Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16J—PISTONS; CYLINDERS; SEALINGS
  • F16J12/00—Pressure vessels in general
• • 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
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
• • 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
  • C08G59/68—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 catalysts used
  • C08G59/72—Complexes of boron halides
• • 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
  • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
• • 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
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
  • F17C1/16—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of plastics materials
• • 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
  • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
  • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
  • C08L33/12—Homopolymers or copolymers of methyl methacrylate
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2203/00—Vessel construction, in particular walls or details thereof
  • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
  • F17C2203/0634—Materials for walls or layers thereof
  • F17C2203/0636—Metals
  • F17C2203/0656—Metals in form of filaments
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2203/00—Vessel construction, in particular walls or details thereof
  • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
  • F17C2203/0634—Materials for walls or layers thereof
  • F17C2203/0658—Synthetics
  • F17C2203/0663—Synthetics in form of fibers or filaments
  • F17C2203/0673—Polymers
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2203/00—Vessel construction, in particular walls or details thereof
  • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
  • F17C2203/0634—Materials for walls or layers thereof
  • F17C2203/0658—Synthetics
  • F17C2203/0675—Synthetics with details of composition
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2209/00—Vessel construction, in particular methods of manufacturing
  • F17C2209/21—Shaping processes
  • F17C2209/2154—Winding

Definitions

• the present invention relates to a thermosetting resin composition and its cured product, a prepreg, a fiber-reinforced composite material, and a high-pressure gas cylinder containing the fiber-reinforced composite material.
• CNG vehicles environmentally friendly natural gas vehicles
• FCVs fuel cell vehicles
• Fuel cell vehicles are powered by fuel cells, so it is essential to develop hydrogen stations where hydrogen, the fuel used in fuel cell vehicles, can be compressed to high pressure and filled into the vehicles.
• Steel tanks have been used so far as high-pressure gas storage tanks used in hydrogen stations for fuel cell vehicles, or as on-board fuel tanks for CNG vehicles, fuel cell vehicles, etc., but progress has been made in the development of lighter high-pressure gas storage tanks that use resin materials for the tank liner or outer layer. Reducing the weight of on-board fuel tanks has the advantage of improving the fuel efficiency of the vehicles that are equipped with them.
• Pressure vessels such as high-pressure gas storage tanks usually have a metal liner and an outer layer that covers the outer surface of the liner, but in recent years, in order to create lighter pressure vessels, the production of pressure vessels with plastic liners and linerless pressure vessels has also been considered.
• a known method for manufacturing pressure vessels is to use a tow prepreg (also called a tow prepreg), in which reinforcing fibers are pre-impregnated with an epoxy resin composition, and manufacture the pressure vessel through filament winding molding.
• a tow prepreg also called a tow prepreg
• reinforcing fibers are pre-impregnated with an epoxy resin composition
• Patent Document 1 discloses a prepreg containing carbon fibers and a matrix resin as a prepreg useful for forming a high-strength and high-toughness fiber-reinforced plastic, the matrix resin being a curable resin composition containing a bisphenol-type epoxy resin, a difunctional or higher (meth)acrylate compound, and a curing agent containing dicyandiamide and a radical polymerization agent, and the cured product of the curable resin composition has a predetermined flexural modulus and breaking elongation. Also disclosed is a method of winding the prepreg around a mandrel to produce a tubular body.
• Patent Document 2 discloses a curable resin composition for prepregs that is useful for molding high-strength and high-toughness fiber-reinforced plastics, the curable resin composition comprising two types of epoxy resins that satisfy predetermined requirements, difunctional or higher functional (meth)acrylate compounds, and a curing agent.
• Thermosetting resin compositions used as the matrix resin of prepregs are required to have a long pot life in order to ensure the long-term storage stability of the prepregs.
• the thermosetting resin compositions used as the matrix resin of prepregs are required to have both a high glass transition temperature and a high elongation percentage in the cured product.
• Patent Documents 1 and 2 it was difficult to satisfy all of these required properties.
• the object of the present invention is to provide a thermosetting resin composition that produces a cured product with a high glass transition temperature and elongation and has a long pot life, a cured product thereof, a prepreg, a fiber-reinforced composite material, and a high-pressure gas container containing the fiber-reinforced composite material.
• the present inventors have found that the above-mentioned problems can be solved by using a predetermined (meth)acrylate compound and an epoxy resin curing agent in a thermosetting resin composition containing an epoxy resin, a (meth)acrylate compound, an epoxy resin curing agent, and a thermal radical polymerization initiator. That is, the present invention relates to the following.
• thermosetting resin composition comprising component (A): an epoxy resin, component (B): a (meth)acrylate compound, component (C): an epoxy resin curing agent, and component (D): a thermal radical polymerization initiator, wherein component (B) comprises poly(butadiene-co-acrylonitrile) (B1) having acryloyloxy groups at both ends and a polyfunctional (meth)acrylate (B2) other than component (B1), and component (C) comprises a boron amine complex.
• component (B2) contains a polyfunctional (meth)acrylate having an aromatic ring.
• thermosetting resin composition according to the above [1] or [2], wherein the content of the component (B) is 5 to 50 parts by mass relative to 100 parts by mass of the component (A) in the thermosetting resin composition.
• thermosetting resin composition according to any one of [1] to [6] above.
• a prepreg comprising the thermosetting resin composition according to any one of [1] to [6] above and reinforcing fibers.
• a fiber-reinforced composite material obtained by curing the prepreg described in [8] or [9] above.
• a high-pressure gas cylinder comprising the fiber-reinforced composite material according to [10] above.
• the present invention provides a thermosetting resin composition having a long pot life and a cured product with a high glass transition temperature and elongation, a cured product thereof, a prepreg, a fiber-reinforced composite material, and a high-pressure gas container containing the fiber-reinforced composite material.
• the high-pressure gas container can be manufactured by filament winding molding using the prepreg of the present invention, and it is possible to produce a high-pressure gas container with a plastic liner or a linerless high-pressure gas container.
• (meth)acrylate encompasses both acrylate and methacrylate.
• room temperature means 25°C unless otherwise specified.
• thermosetting resin composition The thermosetting resin composition of the present invention (hereinafter also referred to as "the composition of the present invention”) is Component (A): epoxy resin, Component (B): (meth)acrylate compound, A thermosetting resin composition comprising: component (C): an epoxy resin curing agent; and component (D): a thermal radical polymerization initiator, wherein the component (B) contains poly(butadiene-co-acrylonitrile) (B1) having acryloyloxy groups at both ends and a polyfunctional (meth)acrylate (B2) other than the component (B1), and the component (C) contains a boron amine complex.
• the composition of the present invention can give a cured product having a high glass transition temperature (Tg) and elongation, and further has a long pot life.
• thermosetting resin composition of the present invention contains an epoxy resin (A) and a (meth)acrylate compound (B) as thermosetting resins.
• the epoxy resin curing agent (C) is a curing agent for the epoxy resin (A)
• the thermal radical polymerization initiator (D) acts as a thermal radical polymerization initiator for curing the (meth)acrylate compound (B).
• Thermosetting (epoxy) resin compositions consisting of an epoxy resin and an epoxy resin curing agent generally have excellent curability, heat resistance, etc., but the low elongation of the cured product is an issue when used for high-pressure gas containers and the like that require high toughness.
• epoxy resin compositions usually cure quickly, it has been necessary to improve the pot life, particularly when used for prepregs that are stored at room temperature.
• the pot life is improved by including a boron amine complex in component (C) used in the thermosetting resin composition of the present invention.
• component (B) used in the present invention contains poly(butadiene-co-acrylonitrile) (B1) having acryloyloxy groups at both ends, and a polyfunctional (meth)acrylate (B2) other than component (B1).
• component (B1) which is a specific diacrylate having a rubber structure
• component (B2) in component (B) suppresses an excessive decrease in Tg of the cured product caused by the use of component (B1).
• the epoxy resin (A) used in the present invention is not particularly limited as long as it is a polyfunctional epoxy resin having two or more epoxy groups. From the viewpoint of improving the Tg of the cured product, however, a polyfunctional epoxy resin containing an aromatic ring or an alicyclic structure in the molecule is preferred.
• the epoxy resin (A) include at least one selected from the group consisting of epoxy resins having a glycidylamino group derived from metaxylylenediamine, epoxy resins having a glycidylamino group derived from paraxylylenediamine, epoxy resins having a glycidylamino group derived from 1,3-bis(aminomethyl)cyclohexane, epoxy resins having a glycidylamino group derived from 1,4-bis(aminomethyl)cyclohexane, epoxy resins having a glycidylamino group derived from diaminodiphenylmethane, epoxy resins having a glycidylamino group and/or a glycidyloxy group derived from paraaminophenol, epoxy resins having a glycidyloxy group derived from resorcinol, epoxy resins having a glycidyloxy group derived from bisphenol A
• the epoxy resin (A) is preferably one having as a main component at least one selected from the group consisting of epoxy resins having a glycidylamino group derived from meta-xylylenediamine, epoxy resins having a glycidylamino group derived from para-xylylenediamine, epoxy resins having a glycidyloxy group derived from bisphenol A, and epoxy resins having a glycidyloxy group derived from bisphenol F, and more preferably one having as a main component at least one selected from the group consisting of epoxy resins having a glycidyloxy group derived from bisphenol A, and epoxy resins having a glycidyloxy group derived from bisphenol F.
• main component means that other components may be contained within a range that does not deviate from the spirit of the present invention, and preferably means 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass of the total.
• the epoxy resin (A) may be either a solid epoxy resin or a liquid epoxy resin, but from the viewpoint of ease of impregnation into reinforcing fibers when applied to prepregs, it is preferable that the epoxy resin (A) contains a liquid epoxy resin as the main component.
• Solid epoxy resin refers to an epoxy resin that does not have fluidity at 25°C
• liquid epoxy resin refers to an epoxy resin that has fluidity at 25°C.
• the epoxy equivalent (functional group equivalent) of the epoxy resin (A) is not particularly limited, but from the viewpoint of facilitating impregnation into reinforcing fibers when applied to a prepreg, it is preferably 1,500 g/equivalent or less, more preferably 1,200 g/equivalent or less, even more preferably 1,000 g/equivalent or less, still more preferably 800 g/equivalent or less, still more preferably 500 g/equivalent or less, more preferably 300 g/equivalent or less, still more preferably 250 g/equivalent or less, still more preferably 220 g/equivalent or less, and still more preferably 200 g/equivalent or less, and from the viewpoint of curability, it is preferably 120 g/equivalent or more.
• the epoxy equivalent of the epoxy resin (A) means the epoxy equivalent of the mixture.
• the (meth)acrylate compound (B) used in the present invention includes poly(butadiene-co-acrylonitrile) (B1) having acryloyloxy groups at both ends, and a polyfunctional (meth)acrylate (B2) other than the component (B1).
• the component (B1) used in the present invention is a diacrylate containing a copolymer structure of butadiene and acrylonitrile and having acryloyloxy groups at both ends of the main chain.
• the content of the structural units derived from acrylonitrile in component (B1) is preferably 5 to 50 mass %, more preferably 10 to 30 mass %, and even more preferably 10 to 25 mass %.
• the weight average molecular weight (Mw) of component (B1) is preferably 1,000 to 30,000, more preferably 2,000 to 10,000, and even more preferably 3,000 to 8,000. If the Mw is 1,000 or more, it is likely to contribute to improving the elongation of the cured product, and if it is 30,000 or less, it is likely to suppress a decrease in the Tg of the cured product.
• An example of a commercially available product of component (B1) is "Hypro 1300X33LC" manufactured by Chori GLEX.
• the content of component (B1) in component (B) is preferably 1 to 70 mass%, more preferably 5 to 60 mass%, even more preferably 10 to 60 mass%, even more preferably 15 to 60 mass%, and even more preferably 15 to 50 mass%. If the content of component (B1) in component (B) is 1 mass% or more, it is likely to contribute to improving the elongation of the cured product, and if it is 70 mass% or less, it is possible to suppress a decrease in the Tg of the cured product and reduce the variation in the physical properties of the cured product.
• the component (B2) used in the present invention may be any (meth)acrylate other than the component (B1) that has two or more (meth)acrylic groups.
• the component (B2) is preferably a (meth)acrylate that does not have a glycidyl group.
• Examples of (meth)acrylates other than component (B1) include epoxy (meth)acrylates having a main skeleton derived from an epoxy compound, urethane (meth)acrylates having a main skeleton derived from a polyisocyanate and a polyol, polyester (meth)acrylates having a main skeleton derived from a polyol, etc.
• at least one selected from the group consisting of urethane (meth)acrylates and polyester (meth)acrylates is preferred.
• the number of (meth)acrylic groups in component (B2) is preferably 2 to 6, more preferably 2 to 4, even more preferably 2 to 3, and even more preferably 2. If the number of (meth)acrylic groups in component (B2) is 2 or more, it is likely to contribute to improving the Tg of the cured product, and if it is 6 or less, the elongation of the cured product can be maintained.
• the component (B2) preferably contains a polyfunctional (meth)acrylate containing an aromatic ring.
• the aromatic ring may be a single ring or a condensed ring, and examples thereof include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring. Among these, at least one ring selected from the group consisting of a benzene ring and a naphthalene ring is preferred, and a benzene ring is more preferred.
• the number of aromatic rings contained in component (B2) may be one or more, and from the viewpoint of improving the Tg of the cured product, it is preferably two or more.
• polyfunctional (meth)acrylates containing an aromatic ring used as component (B2), include di(meth)acrylates having a structure derived from biphenol, di(meth)acrylates having a structure derived from bisphenol A, di(meth)acrylates having a structure derived from bisphenol F, di(meth)acrylates having a fluorene structure, and di(meth)acrylates having a structure derived from an aromatic hydrocarbon formaldehyde resin, and one or more of these can be used.
• the di(meth)acrylate may be any of epoxy di(meth)acrylate, urethane di(meth)acrylate, and polyester di(meth)acrylate.
• the aromatic hydrocarbon formaldehyde resin is a resin obtained by reacting an aromatic hydrocarbon with formaldehyde.
• the aromatic hydrocarbon may be at least one selected from the group consisting of benzene, xylene, toluene, mesitylene, pseudocumene, ethylbenzene, propylbenzene, decylbenzene, cyclohexylbenzene, biphenyl, methylbiphenyl, naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, anthracene, methylanthracene, dimethylanthracene, ethylanthracene, and binaphthyl, and is preferably at least one selected from the group consisting of xylene, toluene, and mesitylene, and more preferably xylene.
• xylene formaldehyde resin is also called "xy
• aromatic ring-containing polyfunctional (meth)acrylate used as component (B2) from the viewpoint of improving the Tg and elongation of the cured product, it is more preferable to use at least one selected from the group consisting of a compound represented by the following general formula (B2-1), a compound represented by the following general formula (B2-2), and a di(meth)acrylate having a structure derived from an aromatic hydrocarbon formaldehyde resin:
• R1 and R2 each independently represent a hydrogen atom or a methyl group
• R3 and R4 each independently represent a hydrogen atom or a methyl group
• m and n each independently represent the number of repeating units and are a number from 0 to 20.
• R1 and R2 are the same as above, and R5 is an alkylene group having 2 to 6 carbon atoms.
• X is a residue of a diisocyanate
• Y is a residue of a diol. Either X or Y contains an aromatic ring.
• r indicates the number of repeating units and is a number of 1 or more. The r+1 Xs and the r Ys may all be the same or different from each other.
• R 1 and R 2 are preferably methyl groups
• R 3 and R 4 are preferably methyl groups.
• m and n are each independently preferably a number from 1 to 15, more preferably a number from 1 to 10, and even more preferably a number from 2 to 6.
• m+n is a number from 0 to 40, and from the viewpoint of further improving the Tg and elongation of the cured product, it is preferably a number from 2 to 30, more preferably a number from 2 to 20, and even more preferably a number from 4 to 12.
• R1 and R2 are preferably methyl groups.
• R5 is an alkylene group having 2 to 6 carbon atoms, which may be either linear or branched.
• R5 is preferably an alkylene group having 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.
• X is a divalent group and is a residue of a diisocyanate represented by OCN-X-NCO.
• the diisocyanate may be a chain aliphatic diisocyanate such as trimethylene diisocyanate, tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, or 3-methyl-1,5-pentamethylene diisocyanate; 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, or methyl-2-methyl-1,5-pentamethylene diisocyanate;
• the diisocyanate is a diisocyanate containing an aromatic ring.
• the diisocyanate is, from the viewpoint of improving the elongation of the cured product, preferably at least one selected from the group consisting of linear aliphatic diisocyanates and aliphatic diisocyanates containing an alicyclic structure, more preferably at least one selected from the group consisting of hexamethylene diisocyanate, 1,2-bis(isocyanatemethyl)cyclohexane, 1,3-bis(isocyanatemethyl)cyclohexane, and isophorone diisocyanate, and even more preferably hexamethylene diisocyanate.
• Y in the general formula (B2-2) is a divalent group and is a residue of a diol represented by HO-Y-OH.
• the diol include linear aliphatic diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; diols containing an alicyclic structure such as cyclohexanedimethanol and tricyclodecanedimethanol; and diols containing an aromatic ring such as biphenol, bisphenol A, bisphenol F, and bisphenoxyfluoreneethanol, as well as diols obtained by adding
• the diol is preferably at least one selected from the group consisting of linear aliphatic diols and diols containing an aromatic ring, more preferably a diol containing an aromatic ring, and even more preferably at least one selected from the group consisting of bisphenol A, bisphenol F, and diols obtained by adding ethylene oxide or propylene oxide to these.
• Y in the general formula (B2-2) is more preferably a divalent group represented by the following general formula (Y1).
• R6 and R7 each independently represent a hydrogen atom or a methyl group, and are preferably a methyl group.
• p and q each independently represent the number of repeating units and are a number from 0 to 20. * represents a bond.
• r is a number of 1 or more, and preferably a number of 1 or more and 200 or less.
• di(meth)acrylates having a structure derived from aromatic hydrocarbon formaldehyde resins which are used as component (B2), include "NIKANOL XUAT” (urethane acrylate xylene resin) manufactured by Fudow Co., Ltd.
• the content of the aromatic ring-containing polyfunctional (meth)acrylate in component (B2) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and 100% by mass or less, from the viewpoint of improving the Tg of the cured product.
• polyfunctional (meth)acrylates that do not contain aromatic rings such as ⁇ , ⁇ -alkanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate, can also be used.
• aromatic rings such as ⁇ , ⁇ -alkanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol
• the content of component (B2) in component (B) is preferably 30 to 99 mass%, more preferably 40 to 95 mass%, even more preferably 40 to 90 mass%, even more preferably 40 to 85 mass%, and even more preferably 50 to 85 mass%. If the content of component (B2) in component (B) is 30 mass% or more, it is likely to contribute to improving the Tg of the cured product, and if it is 99 mass% or less, it is possible to maintain the elongation of the cured product and reduce the variation in the physical properties of the cured product.
• component (B) may also contain a (meth)acrylate other than components (B1) and (B2), such as a monofunctional (meth)acrylate, for the purpose of lowering the viscosity of the composition.
• a (meth)acrylate other than components (B1) and (B2) such as a monofunctional (meth)acrylate
• the total content of component (B1) and component (B2) in component (B) is preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more, and 100 mass% or less.
• the content of component (B) in the thermosetting resin composition is preferably 5 to 50 parts by mass, more preferably 5 to 45 parts by mass, and even more preferably 10 to 45 parts by mass, per 100 parts by mass of component (A). If the content of component (B) in the thermosetting resin composition is 5 parts by mass or more per 100 parts by mass of component (A), a long pot life is easily achieved, and if it is 50 parts by mass or less, the Tg of the cured product is easily maintained.
• the epoxy resin curing agent (C) used in the present invention contains a boron amine complex from the viewpoint of achieving a long pot life.
• the content of the boron amine complex in component (C) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 90% by mass or more, and is 100% by mass or less.
• Examples of boron amine complexes include boron halide amine complexes.
• Examples of boron halide amine complexes include boron trifluoride amine complexes and boron trichloride amine complexes, and from the viewpoint of achieving a long pot life, boron trichloride amine complexes are preferred.
• Examples of the amine component in the boron amine complex include alkylamines, alkanolamines, and cyclic aliphatic amines.
• alkylamines include monoalkylamines such as monoethylamine, monopropylamine, monobutylamine, monohexylamine, monooctylamine, and monolaurylamine; dialkylamines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine, dioctylamine, and dilaurylamine; and trialkylamines such as triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, trilaurylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, N,N-dimethylhexylamine, N,N-dimethyl
• alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-methylethanolamine, N-methylisopropanolamine, N-butylethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, and N-methyldiisopropanolamine.
• Examples of the cyclic aliphatic amine include piperidine and N,N-dicyclohexylmethylamine.
• the amine component in the boron amine complex is preferably a tertiary alkylated amine, i.e., a trialkylamine, more preferably at least one selected from the group consisting of N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, N,N-dimethylhexylamine, N,N-dimethyloctylamine, and N,N-dimethyllaurylamine, and even more preferably N,N-dimethyloctylamine.
• a tertiary alkylated amine i.e., a trialkylamine
• boron amine complexes used as component (C) include HUNTSMAN's "Accelerator DY 9577” (boron trichloride amine complex, amine component: N,N-dimethyl-n-octylamine).
• Component (C) may also contain an epoxy resin curing agent other than the boron amine complex.
• the epoxy resin curing agent other than the boron amine complex include amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and hydrazide-based curing agents, and one or more of these may be used.
• the content of the epoxy resin curing agent other than the boron amine complex in component (C) is preferably 70 mass% or less, more preferably 50 mass% or less, even more preferably 30 mass% or less, still more preferably 20 mass% or less, still more preferably 10 mass% or less, and still more preferably 5 mass% or less, the lower limit being 0 mass%.
• the content of component (C) in the thermosetting resin composition is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of component (A). If the content of component (C) in the thermosetting resin composition is 0.1 parts by mass or more per 100 parts by mass of component (A), it is easy to ensure curability, and if it is 40 parts by mass or less, it is easy to achieve a long pot life.
• the component (D) used in the present invention may be any compound that generates radicals when heated and can cure the component (B), and examples of such compounds include azo compounds and organic peroxides.
• Azo compounds include azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ABVN), 4,4'-azobis(4-cyanopentanoic acid) (ABCVA), 2,2'-azobis(2-methylbutyronitrile) (AMBN), 2,2'-azobis(2-methylpropionamidine) dihydrochloride (AAPH), 2,2'-azobis(2-methylpropionate) dimethyl, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, etc., and one or more of these can be used.
• AIBN azobisisobutyronitrile
• ABSVN 2,2'-azobis(2,4-dimethylvaleronitrile)
• ABSCVA 4,4'-azobis(4-cyanopentanoic acid)
• AMBN 2,2'-azobis(2-methylbutyronitrile)
• AAPH 2,2'-azo
• Organic peroxides include peroxyketals such as 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, 1,1-di(tert-hexylperoxy)cyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, n-butyl-4,4-di(tert-butylperoxy)valerate, and 2,2-di(tert-butylperoxy)butane; hydroperoxides such as tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide; tert-butylcumyl peroxide, di-tert Dialkyl peroxides such as t-butyl peroxide and di-tert-hexyl peroxide; diacy
• organic peroxides are preferred as component (D), more preferably at least one selected from the group consisting of peroxyketals, hydroperoxides, diacyl peroxides, peroxydicarbonates, peroxyesters, and dialkyl peroxides, even more preferably dialkyl peroxides, and even more preferably 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.
• the content of component (D) in the thermosetting resin composition is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, even more preferably 0.1 to 2 parts by mass, and even more preferably 0.5 to 2 parts by mass, per 100 parts by mass of component (B). If the content of component (D) in the thermosetting resin composition is 0.01 parts by mass or more per 100 parts by mass of component (B), it is easy to ensure curability, and if it is 5 parts by mass or less, it is easy to achieve a long pot life.
• the thermosetting resin composition may further contain ground natural silica as component (E).
• component (E) is a general term for natural siliceous rocks produced in Japan and around the world, and includes, for example, quartz sand that contains SiO2 and further contains impurities such as Al and Fe.
• Natural silica pulverized material is the above-mentioned natural silica pulverized material.
• D50 of component (E) measured by a laser scattering/diffraction method is preferably 0.5 to 10 ⁇ m, and the uniformity coefficient K expressed as D60/D10 is preferably 2 to 8.
• the content of component (E) in the thermosetting resin composition is preferably 0.01 to 10 mass%, more preferably 0.05 to 5.0 mass%, and even more preferably 0.1 to 3.0 mass%.
• the content of component (E) in the thermosetting resin composition is 0.01 mass% or more, it contributes to improving the hardness of the obtained cured product, and when it is 10 mass% or less, it is possible to improve the hardness while suppressing a decrease in the elongation of the cured product.
• the content of component (E) includes not only the crushed natural silica stone intentionally blended into the thermosetting resin composition, but also the crushed natural silica stone derived from the raw materials of the composition or mixed in during the production process of the composition.
• thermosetting resin composition may further contain other components, such as modifying components such as fillers and plasticizers, flow adjusting components such as thixotropic agents, reactive or non-reactive diluents, pigments, leveling agents, tackifiers, and stress relaxation components, depending on the application.
• modifying components such as fillers and plasticizers
• flow adjusting components such as thixotropic agents, reactive or non-reactive diluents, pigments, leveling agents, tackifiers, and stress relaxation components, depending on the application.
• examples of the stress relaxation component include elastomer particles such as silicone-based elastomer particles, butyl acrylate-based elastomer particles, polyetheramine-based elastomer particles, and other rubber particles. Liquid rubber components such as epoxidized polybutadiene can also be used. Commercially available products of the stress relaxation component include Kane Ace B series, FM series, M series, and MX series manufactured by Kaneka Corporation, and liquid epoxidized polybutadiene Eboride PB3600 and Eboride PB4700 manufactured by Daicel Corporation.
• the content of the stress relaxation component is preferably 0.1 to 15 mass %, more preferably 0.5 to 10 mass %, based on the solid content of the thermosetting resin composition.
• the "solid content of the thermosetting resin composition” refers to the amount excluding water and organic solvents from the total amount of the thermosetting resin composition.
• the thermosetting resin composition of the present invention may further contain a solvent from the viewpoint of enhancing the impregnation ability into the reinforcing fibers.
• the solvent include alcohol-based solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and 1-propoxy-2-propanol; ester-based solvents such as ethyl acetate and butyl acetate; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether-based solvents such as diethyl ether and diisopropyl ether; and hydrocarbon-based solvents such as toluene.
• alcohol-based solvents such as methanol, ethanol, 1-propano
• the solvent is preferably at least one selected from the group consisting of alcohol-based solvents, ester-based solvents, ketone-based solvents, and hydrocarbon-based solvents having 8 or less carbon atoms, and more preferably at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and toluene.
• the total content of components (A) to (D) in the thermosetting resin composition is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, and 100% by mass or less, based on the solid content of the thermosetting resin composition, from the viewpoint of effectively exerting the effects of the present invention.
• the content thereof is not particularly limited, but from the viewpoint of improving the impregnation into the reinforcing fibers, the content thereof in the thermosetting resin composition is preferably 5 mass% or more, more preferably 10 mass% or more, and even more preferably 15 mass% or more, and from the viewpoint of ease of removing the solvent, the content thereof is preferably 80 mass% or less, more preferably 70 mass% or less.
• the thermosetting resin composition may be a solventless composition that does not substantially contain a solvent.
• a solventless thermosetting resin composition is a thermosetting resin composition in which the content of the solvent is preferably less than 5% by mass, more preferably 2% by mass or less, even more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and even more preferably 0% by mass.
• thermosetting resin composition there are no particular limitations on the method for preparing the thermosetting resin composition, and the components (A) to (D) and other components used as necessary can be mixed and prepared using known methods and equipment. There are no particular limitations on the order in which the components contained in the thermosetting resin composition are mixed, but when components (A) and (B) are highly viscous, it is preferable to first heat and mix components (A) and (B) at 80 to 120°C, then cool to below 80°C, and then mix components (C) and (D). This is to prevent thermal polymerization of component (C) from progressing during the preparation of the thermosetting resin composition.
• the cured product of the thermosetting resin composition of the present invention (hereinafter, simply referred to as "cured product of the present invention") is obtained by thermally curing the above-mentioned thermosetting resin composition of the present invention by a known method.
• the curing conditions of the thermosetting resin composition are appropriately selected depending on the application and form, but the curing temperature is preferably 90 to 160°C, more preferably 100 to 150°C.
• the form of the cured product of the present invention is not particularly limited and can be selected according to the application.
• the application of the thermosetting resin composition is a paint
• the cured product of the composition is usually in the form of a film.
• the cured product of the present invention is preferably a matrix resin of a fiber-reinforced composite material described later.
• the glass transition temperature (Tg) of the cured product of the present invention is preferably 80°C or higher, more preferably 85°C or higher, even more preferably 87°C or higher, and even more preferably 90°C or higher, from the viewpoint of use as a matrix resin for fiber-reinforced composite materials described below, as well as in high-pressure gas containers, etc., and is usually 200°C or lower.
• the Tg of the cured product can be measured by the method described in the Examples.
• the prepreg of the present invention contains the thermosetting resin composition and reinforcing fibers.
• the form of the reinforcing fiber used in the prepreg include short fiber, long fiber, and continuous fiber.
• long fiber or continuous fiber is preferred, and continuous fiber is more preferred.
• short fibers refer to fibers having a fiber length of 0.1 mm or more and less than 10 mm
• long fibers refer to fibers having a fiber length of 10 mm or more and 100 mm or less
• continuous fibers refer to fiber bundles having a fiber length of more than 100 mm.
• the continuous fibers may be in the form of a tow, a sheet, a tape, etc., and the continuous fibers constituting a sheet or a tape may be unidirectional (UD) materials, woven fabrics, nonwoven fabrics, etc.
• the shape of the continuous fibers is preferably a tow or tape, more preferably a tow.
• the number of continuous fiber bundles (filament number) constituting a tow is preferably 3K to 50K, more preferably 6K to 40K, from the viewpoint of easily obtaining high strength and high elastic modulus.
• the average fiber length of the continuous fiber bundle is not particularly limited, but from the viewpoint of molding processability, it is preferably 1 to 10,000 m, more preferably 100 to 10,000 m.
• the average fineness of the continuous fiber bundle is preferably 50 to 2000 tex (g/1000 m), more preferably 200 to 1500 tex, and even more preferably 500 to 1500 tex, from the viewpoint of moldability and the viewpoint of facilitating obtaining high strength and high elastic modulus.
• the average tensile modulus of the continuous fiber bundle is preferably 50 to 1000 GPa.
• Examples of materials for the reinforcing fibers include inorganic fibers such as carbon fibers, glass fibers, basalt fibers, metal fibers, boron fibers, and ceramic fibers, and organic fibers such as aramid fibers, polyoxymethylene fibers, aromatic polyamide fibers, polyparaphenylene benzobisoxazole fibers, and ultra-high molecular weight polyethylene fibers.
• inorganic fibers are preferred from the viewpoint of obtaining high strength, and at least one type selected from the group consisting of carbon fibers, glass fibers, and basalt fibers is preferred because they are lightweight, have high strength, and have a high elastic modulus, and carbon fibers are more preferred from the viewpoints of strength and light weight.
• Examples of carbon fibers include polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, etc. Carbon fibers made from plant-derived raw materials such as lignin and cellulose can also be used.
• the reinforcing fibers may be treated with a treatment agent, such as a surface treatment agent or a sizing agent.
• the surface treatment agent is preferably a silane coupling agent, for example, a silane coupling agent having a vinyl group, a silane coupling agent having an amino group, a silane coupling agent having an epoxy group, a silane coupling agent having a (meth)acrylic group, a silane coupling agent having a mercapto group, etc.
• bundling agents examples include urethane-based bundling agents, epoxy-based bundling agents, acrylic-based bundling agents, polyester-based bundling agents, vinyl ester-based bundling agents, polyolefin-based bundling agents, polyether-based bundling agents, and carboxylic acid-based bundling agents, and among these, one or more of these may be used in combination.
• bundling agents that combine two or more types include urethane/epoxy-based bundling agents, urethane/acrylic-based bundling agents, and urethane/carboxylic acid-based bundling agents.
• the amount of the treatment agent is preferably 0.001 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.5 to 2% by mass relative to the reinforcing fiber, from the viewpoint of improving the interfacial adhesion with the cured product of the thermosetting resin composition and further improving the strength and impact resistance of the resulting prepreg and composite material.
• continuous carbon fibers include, for example, Toray Industries, Inc.'s Torayca yarns "T300”, “T300B”, “T400HB”, “T700SC”, “T800SC”, “T800HB”, “T830HB”, “T1000GB”, “T100GC”, “M35JB”, “M40JB”, “M46JB”, “M50JB”, “M55J”, “M55JB”, “M60JB”, “M30SC”, and “Z600”series; and TENAX "HTA40" series, “HTS40” series, “HTS45” series, and “HTS45P12” series manufactured by Teijin Ltd.
• examples of commercially available continuous carbon fibers other than tow include Torayca cloths "CO6142", “CO6151B”, “CO6343”, “CO6343B”, “CO6347B”, “CO6644B”, "CK6244C”, “CK6273C”, "CK6261C”, "UT70” series, "UM46” series, "BT70” series, "T300” series, “T300B” series, “T400HB” series, “T700SC” series, “T800SC” series, “T800HB” series, "T1000GB” series, "M35JB” series, and “M40 JB series, “M46JB” series, “M50JB” series, “M55J” series, “M55JB” series, “M60JB” series, “M30SC” series, and "Z600GT”series; carbon fiber fabrics such as PYROFIL "TR3110M", “TR3523M”, “TR3524M”, “TR6110HM”, “TR6120HM”, “TRK101
• the content of the reinforcing fibers in the prepreg is preferably in a range such that the volume fraction of the reinforcing fibers in the prepreg is 0.10 or more, more preferably 0.20 or more, even more preferably 0.30 or more, and even more preferably 0.40 or more, from the viewpoints of obtaining high strength and high elastic modulus. Also, from the viewpoints of gas barrier properties, impact resistance, and moldability, the content is preferably in a range such that the volume fraction is 0.85 or less, more preferably 0.80 or less, and even more preferably 0.70 or less.
• the volume fraction Vf1 of the reinforcing fibers in the prepreg can be calculated from the following formula.
• Vf 1 ⁇ mass (g) of reinforcing fiber/specific gravity of reinforcing fiber ⁇ ⁇ [ ⁇ mass (g) of reinforcing fiber/specific gravity of reinforcing fiber ⁇ + ⁇ mass (g) of solid content of impregnated thermosetting resin composition/specific gravity of solid content of thermosetting resin composition ⁇ ]
• the total content of the solids of the thermosetting resin composition constituting the prepreg and the reinforcing fibers is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, with the upper limit being 100% by mass.
• the shape of the prepreg varies depending on the form of the reinforcing fibers used, but from the viewpoint of producing a high-pressure gas container by a filament winding method, a tow prepreg is preferred.
• a prepreg in the form of a tape or sheet can be used.
• a tape-shaped prepreg is preferred, and a UD tape is more preferred.
• the method for producing the prepreg is not particularly limited, and it can be produced according to a conventional method.
• the prepreg after impregnating the reinforcing fibers with the thermosetting resin composition, the prepreg can be obtained by removing the solvent through a drying process as necessary.
• the method of impregnating the reinforcing fiber with the thermosetting resin composition is not particularly limited, and a known method can be used as appropriate depending on the form of the reinforcing fiber, etc.
• a method can be mentioned in which a continuous fiber bundle unwound from a roll is immersed in a resin bath filled with the above-mentioned thermosetting resin composition, and after impregnation with the composition, the bundle is pulled up from the resin bath. Then, a step of removing excess thermosetting resin composition using a squeeze roll or the like can be performed.
• the impregnation with the thermosetting resin composition can be carried out under pressurized or reduced pressure conditions, if necessary.
• the reinforcing fibers impregnated with the thermosetting resin composition are subjected to a drying process to remove the solvent.
• a drying process to remove the solvent.
• the drying conditions can be selected in the range of 30 to 120°C, and the drying time can be selected in the range of 10 seconds to 5 minutes.
• the prepreg obtained through the above drying process can be wound up or otherwise processed to form a prepreg product, or it can be used for the continuous production of fiber-reinforced composite materials after the drying process without being wound up or otherwise processed.
• the fiber-reinforced composite material of the present invention (hereinafter, simply referred to as "composite material") is obtained by curing the prepreg, and contains a cured product of the thermosetting resin composition and reinforcing fibers.
• the fiber-reinforced composite material of the present invention has high heat resistance and impact resistance because it contains the cured product of the thermosetting resin composition.
• the prepreg, the thermosetting resin composition, the reinforcing fiber, and the preferred embodiments thereof used in the production of the composite material are the same as those described above.
• the content of the reinforcing fibers in the fiber-reinforced composite is preferably in a range such that the volume fraction of the reinforcing fibers in the fiber-reinforced composite is 0.10 or more, more preferably 0.20 or more, even more preferably 0.30 or more, and even more preferably 0.40 or more, from the viewpoints of obtaining high strength and high elastic modulus, and is preferably in a range such that the volume fraction is 0.85 or less, more preferably 0.80 or less, and even more preferably 0.70 or less, from the viewpoints of gas barrier properties, impact resistance, and moldability.
• the volume fraction Vf of the reinforcing fibers in the fiber-reinforced composite material can be calculated from the following formula.
• Vf ⁇ mass (g) of reinforcing fiber/specific gravity of reinforcing fiber ⁇ [ ⁇ mass (g) of reinforcing fiber/specific gravity of reinforcing fiber ⁇ + ⁇ mass (g) of cured product of thermosetting resin composition/specific gravity of cured product of thermosetting resin composition ⁇ ]
• the composite material can be produced by premolding the prepreg into a desired shape and then curing the prepreg.
• a tow or tape-shaped prepreg can be used to produce the composite material by molding the prepreg by a filament winding method, a tape winding method, a braiding method, a 3D printer method, etc.
• a prepreg in tow or tape form is wound around the outer surface of a balloon, mandrel, or liner, and then heat cured to produce a composite material of the desired shape.
• a balloon or a mandrel is used to braid a tow- or tape-shaped prepreg into a unidirectional or braided structure by a braider to form a prepreg, and then the prepreg is heated and cured.
• a tow- or tape-shaped prepreg can also be braided and formed without using a balloon or a mandrel.
• a composite material can be produced by placing one or more prepregs in a mold and heating and curing them under vacuum or pressurized conditions.
• the method of curing the prepreg in the manufacture of the composite material is not particularly limited, and is carried out by a known method at a temperature and for a time sufficient to cure the thermosetting resin composition contained in the prepreg.
• the prepreg curing conditions depend on the thickness of the prepreg and the composite material to be formed, but for example, the curing temperature can be selected in the range of 10 to 180°C and the curing time in the range of 5 minutes to 200 hours, and from the viewpoint of productivity, the curing temperature is preferably 80 to 180°C and the curing time in the range of 10 minutes to 5 hours.
• the composite material of the present invention is suitable for use in hollow molded articles such as pipes, shafts, cylinders, and tanks, as it is manufactured using tow or tape-shaped prepregs.
• the composite material is suitable as a material for forming high-pressure gas containers.
• the high pressure gas container of the present invention contains the fiber reinforced composite material. It is sufficient that at least a part of the high pressure gas container of the present invention is made of the fiber reinforced composite material.
• the fiber reinforced composite material for example, in the case of a high pressure gas container having a liner and an outer layer provided so as to cover the outer surface of the liner, at least one of the liner and the outer layer may be made of the fiber reinforced composite material.
• the entire container may be made of the fiber reinforced composite material.
• high-pressure gas containers containing fiber-reinforced composite materials include: (1) a configuration having a metal liner and an outer layer made of the fiber-reinforced composite material of the present invention; (2) a configuration having a resin liner and an outer layer made of the fiber-reinforced composite material of the present invention; (3) a configuration having a liner made of the fiber-reinforced composite material of the present invention and an outer layer made of a material other than the fiber-reinforced composite material; and (4) a configuration consisting only of a container made of the fiber-reinforced composite material of the present invention (linerless).
• Examples of the metal used in the "metallic liner" in (1) above include light alloys such as aluminum alloys and magnesium alloys.
• the resin used in the "resin liner” in (2) above is not particularly limited as long as it is a resin excellent in gas barrier properties and pressure resistance, and examples of the resin include thermoplastic resins, cured products of thermosetting resins, cured products of photocurable resins, etc. Among these, thermoplastic resins are preferred from the viewpoint of ease of molding the liner.
• thermoplastic resin examples include polyamide resins, polyester resins, polyolefin resins, polyimide resins, polycarbonate resins, polyetherimide resins, polyamideimide resins, polyphenylene etherimide resins, polyphenylene sulfide resins, polysulfone resins, polyethersulfone resins, polyarylate resins, liquid crystal polymers, polyetheretherketone resins, polyetherketone resins, polyetherketoneketone resins, polyetheretherketoneketone resins, polybenzimidazole resins, and the like. These may be used alone or in combination of two or more.
• thermoplastic resins At least one selected from the group consisting of polyamide resins and polyolefin resins is preferred, and polyamide resins are more preferred.
• the resin liner may contain the above-mentioned stress relaxation component.
• the "outer layer made of a material other than the fiber-reinforced composite material” in (3) above is preferably an outer layer made of a fiber-reinforced composite material other than the fiber-reinforced composite material of the present invention, from the viewpoint of improving reinforcement.
• the outer layer can be formed so as to cover the outer surface of the main body portion of the liner without any gaps.
• the outer layer may be provided directly on the outer surface of the liner.
• one or more other layers may be provided on the outer surface of the liner, and the outer layer may be provided on the surface of the other layers.
• an adhesive layer may be provided between the liner and the outer layer to improve adhesion between the liner and the outer layer.
• the thickness of the outer layer made of the fiber-reinforced composite material of the present invention can be appropriately selected depending on the capacity, shape, etc. of the high-pressure gas container, but from the viewpoint of imparting high gas barrier properties and impact resistance, it is preferably 100 ⁇ m or more, more preferably 200 ⁇ m or more, and even more preferably 400 ⁇ m or more, and from the viewpoint of reducing the size and weight of the high-pressure gas container, it is preferably 80 mm or less, more preferably 60 mm or less.
• the thickness of the liner made of the fiber-reinforced composite material of the present invention can be appropriately selected according to the capacity, shape, etc. of the high-pressure gas container, but from the viewpoint of gas barrier properties and pressure resistance, it is preferably 100 ⁇ m or more, more preferably 200 ⁇ m or more, and even more preferably 400 ⁇ m or more, and from the viewpoint of miniaturization and weight reduction of the high-pressure gas container, it is preferably 60 mm or less, more preferably 40 mm or less.
• the thickness of the container made of the fiber-reinforced composite material of the present invention can be appropriately selected depending on the capacity, shape, etc. of the high-pressure gas container, but from the viewpoint of gas barrier properties and pressure resistance, it is preferably 1 mm or more, more preferably 2 mm or more, and even more preferably 5 mm or more, and from the viewpoint of miniaturization and weight reduction of the high-pressure gas container, it is preferably 80 mm or less, more preferably 60 mm or less.
• the content of the reinforcing fibers in the liner, outer layer or high-pressure gas container made of the fiber-reinforced composite material of the present invention is preferably in a range such that the volume fraction of the reinforcing fibers is 0.10 or more, more preferably 0.20 or more, even more preferably 0.30 or more, and even more preferably 0.40 or more, from the viewpoint of obtaining high strength and high elastic modulus. Also, from the viewpoint of gas barrier properties, impact resistance and moldability, the volume fraction is preferably in a range such that the volume fraction is 0.85 or less, more preferably 0.80 or less, even more preferably 0.75 or less, and even more preferably 0.70 or less.
• the volume fraction of the reinforcing fibers can be calculated in the same manner as described above.
• the high-pressure gas container is preferably in the above-mentioned form (2), (3) or (4), and more preferably in the form (3) or (4).
• the high-pressure gas container may further include components such as a nozzle and a valve that are made of a material other than the fiber-reinforced composite material.
• any layer such as a protective layer, a paint layer, or a rust-preventing layer may be formed on the surface of the high-pressure gas container.
• the gas to be stored in the high-pressure gas container may be any gas that is in a gaseous state at 25°C and 1 atm, and examples of such gas include hydrogen, oxygen, carbon dioxide, nitrogen, argon, LPG, alternative fluorocarbons, methane, etc. Among these, hydrogen is preferred from the viewpoint of the effectiveness of the present invention.
• the production method described in the above-mentioned method for producing a fiber reinforced composite material can be appropriately used depending on the form of the reinforcing fiber or prepreg used.
• the tow or tape-shaped prepreg can be molded by a filament winding method, a tape winding method, a braiding method, a 3D printer method, or the like to produce the high pressure gas container.
• a tow- or tape-shaped prepreg is wound using a filament winding method or a tape winding method so as to cover the outer surface of a metal or resin liner, and then the prepreg is heat-cured to form an outer layer made of a fiber-reinforced composite material, thereby manufacturing the high-pressure gas container.
• the high-pressure gas container is of the above embodiment (3) or (4), the high-pressure gas container can be manufactured by forming a tow- or tape-shaped prepreg into a container shape by a filament winding method, a tape winding method, a braiding method, a 3D printer method, or the like, and then heat-curing the prepreg.
• Tg Glass transition temperature
• DSC25 differential scanning calorimeter
• thermosetting resin composition prepared in each example was molded into a flat plate of 200 mm ⁇ 200 mm ⁇ 2 mm thickness, and cured for 180 minutes in a hot air oven at 130° C. to produce a cured product.
• a rectangular piece measuring 180 mm ⁇ 15 mm ⁇ 2 mm thickness was cut out from the cured product to prepare a tensile test specimen.
• Elongation (%) (length of test piece at break ⁇ initial length of test piece)/(initial length of test piece) ⁇ 100
• thermosetting resin composition A cured product (test piece) of the thermosetting resin composition was prepared in the same manner as in the elongation measurement.
• the test piece was placed on a horizontal surface in an environment of 23° C., and the Shore D hardness was measured by pressing an Asker Rubber Hardness Tester Type D (manufactured by Kobunshi Keiki Co., Ltd.) against the test piece. The results are shown in the table. The higher the value, the higher the hardness.
• thermosetting resin composition prepared in each example at 23° C. was measured, and then 10 g of the thermosetting resin composition was placed in a plastic cup (diameter 46 mm) and stored at 23° C. The time (weeks) until the viscosity of the thermosetting resin composition became at least twice the initial viscosity was measured and shown in the table.
• the viscosity of the thermosetting resin composition was measured using an E-type viscometer "TVE-22H type viscometer, cone plate type" (manufactured by Toki Sangyo Co., Ltd.).
• thermosetting resin composition examples 1 to 15 and Comparative Examples 1 to 2 (Preparation and Evaluation of Thermosetting Resin Compositions)
• the components shown in Table 1 were blended and mixed in the parts by mass shown in Table 1 to obtain a thermosetting resin composition.
• the thermosetting resin composition thus obtained was evaluated by the above-mentioned method. The results are shown in Table 1.
• the blend amounts (parts by mass) in Table 1 are all amounts of active ingredients.
• thermosetting resin composition of the present invention has a glass transition temperature of 80° C. or higher and an elongation of 4% or higher.
• the pot life of the thermosetting resin composition is long.
• the thermosetting resin compositions of Examples 1 to 7 and 10 to 15 had little variation in the measured elongation values, and further achieved a cured product Tg of 85° C. or higher.
• the thermosetting resin composition (epoxy resin composition) of Comparative Example 1 which did not contain components (B) and (D), had a short pot life and the elongation of the cured product did not reach 4%.
• the thermosetting resin composition of Comparative Example 2 which did not contain component (B1), did not reach 4% elongation of the cured product.
• thermosetting resin composition which can give a cured product having a high glass transition temperature and a high elongation and has a long pot life, a cured product thereof, a prepreg, a fiber-reinforced composite material, and a high-pressure gas container containing the fiber-reinforced composite material.
• the high-pressure gas container can be produced by filament winding molding using the prepreg of the present invention, and it is also possible to produce a high-pressure gas container with a plastic liner or a linerless high-pressure gas container.

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• 2023
  • 2023-09-13 JP JP2024555685A patent/JPWO2024075480A1/ja active Pending
  • 2023-09-13 CN CN202380069423.6A patent/CN119948078A/zh active Pending
  • 2023-09-13 US US19/117,894 patent/US20260035557A1/en active Pending
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