours or longer, more preferably 2 hours or longer, although it depends on other conditions.
• the acetalization reaction can be allowed to proceed sufficiently by setting the holding time as described above.
• the holding temperature after the reaction is preferably 15° C. or higher, more preferably 20° C. or higher. By setting it as the said holding temperature, an acetalization reaction can fully be advanced.
• the polyvinyl alcohol resin usually contains a carboxylate, which is a basic component generated during saponification, it is preferable to use it after washing away or neutralizing it.
• the washing method in the washing step include a method of extracting basic components with a solvent, a method of dissolving the resin in a good solvent and then adding a poor solvent to reprecipitate only the resin, and a method of reprecipitating only the resin. and a method of adding an adsorbent to a solution containing to adsorb and remove basic components.
• Examples of the neutralizing agent used in the neutralization step include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; inorganic acids such as carbonic acid; and carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid and hexanoic acid. , aliphatic sulfonic acids such as methanesulfonic acid and ethanesulfonic acid, aromatic sulfonic acids such as benzenesulfonic acid, and phenols such as phenol.
• the content of the thermoplastic resin in the carbon fiber reinforced composite material of the present invention is preferably 0.01 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the epoxy resin. When the content of the thermoplastic resin is within the above range, the mechanical strength of the obtained carbon fiber reinforced composite material can be sufficiently increased. Further, the content of the thermoplastic resin in the carbon fiber reinforced composite material of the present invention is preferably 0.001% by weight or more and preferably 35% by weight or less with respect to the entire composite material. When the content of the thermoplastic resin is within the above range, the mechanical strength of the obtained carbon fiber reinforced composite material can be sufficiently increased.
• the carbon fiber reinforced composite material of the present invention contains carbon fibers.
• the carbon fiber include PAN-based carbon fiber, pitch-based carbon fiber, cellulose-based carbon fiber, and vapor-grown carbon fiber.
• the carbon fiber As the form of the carbon fiber, twisted yarn, untwisted yarn, non-twisted yarn, etc. can be used. Untwisted yarn or untwisted yarn, which has a good balance between the formability and strength characteristics of the carbon fiber reinforced composite material, is preferably used because it causes deterioration of the mechanical properties of the material.
• the carbon fiber may be subjected to an oxidation treatment to introduce an oxygen-containing functional group in order to improve adhesion to the matrix resin.
• Gas-phase oxidation, liquid-phase oxidation, and liquid-phase electrolytic oxidation are used as the oxidation treatment method. Liquid-phase electrolytic oxidation is preferably used from the viewpoint of high productivity and uniform treatment.
• the carbon fiber preferably has a single fiber fineness of 0.2 to 2.0 dtex, more preferably 0.4 to 1.8 dtex.
• the single fiber fineness is 0.2 dtex or more, the carbon fibers are less likely to be damaged due to contact with guide rollers during twisting, and the same damage is less likely to occur during the resin composition impregnation process.
• the single fiber fineness is 2.0 dtex or less, the carbon fibers can be sufficiently impregnated with the resin composition, resulting in improved fatigue resistance.
• the fineness of the carbon fiber is preferably 50 to 1800 tex.
• the number of filaments in one fiber bundle of the carbon fibers is preferably in the range of 2,500 to 100,000.
• the fiber arrangement tends to meander, which tends to cause a decrease in strength. Further, if the number of filaments exceeds 100,000, it may be difficult to impregnate the prepreg with the resin during fabrication or molding.
• the number of filaments is more preferably in the range of 2800-80000.
• the average fiber diameter of the carbon fibers is preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more, preferably 30 ⁇ m or less, and more preferably 26 ⁇ m or less.
• the average fiber length of the carbon fibers is preferably 2 mm or longer, more preferably 4 mm or longer, preferably 100 mm or shorter, and more preferably 80 mm or shorter.
• the form of the carbon fiber is not particularly limited, but examples thereof include fibrous form, woven fabric, knitted fabric, sheet form of nonwoven fabric, and the like.
• the basis weight of the fibers is preferably 100 g/m 2 or more, more preferably 350 g/m 2 or more, and preferably 1000 g/m 2 or less. It is more preferably 650 g/m 2 or less.
• the density of the carbon fibers is preferably 1.0 g/cm 3 or more and 3.0 g/cm 3 or less.
• the carbon fiber content in the carbon fiber reinforced composite material of the present invention is preferably 35% by weight or more and preferably 100% by weight or less. When the carbon fiber content is within the above range, the mechanical strength of the obtained carbon fiber reinforced composite material can be sufficiently increased. Also, the content of the carbon fiber is preferably 50 to 3800 parts by weight with respect to 100 parts by weight of the epoxy resin.
• the carbon fiber reinforced composite material of the present invention contains epoxy resin.
• cross-linking can be achieved by applying energy such as heating, and high adhesiveness can be achieved.
• epoxy resin examples include monofunctional epoxy compounds, bifunctional epoxy compounds, and polyfunctional epoxy compounds such as trifunctional or higher epoxy compounds, and more preferably include monofunctional epoxy compounds and bifunctional epoxy compounds.
• Examples of the monofunctional epoxy compound include (meth)acrylic acid esters having a glycidyl group, aliphatic epoxy resins, aromatic epoxy resins, and the like. Among them, it is preferable to contain a (meth)acrylic acid ester having a glycidyl group.
• Examples of the (meth)acrylic ester having a glycidyl group include glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate glycidyl ether, 2-hydroxypropyl (meth)acrylate glycidyl ether, 3-hydroxypropyl (meth)acrylate ) acrylate glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, polyethylene glycol-polypropylene glycol (meth)acrylate glycidyl ether, and the like.
• Examples of the aliphatic epoxy resin include glycidyl ethers of aliphatic alcohols such as butyl glycidyl ether and lauryl glycidyl ether.
• Examples of the aromatic epoxy resin include phenylglycidyl ether and 4-t-butylphenylglycidyl ether. Among them, (meth)acrylic acid esters having glycidyl groups and aromatic epoxy resins are preferable.
• bifunctional epoxy compound examples include phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alkylphenol type epoxy resin, resorcinol type epoxy resin, and bifunctional naphthalene type epoxy resin.
• Bifunctional aromatic epoxy resins such as resins, bifunctional alicyclic epoxy resins such as dicyclopentadiene dimethanol diglycidyl ether, polyalkylene glycol diglycidyl ethers such as polypropylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether , diglycidyl phthalate, diglycidyl tetrahydrophthalate, difunctional glycidyl ester type epoxy resins such as diglycidyl ester of dimer acid, diglycidyl aniline, difunctional glycidyl amine type epoxy resins such as diglycidyl toluidine, bifunctional heterocyclic Epoxy resins, bifunctional diarylsulfone type epoxy resins, hydroquinone type epoxy resins such as hydroquinone diglycidyl ether, 2,5-di-tert-butylhydroquinone diglycidyl ether, resorcinol diglycidyl ether, butane
• bifunctional epoxy compounds may be used alone or in combination of two or more.
• bifunctional aromatic epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins
• bifunctional alicyclic epoxy resins such as dicyclopentadiene dimethanol diglycidyl ether Epoxy resins and polyalkylene glycol diglycidyl ethers such as polypropylene glycol diglycidyl ethers are preferred.
• tri- or more functional epoxy compounds examples include tri- or more functional aromatic epoxy resins such as tri- or more functional phenol novolac epoxy resins, tri- or more functional alicyclic epoxy resins, and tri- or more functional glycidyl ester type epoxy resins.
• Epoxy resins tri- or higher functional glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenylmethane, triglycidyl-m-aminophenylmethane, tetraglycidyl-m-xylylenediamine, tri- or higher functional Heterocyclic epoxy resins, tri- or more functional diarylsulfone type epoxy resins, tri- or more functional alkylene glycidyl ether compounds such as glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, tri- or more functional glycidyl Examples include group-containing hydantoin compounds, tri- or more functional glycidyl group-containing siloxanes, modified products thereof, and the like.
• the content of the epoxy resin has a preferred lower limit of 3% by weight, a more preferred lower limit of 6.5% by weight, a preferred upper limit of 66% by weight, and a more preferred upper limit of 56% by weight. be. Further, in the present invention, it is preferable to contain 0.5 parts by weight or more and 300 parts by weight or less of the epoxy resin with respect to 100 parts by weight of the carbon fiber. As a result, the curing speed can be shortened and high toughness can be imparted.
• the epoxy equivalent (molecular weight per epoxy group) of the epoxy resin preferably has a lower limit of 100 and a preferred upper limit of 5,000.
• the molecular weight of the epoxy resin has a preferred lower limit of 100 and a preferred upper limit of 70,000.
• the ratio of the thermoplastic resin content to the epoxy resin content preferably has a lower limit of 0.0001.
• a more preferable lower limit is 0.001, a preferable upper limit is 0.4, and a more preferable upper limit is 0.35.
• the carbon fiber reinforced composite material of the present invention contains a curing agent.
• the curing agent include phenol-based curing agents, thiol-based curing agents, amine-based curing agents, imidazole-based curing agents, acid anhydride-based curing agents, cyanate-based curing agents, and active ester-based curing agents.
• amine-based curing agents are preferred.
• amine curing agent examples include trimethylamine, triethylamine, N,N-dimethylpiperazine, triethylenediamine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol. , 1,8-diazabicyclo(5,4.0)-undecene-7, 1,5-diazabicyclo(4,3.0)-nonene-5 and the like.
• imidazole curing agent examples include imidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole and the like.
• the content of the curing agent in the carbon fiber reinforced composite material of the present invention has a preferred lower limit of 0.5 parts by weight, a more preferred lower limit of 1.0 parts by weight, and a preferred upper limit of 100 parts by weight, and a more preferable upper limit is 50 parts by weight. Moreover, the content of the curing agent in the carbon fiber reinforced composite material of the present invention is preferably 0.01 to 80% by weight.
• the carbon fiber reinforced composite material of the present invention may further contain a curing accelerator and an organic solvent.
• the curing accelerator include phosphorus compounds, amine compounds and organometallic compounds.
• the content of the curing accelerator in the carbon fiber reinforced composite material of the present invention has a preferred lower limit of 0.1 parts by weight, a more preferred lower limit of 0.5 parts by weight, and a preferred upper limit of 0.5 parts by weight with respect to 100 parts by weight of the epoxy resin. is 30 parts by weight, and the more preferred upper limit is 10 parts by weight.
• Examples of the organic solvent include ketones, alcohols, aromatic hydrocarbons, esters and the like.
• Examples of the ketones include acetone, methyl ethyl ketone, dipropyl ketone and diisobutyl ketone.
• Examples of alcohols include methanol, ethanol, isopropanol, and butanol. Toluene, xylene, etc. are mentioned as said aromatic hydrocarbons.
• esters examples include methyl propionate, ethyl propionate, butyl propionate, methyl butanoate, ethyl butanoate, butyl butanoate, methyl pentanoate, ethyl pentanoate, butyl pentanoate, methyl hexanoate, ethyl hexanoate, butyl hexanoate, 2-ethylhexyl acetate, 2-ethylhexyl butyrate and the like.
• methyl cellosolve, ethyl cellosolve, butyl cellosolve, terpineol, dihydroterpineol, butyl cellosolve acetate, butyl carbitol acetate, terpineol acetate, dihydroterpineol acetate and the like can also be used.
• the preferable upper limit of the content of the organic solvent in the carbon fiber reinforced composite material of the present invention is 5.0% by weight, and 0% by weight is particularly preferable.
• the carbon fiber reinforced composite material of the present invention may contain resins other than epoxy resins and thermoplastic resins within a range that does not impair the effects of the present invention.
• the content of other resins is preferably 10% by weight or less.
• the carbon fiber reinforced composite material of the present invention may further include a tackifying resin, an adhesive strength modifier, an emulsifier, an antioxidant, a softening agent, a filler, a pigment, a dye, and a silane coupling agent, as long as the effects of the present invention are not impaired. It may contain known additives such as agents, antioxidants, surfactants, and waxes.
• the method for producing the carbon fiber reinforced composite material of the present invention is not particularly limited.
• a method for producing a carbon fiber reinforced composite material can be used.
• the epoxy resin, the curing agent, the thermoplastic resin, and various additives to be added as necessary are mixed in a ball mill, a blender mill, a three-roll mill, a disper, a planetary mixer, or the like. After mixing using various mixers, a method of impregnating the carbon fiber, and the like.
• the epoxy resin and the thermoplastic resin may be mixed and then the curing agent may be added, or the epoxy resin, the curing agent, and the thermoplastic resin are added at the same time. It may be produced by
• Examples of the method for combining the resin composition with the carbon fiber include a method of impregnating the carbon fiber. Specifically, for example, autoclave method, press method, hand lay-up method, pultrusion method, filament winding method, RTM method, pin winding method, infusion method, hot (cold) press method, spray-up method, continuous press method. etc.
• Carbon fiber reinforced composite materials are not particularly limited, and they can be used for structural materials for aircraft, automobile applications, ship applications, sports applications, and other general industrial applications such as windmills and rolls. Among them, however, application to prepregs and sheet molding compounds (SMC) as intermediate members is preferable, and application to those using prepregs is particularly preferable.
• SMC sheet molding compounds
• the carbon fiber reinforced composite material which can shorten hardening time, and can implement
• Example 1 (Production of polyvinyl acetal resin) 2700 g of pure water was added to 250 g of polyvinyl alcohol resin having an average degree of polymerization of 800 and a degree of saponification of 95.0 mol %, and the mixture was stirred at 90° C. for about 2 hours to dissolve. This solution was cooled to 40° C., and 100 g of hydrochloric acid having a concentration of 35% by weight and 160 g of butyraldehyde were added to carry out an acetalization reaction to precipitate a reaction product.
• the acetalization reaction was completed at 40° C., and neutralization, washing with water and drying were carried out by a conventional method to obtain a white powder of polyvinyl acetal resin (polyvinyl butyral resin).
• the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 at a concentration of 10% by weight, and 13 C-NMR was used to measure the amount of acetal groups (degree of acetalization), the amount of hydroxyl groups, and the amount of acetyl groups.
• Example 2 to 10 Polyvinyl acetal resin, resin composition, A prepreg was produced.
• Example 6 Two different aldehydes were used.
• bisphenol F type epoxy resin NPEF-170, manufactured by Nana Plastic Co., Ltd.
• JER828, manufactured by Japan Epoxy Resin Co., Ltd. bisphenol F type epoxy resin
• NPEF-170 bisphenol F type epoxy resin
• JER828, manufactured by Japan Epoxy Resin Co., Ltd. bisphenol F type epoxy resin
• a non-aromatic [alicyclic] epoxy resin (Celoxide 2021P, manufactured by Daicel) was used instead of the bisphenol A type epoxy resin (JER828, manufactured by Japan Epoxy Resins).
• Example 11-13 Comparative Examples 10-11
• a resin composition and a prepreg were produced in the same manner as in Example 1, except that the resin composition was prepared with the composition shown in Table 2 (epoxy resin, curing agent, polyvinyl acetal resin, carbon fiber).
• Comparative Example 11 instead of the bisphenol A type epoxy resin (JER828, manufactured by Japan Epoxy Resin Co., Ltd.), a phenol novolak type epoxy resin (NPPN-631, manufactured by Nanya Epoxy Resin Co., Ltd., a glycidyl ether type epoxy resin with more than two functional resin) was used.
• NPPN-631 phenol novolak type epoxy resin
• Example 1 means that the same polyvinyl acetal resin as in Example 1 was used.
• Tg glass transition temperature
• the curing completion time was measured using DSC. Specifically, DSC measurement was performed under the following conditions, and a line connecting the point where the slope of the exothermic peak became 0 and the reaction start point was set as the baseline value. After that, the area surrounded by the baseline and the DSC curve was used as reaction heat to calculate the curing reaction rate for each hour, and the time when the curing reaction rate reached 95% was defined as the curing completion time.
• Resin composition residual ratio the amount of the resin composition remaining in the carbon fiber (resin composition residual ratio) with respect to the amount of the impregnated resin composition was calculated and calculated according to the following criteria. evaluated. In addition, it can be said that the higher the resin composition residual ratio, the less the amount of the resin or the like exuding from the prepreg.
• Resin composition residual rate is 90% or more
• Resin composition residual rate is 80% or more and less than 90%
• Resin composition residual rate is 65% or more and less than 80% ⁇ : Resin composition residual rate is less than 65%
• a carbon fiber reinforced composite material and a method for producing the carbon fiber reinforced composite material, which can reduce resin exudation, shorten the curing time, and achieve high mechanical strength. can be done.

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