WO2023149258A1 - Composition réactive en deux parties pour former une résine de matrice thermoplastique, résine de matrice pour matériau composite de résine thermoplastique, et matériau composite de résine thermoplastique et son procédé de production - Google Patents

Composition réactive en deux parties pour former une résine de matrice thermoplastique, résine de matrice pour matériau composite de résine thermoplastique, et matériau composite de résine thermoplastique et son procédé de production Download PDF

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Publication number
WO2023149258A1
WO2023149258A1 PCT/JP2023/001897 JP2023001897W WO2023149258A1 WO 2023149258 A1 WO2023149258 A1 WO 2023149258A1 JP 2023001897 W JP2023001897 W JP 2023001897W WO 2023149258 A1 WO2023149258 A1 WO 2023149258A1
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Prior art keywords
diisocyanate
blocked
thermoplastic
isocyanate
matrix resin
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PCT/JP2023/001897
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English (en)
Japanese (ja)
Inventor
紀夫 平山
欣範 山田
雄大 塩路
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DKS Co Ltd
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DKS Co Ltd
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Priority to CN202380018991.3A priority Critical patent/CN118679212A/zh
Publication of WO2023149258A1 publication Critical patent/WO2023149258A1/fr
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs

Definitions

  • the present invention relates to a two-component reaction type composition used for forming a thermoplastic matrix resin of a thermoplastic resin composite containing fibers as a reinforcing material, a matrix resin for the thermoplastic resin composite, and
  • the present invention relates to a thermoplastic resin composite and a method for producing a thermoplastic resin composite.
  • Fiber reinforced composite materials which are resin composites containing fibers as a reinforcing material, are lightweight and have excellent performance, so they are used in a wide range of applications such as electrical and electronic parts, vehicles, and aviation.
  • Thermosetting resins such as epoxy resins are often used as matrix resins for fiber-reinforced composite materials.
  • thermosetting resins have a three-dimensional crosslinked structure after a polymerization reaction (curing), and cannot be remelted after being impregnated with fibers and cured, so they cannot be reprocessed or reused.
  • thermoplastic resin composites which are fiber-reinforced composite materials with a thermoplastic resin matrix
  • thermoplastic resin which is the base material
  • thermoplastic resins since thermoplastic resins are generally supplied in the form of macromolecules such as pellets and films at the time of molding, their viscosities are high when they are melted to impregnate fibers. Therefore, it is not easy to produce a thermoplastic resin composite with good impregnation.
  • thermoplastic resin composite In order to reduce the resin viscosity during molding of the thermoplastic resin composite, it is advantageous to use an in-situ polymerization type thermoplastic resin and impregnate the fiber in the state of a monomer. That is, it is desirable to produce a thermoplastic resin composite by impregnating fibers with a low-viscosity liquid monomer and polymerizing the fibers after the impregnation to form a thermoplastic resin.
  • Patent Document 1 fibers are impregnated with a polymerizable lactam mixed solution, the impregnated fibers are passed through a heated mold, and the polymerization of the lactam monomer and the molding of the thermoplastic polyamide resin obtained thereby are performed simultaneously. disclosed to do.
  • Patent Literature 1 also discloses obtaining a plate material as a primary molded body by the above molding, stacking the plate materials, and performing heat compression molding to obtain a laminate as a secondary molded body.
  • Patent Document 2 discloses a two-component reaction type composition comprising an active hydrogen component and an isocyanate component as a composition used for forming a matrix resin of a thermoplastic resin composite. are mixed and impregnated into the fibers, and then the two-part reactive composition is cured by heating.
  • the active hydrogen component contains an aromatic diamine having an alkylthio group
  • the isocyanate component is at least one selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates and modified products thereof. of diisocyanates.
  • JP 2017-007266 A Japanese Patent No. 6580774
  • the thermoplastic resin composite can melt the thermoplastic resin by heating. Therefore, after the thermoplastic resin is combined with fibers to obtain a primary molded body, the primary molded body can be laminated and integrated by hot pressing to obtain a laminate as a secondary molded body.
  • the heat-sealing between the layers of the laminate may be insufficient and delamination may occur. Increased adhesion is required.
  • an embodiment of the present invention provides a thermoplastic matrix resin-forming resin that can improve the adhesion between layers of the laminate when the laminate is formed by lamination and integration by thermoforming, for example.
  • An object of the present invention is to provide a two-part reaction type composition, a matrix resin for a thermoplastic resin composite, and a thermoplastic resin composite.
  • a two-part reaction type composition used for forming a thermoplastic matrix resin of a thermoplastic resin composite containing fibers as a reinforcing material the composition comprising an active hydrogen component containing an aromatic diamine having an alkylthio group; and an isocyanate component containing at least one diisocyanate selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates and modified products thereof, wherein the diisocyanate is a blocked diisocyanate in which at least one isocyanate group is blocked and an unblocked diisocyanate in which the isocyanate groups are unblocked.
  • thermoplastic matrix resin for forming a thermoplastic matrix resin according to [1], wherein the blocking rate, which is the molar ratio of blocked isocyanate groups to isocyanate groups in the entire isocyanate component, is 1 to 56%.
  • a matrix resin for a thermoplastic resin composite containing fibers as a reinforcing material comprising an active hydrogen component containing an aromatic diamine having an alkylthio group, an aliphatic diisocyanate, an alicyclic diisocyanate, and modified products thereof
  • thermoplastic matrix resin obtained by reacting the two-component reactive composition according to [1] or [2] or the matrix resin according to [3], and a fiber as a reinforcing material, Thermoplastic resin composite.
  • thermoplastic matrix resin obtained by reacting the two-component reactive composition according to [1] or [2] or the matrix resin according to claim 3, and a plurality of fibers as reinforcing materials A thermoplastic resin composite, which is a laminate obtained by stacking the primary molded bodies of (1) and laminating and integrating them by thermoforming.
  • thermoplastic resin composite containing fibers as a reinforcing material comprising: A thermoplastic matrix resin formulation comprising an active hydrogen component and an isocyanate component, wherein the isocyanate component comprises a blocked diisocyanate in which at least one isocyanate group is blocked and an unblocked diisocyanate in which the isocyanate group is unblocked. impregnating the fibers with a composition for By heating the fibers at a temperature lower than the dissociation temperature of the blocked diisocyanate, the thermoplastic matrix resin-forming composition is polymerized while retaining the blocked isocyanate groups, thereby obtaining a thermoplastic matrix.
  • thermoplastic resin composite comprising obtaining a primary molded article containing a resin.
  • thermoplastic resin according to [6] wherein the composition for forming a thermoplastic matrix resin has a blocking rate, which is a molar ratio of blocked isocyanate groups to isocyanate groups in the entire isocyanate component, of 1 to 56%.
  • a method for manufacturing a composite [8]
  • the active hydrogen component of the thermoplastic matrix resin-forming composition contains an aromatic diamine having an alkylthio group, and the isocyanate component is selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates and modified products thereof.
  • thermoplastic resin composite according to [6] or [7], wherein the diisocyanate contains at least one kind of diisocyanate that has been fused with the above-mentioned diisocyanate, and the diisocyanate contains the blocked diisocyanate and the unblocked diisocyanate.
  • a method for producing a thermoplastic resin composite [10] The thermoplastic resin composite according to any one of [6] to [9], wherein the temperature for heating the fibers is lower than the glass transition temperature of the thermoplastic matrix resin in the primary molded body. manufacturing method.
  • the following effects are achieved by using both a blocked diisocyanate and an unblocked diisocyanate as the isocyanate component to be reacted with the active hydrogen component.
  • the unblocked diisocyanate and the active hydrogen component can be reacted while retaining the blocked isocyanate groups. It can be polymerized to obtain a thermoplastic resin. Therefore, it is possible to obtain a primary molding of a thermoplastic resin composite comprising a thermoplastic matrix resin and fibers.
  • thermoforming is performed under conditions in which the blocking agent of the blocked diisocyanate is dissociated, so that the dissociated isocyanate groups react with each other. Bonds can be made between the layers of the laminate. Therefore, it is possible to improve the adhesion between layers in the thermoplastic resin composite laminate, which is a secondary molded product.
  • thermoplastic matrix resin [Two-liquid reactive composition for forming thermoplastic matrix resin]
  • a two-component reaction type composition for forming a thermoplastic matrix resin according to one embodiment comprises an active hydrogen component containing an aromatic diamine (A) having an alkylthio group; and an isocyanate component containing at least one diisocyanate (B) selected from the group consisting of group diisocyanates, alicyclic diisocyanates and modified products thereof.
  • a two-component reaction type composition for forming a thermoplastic matrix resin comprises an active hydrogen component containing an aromatic diamine (A) having an alkylthio group; and an isocyanate component containing at least one diisocyanate (B) selected from the group consisting of group diisocyanates, alicyclic diisocyanates and modified products thereof.
  • the active hydrogen component contains an aromatic diamine (A) having an alkylthio group.
  • the aromatic diamine (A) having an alkylthio group a compound having two amino groups directly bonded to the aromatic ring and an alkylthio group directly bonded to the aromatic ring is preferred.
  • the alkylthio group is a group represented by -SC n H 2n+1 (where n is an integer of 1 or more, preferably an integer of 1 to 5).
  • the aromatic diamine (A) may have one, two or more alkylthio groups in one molecule. Preference is given to having two alkylthio groups directly attached to the aromatic ring.
  • aromatic diamine (A) it is preferable to use, for example, dialkylthiotoluene diamines such as dimethylthiotoluene diamine, diethylthiotoluene diamine, and dipropylthiotoluene diamine.
  • diamines such as other aromatic diamines may be used together with the aromatic diamine (A).
  • Other diamines include, for example, 4,4'-methylenedianiline, 4,4'-methylenebis(2-methylaniline), 4,4'-methylenebis(2-ethylaniline), 4,4'-methylenebis ( 2-isopropylaniline), 4,4′-methylenebis(2,6-dimethylaniline), 4,4′-methylenebis(2,6-diethylaniline), 4,4′-methylenebis(N-methylaniline), 4 ,4′-methylenebis(N-ethylaniline), 4,4′-methylenebis(N-sec-butylaniline), diethyltoluenediamine and the like. These may be used either singly or in combination of two or more.
  • the diamine used as the active hydrogen component preferably contains the aromatic diamine (A) as a main component, preferably 50% by mass or more of the diamine is the aromatic diamine (A), more preferably 70% by mass of the diamine.
  • the above is the aromatic diamine (A), and more preferably 90% by mass or more of the diamine is the aromatic diamine (A).
  • 15% by mass or more of the active hydrogen component is preferably the aromatic diamine (A), more preferably 40% by mass or more of the active hydrogen component is the aromatic diamine (A), and still more preferably the active hydrogen component.
  • 70% by mass or more of the aromatic diamine (A), more preferably 90% by mass or more of the active hydrogen component is the aromatic diamine (A).
  • the active hydrogen component may contain a diol together with a diamine.
  • diols include alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol and 1,6-hexanediol, diethylene glycol, Polyalkylene glycols such as triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, bisphenol S, bisphenol F and the like. These may be used either singly or in combination of two or more.
  • the active hydrogen component forms a thermoplastic resin, it is bifunctional, that is, diamines and diols are used. may contain.
  • the isocyanate component contains at least one diisocyanate (B) selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates and modified products thereof.
  • Aliphatic diisocyanates that is, chain aliphatic diisocyanates
  • HDI hexamethylene diisocyanate
  • 2,2,4-trimethylhexamethylene diisocyanate 2,4,4-trimethyl hexamethylene diisocyanate
  • lysine diisocyanate 2-methylpentane-1,5-diisocyanate
  • 3-methylpentane-1,5-diisocyanate and the like.
  • modified aliphatic diisocyanate examples include an isocyanate group-terminated urethane prepolymer obtained by reacting an aliphatic diisocyanate with a diol, a bifunctional adduct modified, and a bifunctional allophanate modified.
  • the aliphatic diisocyanate at least one selected from the group consisting of hexamethylene diisocyanate (HDI) and its modified products because the viscosity during molding is lower and the tensile breaking strain of the resulting resin is better. is preferably used.
  • HDI hexamethylene diisocyanate
  • alicyclic diisocyanates examples include isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate (H12MDI), 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (Isocyanatomethyl)cyclohexane and the like can be mentioned.
  • the modified alicyclic diisocyanate examples include an isocyanate group-terminated urethane prepolymer obtained by reacting an alicyclic diisocyanate with a diol, a bifunctional adduct modified, and a bifunctional allophanate modified.
  • the alicyclic diisocyanate it is preferable to use at least one selected from the group consisting of isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), and modified products thereof.
  • IPDI isophorone diisocyanate
  • H12MDI 4,4'-dicyclohexylmethane diisocyanate
  • a blocked diisocyanate (B1) in which at least one isocyanate group is blocked and an unblocked diisocyanate (B2) in which the isocyanate group is not blocked are used in combination.
  • the blocked diisocyanate (B1) is a compound obtained by reacting the isocyanate group of the diisocyanate (B) with a blocking agent, and one or both of the two isocyanate groups of the diisocyanate are blocked by the blocking agent.
  • the blocked diisocyanate (B1) may be a single diisocyanate in which one isocyanate group is blocked, a diisocyanate in which both isocyanate groups are blocked, or a mixture thereof.
  • blocking agents include oximes such as MEK oxime (methyl ethyl ketone oxime) and cyclohexanone oxime, lactams such as caprolactam and butyrolactam, alcohols such as methanol, ethanol, and benzyl alcohol, and phenols such as phenol, para-t-butylphenol, and cresol. , dimethylamine, diisopropylamine, dicyclohexylamine, amines such as aniline, and ammonia. These may be used either singly or in combination of two or more.
  • oximes such as MEK oxime (methyl ethyl ketone oxime) and cyclohexanone oxime
  • lactams such as caprolactam and butyrolactam
  • alcohols such as methanol, ethanol, and benzyl alcohol
  • phenols such as phenol, para-t-butylphenol, and cresol.
  • the blocked diisocyanate (B1) is obtained by blocking the diisocyanate (B) with a blocking agent, it may be a blocked aliphatic diisocyanate, a blocked alicyclic diisocyanate, or a blocked modified aliphatic diisocyanate. It may be a blocked modified alicyclic diisocyanate, or a combination of two or more thereof.
  • the unblocked diisocyanate (B2) is a diisocyanate in which both of the two isocyanate groups of the diisocyanate (B) are not blocked with a blocking agent. Therefore, the unblocked diisocyanate (B2) may be an unblocked aliphatic diisocyanate, an unblocked alicyclic diisocyanate, an unblocked modified aliphatic diisocyanate, or an unblocked modified alicyclic diisocyanate. , a combination of two or more thereof.
  • Examples of the unblocked diisocyanate (B2) include the above-listed aliphatic diisocyanates and modified products thereof, and alicyclic diisocyanates and modified products thereof, and one or more of them can be used as they are.
  • the blocked diisocyanate (B1) and the unblocked diisocyanate (B2) may be the same diisocyanate or different diisocyanates except for the presence or absence of blocking. That is, for example, a blocked aliphatic diisocyanate and an unblocked aliphatic diisocyanate may be used in combination, a blocked modified aliphatic diisocyanate and an unblocked modified aliphatic diisocyanate may be used in combination, and a blocked alicyclic diisocyanate and an unblocked alicyclic diisocyanate may be used in combination. Also, a blocked alicyclic diisocyanate and a non-blocked modified aliphatic diisocyanate may be used in combination.
  • a blocked aliphatic diisocyanate and an unblocked modified aliphatic diisocyanate may be used in combination.
  • a blocked modified alicyclic diisocyanate and an unblocked aliphatic diisocyanate may be used in combination.
  • a blocked aliphatic diisocyanate, a blocked alicyclic diisocyanate and a non-blocked alicyclic diisocyanate may be used in combination.
  • the blending ratio of the blocked diisocyanate (B1) and the unblocked diisocyanate (B2) is not particularly limited, it is the molar ratio of the blocked isocyanate groups to the isocyanate groups of the entire isocyanate component (preferably the entire diisocyanate (B)). It is preferable that the block rate is 1 to 56%.
  • the blocking ratio of the isocyanate component By setting the blocking ratio of the isocyanate component to 1% or more, the adhesion between the layers of the laminate can be improved.
  • the block ratio is 56% or less, the viscosity of the second liquid containing the isocyanate component can be reduced, and the miscibility with the first liquid containing the active hydrogen component can be improved.
  • the viscosity of the second liquid it is possible to reduce the resistance when it flows through the piping and increase the flow velocity.
  • the viscosity of the liquid mixture obtained by mixing the first liquid and the second liquid can be reduced to improve the impregnation of the fibers.
  • the blocking agent evaporates when it dissociates, and when the block ratio is 56% or less, voids in the resin caused by vaporization and thinning due to a decrease in the amount of resin can be reduced.
  • the blocking rate of the isocyanate component is more preferably 5% or more, still more preferably 10% or more, still more preferably 15% or more. Also, the block rate is more preferably 55% or less, still more preferably 45% or less, and even more preferably 40% or less.
  • the isocyanate component preferably consists essentially of the diisocyanate (B), preferably 80% by mass or more of the isocyanate component is the diisocyanate (B), more preferably 90% by mass or more, and still more preferably 95% by mass. It is at least 98% by mass, particularly preferably at least 98% by mass.
  • a bifunctional isocyanate that is, a diisocyanate is used in order to form a thermoplastic resin.
  • the two-component reactive composition according to the present embodiment contains the active hydrogen component and the isocyanate component, and the active hydrogen component and the isocyanate component react to form a thermoplastic resin. That is, the two-liquid reaction type composition has the property that the reaction product becomes a thermoplastic resin.
  • the two-component reaction type composition uses an active hydrogen component as the first component and an isocyanate component as the second component. It is a two-component curable resin composition that can be (that is, solidified).
  • the two-liquid reaction type composition has two liquids, the first liquid and the second liquid, but may have three liquids or more as long as there are at least two liquids.
  • the two-part reaction type composition may contain a catalyst for promoting the reaction between the active hydrogen component and the isocyanate component.
  • a metal catalyst or an amine catalyst can be used as the catalyst.
  • Metal catalysts include tin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dioctate; lead catalysts such as lead octylate, lead octenoate, and lead naphthenate; and bismuth catalysts, such as bismuth octylate and bismuth neodecanoate. can be mentioned.
  • Examples of amine-based catalysts include tertiary amine compounds such as triethylenediamine. These catalysts can be used alone or in combination.
  • the two-component reaction type composition may contain a plasticizer, a flame retardant, an antioxidant, a moisture absorbent, an anti-mold agent, a silane coupling agent, an antifoaming agent, a surface control agent, and an internal release agent.
  • a plasticizer such as polyethylene glycol dimethacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium sulfate, sodium bicarbonate, sodium sulfate, sodium
  • the molar ratio (NCO/active hydrogen group) of isocyanate groups (total of blocked and unblocked groups) to active hydrogen groups (total of amino groups and hydroxyl groups) is It is not particularly limited, and may be 1.0 or more, or 1.1 or more. Also, the molar ratio (NCO/active hydrogen group) may be 2.0 or less, 1.5 or less, or 1.2 or less.
  • a matrix resin for a thermoplastic resin composite is a thermoplastic resin containing a reaction product of the active hydrogen component and the isocyanate component. It is obtained by curing a two-part reaction type composition.
  • the resulting resin is a thermoplastic polyurea resin
  • the active hydrogen component contains a diol
  • the resulting resin is a thermoplastic polyurethane/urea resin.
  • the thermoplastic polyurethane/urea resin is a resin containing both a urethane bond and a urea bond in its main chain.
  • the matrix resin may contain the blocked isocyanate groups of the blocked diisocyanate (B1) contained in the diisocyanate (B) while retaining the blocked isocyanate groups.
  • the blocking agent of the blocked diisocyanate (B1) may be dissociated so that the isocyanate group reacts with the remaining active hydrogen component to form a urea bond or a urethane bond. That is, the matrix resin may be at the stage of a primary molded product obtained by reacting an active hydrogen component with an unblocked diisocyanate (B2), dissociating the blocking agent of the blocked diisocyanate (B1) to form an active hydrogen component. It may be a secondary molded product obtained by reacting with.
  • the glass transition temperature (Tg) of the matrix resin is not particularly limited.
  • the glass transition temperature is, for example, preferably 100° C. or higher, more preferably 120° C. or higher, and even more preferably 150° C. or higher.
  • the upper limit of the glass transition temperature is not particularly limited, and may be, for example, 220° C. or lower, or 200° C. or lower.
  • thermoplastic resin composite is a fiber-reinforced composite material (FRP) containing a cured product of the two-part reaction type composition or the matrix resin, and fibers as reinforcing materials.
  • FRP fiber-reinforced composite material
  • the fibers include, for example, carbon fiber, glass fiber, aramid fiber, alumina fiber, silicon carbide fiber, boron fiber, metal fiber, natural fiber, mineral fiber, etc. Any one or a combination of two or more thereof may be used. may be configured.
  • Examples of carbon fibers include PAN-based, pitch-based, and rayon-based fibers.
  • As the fiber at least one selected from the group consisting of carbon fiber, glass fiber, and aramid fiber is preferable.
  • the fibers may be applied with glue or paint to promote bonding with the resin.
  • forms of fibers include continuous fibers such as filaments, fibers, strand rovings or fabrics, woven mats, non-woven mats, and other forms.
  • the ratio of fiber to thermoplastic resin in the thermoplastic resin composite is not particularly limited.
  • the volume content of fibers per unit volume of the thermoplastic resin composite may be 30 to 70% or 50 to 60%.
  • the volume content of the thermoplastic resin is preferably 30 to 70%, more preferably 40 to 50%, per unit volume of the thermoplastic resin composite.
  • the thermoplastic resin composite is preferably an in-situ polymerization type thermoplastic resin composite that uses the two-component reaction type composition as a thermoplastic resin as a matrix. That is, it is preferable to produce a thermoplastic resin composite by impregnating a fiber with a monomer mixed liquid obtained by mixing the two-part reaction type composition, and polymerizing the fibers after the impregnation to form a thermoplastic resin.
  • the thermoplastic resin composite comprises a matrix resin (preferably a thermoplastic matrix resin obtained by reacting the two-component reactive composition) and a plurality of primary fibers as reinforcing materials. It is preferably a laminate obtained by stacking molded bodies and laminating and integrating them by thermoforming.
  • the matrix resin in the primary molding preferably contains blocked isocyanate groups.
  • the laminate is a secondary molded body obtained by thermoforming a plurality of the primary molded bodies, and the isocyanate groups are reacted during secondary molding by dissociation of the blocking agent for the blocked isocyanate groups. can be done. Therefore, between the layers of the laminate, not only thermal fusion bonding is formed by heating the thermoplastic resin, but also chemical bonds are formed by reaction of dissociated isocyanate groups. Therefore, the layers can be bonded more firmly.
  • the shape of the primary molded body is not particularly limited, but for example, it may be plate-shaped (a concept that includes thin ones such as sheet-like), and a plurality of plate-shaped primary molded bodies are laminated and integrated.
  • a laminate may be obtained by
  • thermoplastic resin composite as the primary molded body can be processed into various shapes by secondary molding and used. suitable for forming.
  • thermoplastic resin composite examples include, for example, housings for electronic equipment, which are suitably used for computers, televisions, cameras, audio players, and the like.
  • the thermoplastic resin composite is also suitable for electrical and electronic component applications, such as connectors, LED lamps, sockets, optical pickups, terminal boards, printed circuit boards, speakers, motors, magnetic heads, power modules, generators, electric motors, It can be suitably used for parts of transformers, current transformers, voltage regulators, rectifiers and inverters.
  • thermoplastic resin composite is also suitable for automotive parts, vehicle-related parts, and the like, such as safety belt parts, instrument panels, console boxes, pillars, roof rails, fenders, bumpers, door panels, roof panels, hood panels, Trunk lid, door mirror stay, spoiler, hood louver, wheel cover, wheel cap, garnish, intake manifold, fuel pump, engine coolant joint, window washer nozzle, wiper, battery peripheral parts, wire harness connector, lamp housing, lamp reflector, Suitable for use in lamp sockets and the like.
  • safety belt parts such as safety belt parts, instrument panels, console boxes, pillars, roof rails, fenders, bumpers, door panels, roof panels, hood panels, Trunk lid, door mirror stay, spoiler, hood louver, wheel cover, wheel cap, garnish, intake manifold, fuel pump, engine coolant joint, window washer nozzle, wiper, battery peripheral parts, wire harness connector, lamp housing, lamp reflector, Suitable for use in lamp sockets and the like.
  • thermoplastic resin composite is also suitable as a building material, and can be It is suitably used for parts, lifeline-related parts, and the like.
  • the fiber-reinforced composite material is also suitable for use as sports goods, such as golf club shafts, golf balls and other golf-related goods, tennis rackets and badminton rackets and other sports racket-related goods, American football, baseball, softball and the like. It is suitably used for body protective equipment for sports such as masks, helmets, chest pads, elbow pads and knee pads, fishing gear-related equipment such as fishing rods, reels and lures, and winter sports-related equipment such as skis and snowboards.
  • delamination between the layers of the laminate can be suppressed by including the blocked diisocyanate in the two-liquid reaction type composition.
  • a method for producing a thermoplastic resin composite includes the following steps (1) and (2), and preferably further includes the following step (3).
  • the thermoplastic matrix resin-forming composition is polymerized while retaining the blocked isocyanate groups to obtain a primary molded article containing the thermoplastic matrix resin obtained by polymerization. molding process.
  • the composition for forming a thermoplastic matrix resin (hereinafter also referred to as a monomer mixed solution) used in the impregnation step contains an active hydrogen component and an isocyanate component. and diisocyanate.
  • the isocyanate component By including the blocked diisocyanate as the isocyanate component in this way, the isocyanate group can be reacted during secondary molding, and the adhesion between the layers of the laminate can be improved.
  • the active hydrogen component of the monomer mixture preferably contains an aromatic diamine (A) having an alkylthio group.
  • the isocyanate component contains at least one diisocyanate (B) selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates and modified products thereof, and the diisocyanate (B) is a blocked diisocyanate and an unblocked diisocyanate. is preferably included.
  • the details of such a mixed monomer solution are as described above for the two-component reaction type composition.
  • the fibers used in the impregnation step are as described for the thermoplastic resin composite, and similar fibers can be used.
  • FIG. 1 shows an example of a manufacturing apparatus 1 applicable to the manufacturing method.
  • the manufacturing apparatus 1 includes an impregnation unit 20 that impregnates the fibers 10 with the monomer mixture, and a thermoforming unit 30 that heats the fibers 10 impregnated with the monomer mixture to form a thermoplastic resin composite (primary molded body 12). and a drawing device 40 for continuously drawing out the molded primary molded body 12.
  • the manufacturing apparatus 1 further includes a fiber supply section 50 that supplies the fibers 10 to the impregnation section 20 and a monomer supply section 60 that supplies the monomer mixture to the impregnation section 20 .
  • the fibers 10 supplied from the fiber supply section 50 are continuously impregnated with the monomer mixed liquid supplied from the monomer supply section 60.
  • the fiber supply unit 50 collects the fibers drawn out from the plurality of bobbins 51 into one and supplies the fibers 10 to the impregnation unit 20 .
  • the monomer supply unit 60 includes a first tank 61 storing a first liquid containing an active hydrogen component, a second tank 62 storing a second liquid containing an isocyanate component, and a mixer 63 .
  • the mixer 63 is a device that mixes the first liquid sent from the first tank 61 and the second liquid sent from the second tank 62 .
  • the mixer 63 may perform stirring and mixing using stirring blades, or may perform stirring and mixing with a mixing head arranged in a static mixer.
  • the monomer liquid mixture mixed by the mixer 63 is supplied to the impregnation section 20 .
  • the impregnation section 20 is composed of a plurality of impregnation rollers 21 . Specifically, the impregnating section 20 drops the monomer liquid mixture at a plurality of locations on the fibers 10 running through the conveying rollers 22 , and impregnates the fibers 10 with the monomer liquid mixture by the plurality of impregnation rollers 21 . is configured as
  • a heating device for preheating the fibers 10 may be installed before the impregnating section 20 . By heating in advance, the impregnation of the monomer mixed solution can be carried out quickly. In addition, the moisture absorbed by the fibers 10 can be evaporated immediately before the impregnation, and the influence of the moisture during the polymerization of the monomer mixed solution can be removed more favorably. Therefore, the polymerization reaction of the monomer mixture can be stabilized.
  • the fibers 10 impregnated in the impregnating section 20 are passed through the thermoforming section 30 at a predetermined heating temperature T, thereby polymerizing the monomer mixture and the thermoplastic resin obtained by the polymerization.
  • the composite (primary molded body 12) is molded. That is, the fiber 10 impregnated with the monomer mixture is shaped and polymerized by heating.
  • the thermoforming unit 30 includes a thermoforming mold 31 for forming the fibers 10 impregnated with the monomer mixture into a predetermined thickness and width, and a primary molded body 12 pulled out from the thermoforming mold 31. and a heating device 32 for heating to promote the polymerization reaction. Note that the heating device 32 may not be provided.
  • the fibers 10 impregnated with the monomer mixture are heated at a temperature lower than the dissociation temperature Td of the blocked diisocyanate (B1). This allows the monomer mixture to be polymerized to form a thermoplastic matrix resin while retaining the blocked isocyanate groups.
  • the heating temperature T which is the set temperature of the thermoforming unit 30, is set to a temperature lower than the dissociation temperature Td.
  • the temperature set as the heating temperature T may be a single temperature, or may be set in a predetermined temperature range with a temperature distribution depending on the portion of the thermoforming unit 30 .
  • the maximum temperature is set to a temperature lower than the dissociation temperature Td.
  • the dissociation temperature Td of the blocked diisocyanate (B1) is the temperature at which the blocking agent dissociates from the blocked isocyanate groups. Since the temperature at which the blocking agent dissociates generally has a range, it is preferable to heat the fiber 10 at a temperature lower than the minimum temperature, that is, the temperature at which the blocking agent starts to dissociate during heating (dissociation start temperature).
  • the dissociation temperature Td of the blocked diisocyanate (B1) is not particularly limited.
  • the temperature for heating the fibers 10 is set to a temperature lower than the glass transition temperature Tg of the thermoplastic matrix resin in the primary molded body 12 obtained by polymerizing the monomer mixture. That is, the temperature for heating the fibers 10 is preferably lower than the dissociation temperature Td of the blocked diisocyanate (B1) and lower than the glass transition temperature Tg of the thermoplastic matrix resin after primary molding.
  • the glass transition temperature after primary molding is the glass transition temperature of a thermoplastic matrix resin obtained by polymerization while retaining blocked isocyanate groups.
  • the heating temperature T in the thermoforming unit 30 is set to a temperature lower than the dissociation temperature Td and lower than the glass transition temperature Tg. More preferably, the heating temperature T is set to a temperature 20° C. or more lower than the glass transition temperature Tg (T ⁇ Tg ⁇ 20° C.).
  • the primary molding process includes a drawing process in which the primary molded body 12 is continuously drawn out from the thermoforming unit 30 by the drawing device 40 .
  • the drawing device 40 is composed of a pair of upper and lower rollers 41, 41 for drawing out the primary molded body 12 with it sandwiched therebetween.
  • the heating temperature T in the thermoforming part 30 is lower than the glass transition temperature Tg after the primary molding of the thermoplastic matrix resin, so that the primary molded body 12 pulled out from the thermoforming part 30 has a thermoplastic property.
  • the matrix resin is in a glass state below the glass transition temperature Tg. That is, at the stage of coming out of the thermoforming unit 30, although the polymerization is not completed, it is in a non-sticky, pseudo-cured state. Therefore, the pulled out primary molded body 12 is unlikely to lose its shape and can maintain its shape. Therefore, a thermoplastic resin composite can be efficiently produced by continuous pultrusion.
  • the resin in continuous pultrusion, generally, the resin is polymerized and cured by heating in the thermoforming unit, so the temperature of the primary molded product at the exit of the thermoforming unit is the polymerization temperature of the resin set in the thermoforming unit. becomes approximately equal to Therefore, in continuous pultrusion, if the polymerization temperature is higher than the glass transition temperature of the matrix resin, the primary molded product at the exit of the thermoforming unit is in a soft rubber state and cannot maintain a predetermined cross-sectional shape. . On the other hand, for example, it is possible to provide a cooling process after heat molding to cool the temperature below the glass transition temperature, but the apparatus is correspondingly large, and in addition, the drawing speed of the primary molded body is not slowed down.
  • thermoforming section Since the inside of the body cannot be cooled, the production efficiency is inferior.
  • polymerization is performed in the thermoforming section at a temperature lower than the glass transition temperature, and the primary molded body in which the thermoplastic matrix resin is in a glass state is pulled out from the thermoforming section. It is easy to maintain the shape of the molded body, and therefore the manufacturing efficiency can be improved.
  • a heating device may be provided after the drawing device 40 for further heating the primary molded body 12 to accelerate or complete the polymerization.
  • a cutting device such as a cutter may be provided after the drawing device 40 or after the additional heating device, thereby obtaining a plate material, a channel material, a round bar material, a strand material, or the like as the primary formed body 12.
  • the impregnating section 20 is composed of a plurality of impregnating rollers 21 provided in front of the heating mold 31, but the impregnating section may be provided inside the heating mold 31.
  • the impregnated portion is incorporated as part of the thermoformed portion 30 at its front end.
  • FIG. 2 shows an example thereof.
  • the fibers 10 let out from the bobbin 51 of the fiber supplying section 50 are fed into the thermoforming mold 31 of the thermoforming section 30 through the feed rollers 52 .
  • the monomer mixture supplied from the monomer supply unit 60 is directly injected into the thermoforming mold 31 by the injection jig 71 provided at the front end of the thermoforming mold 31, and the monomer mixture is injected in the thermoforming mold 31. is impregnated into the fiber 10. Therefore, the front end portion of the heat molding die 31 also serves as the impregnation portion 70 .
  • An impregnating jig such as an impregnating roller may be provided inside the heating mold 31 .
  • the fibers 10 can be impregnated with the monomer mixed liquid injected into the heating mold 31 by the injection jig 71 in a short period of time.
  • Such devising of the impregnation part 70 has a high effect of impregnating the fibers 10 with the monomer mixture in a short time while removing excess air. Fine voids (cavities) inside the subsequent primary molded body 12 can be reduced.
  • a plurality of the above primary molded bodies are stacked and integrated by thermoforming under conditions where the blocking agent is dissociated.
  • a laminate as a secondary molded body can be obtained by stacking a plurality of plate-shaped primary molded bodies and laminating and integrating them by hot pressing.
  • thermoforming is performed at a temperature equal to or higher than the dissociation temperature Td of the blocked diisocyanate (B1) in order to dissociate the blocking agent from the blocked isocyanate groups contained in the primary molded product.
  • Td dissociation temperature
  • the dissociated isocyanate groups of the blocking agent react with the active hydrogen components remaining in the primary molding to form additional chemical bonds. Therefore, the layers of the laminate can be strongly bonded and the adhesion between the layers can be improved.
  • a laminate when a laminate is obtained by hot pressing using a plate-shaped primary formed body, it may be laminated and integrated into a flat plate shape as it is. It may be formed into various shapes such as shape, box shape, and the like. Moreover, once it is laminated and integrated into a flat plate shape, it may be shaped into a desired shape by applying heat again.
  • (Diisocyanate) - Modified HDI NCO-terminated bifunctional urethane prepolymer of HDI, isocyanate value 230 mgKOH/g, "Duranate A201H” manufactured by Asahi Kasei Corporation ⁇ HDI: hexamethylene diisocyanate, isocyanate value 668 mgKOH / g, "Duranate HDI” manufactured by Asahi Kasei Corporation ⁇ IPDI: isophorone diisocyanate, isocyanate value 505 mgKOH / g, "VESTANATE IPDI” manufactured by EVONIK ⁇ H12MDI: 4,4′-dicyclohexylmethane diisocyanate, isocyanate value 427 mgKOH/g, “Desmodur W” manufactured by Covestro
  • BL1 to BL6 were synthesized as blocked diisocyanate (B1) according to the formulation (parts by mass) shown in Table 1 below. Specifically, a diisocyanate component was placed in a separable flask, each blocking agent was added, and the synthesis was performed by heating. At that time, those with high viscosity were appropriately diluted with a solvent such as toluene, and the solvent was recovered by an evaporator or the like after the synthesis.
  • B1 blocked diisocyanate
  • All of the obtained blocked diisocyanates BL1 to BL6 had a blocking rate of 100%, that is, they were diisocyanates in which all of the two isocyanate groups possessed by the diisocyanate were blocked with a blocking agent.
  • the dissociation temperature (dissociation start temperature) of the blocking agent in the blocked diisocyanates of BL1 to BL6 was measured.
  • weight change was measured while heating the sample at 15° C./min using “TG-DTA8122/S-SL” manufactured by RICOH Co., Ltd. to investigate the dissociation start temperature. Table 1 shows the results.
  • a first liquid containing an active hydrogen component was prepared by mixing diamine according to the formulation shown in Table 2 below. Also, according to Table 2, a blocked diisocyanate and an unblocked diisocyanate were mixed to prepare a second liquid containing an isocyanate component.
  • Table 2 shows the blocking rate, which is the molar ratio of blocked isocyanate groups to isocyanate groups in the entire isocyanate component, for the second liquid.
  • the blocking rate was calculated from the ratio of the total amount of isocyanate groups and the amount of blocked isocyanate groups obtained from the mass ratio of the blended diisocyanate.
  • the block rate of BL1 to BL6 was set to 100% as described above.
  • the molecular weight was determined from the isocyanate value of the diisocyanate, and the amount of the isocyanate group was determined using the molecular weight.
  • the viscosity of the second liquid was measured.
  • the viscosity was measured at 25° C. using a BM viscometer (manufactured by Toki Sangyo Co., Ltd.) according to JIS K7117-1:1999. Table 2 shows the results.
  • the glass transition temperature (corresponding to the glass transition temperature after primary molding) of the resin after polymerization while retaining the blocked isocyanate group was measured. .
  • the first liquid was adjusted to 25 ° C.
  • the second liquid adjusted to 25 ° C. was added thereto at the mass ratio and NCO/active hydrogen group molar ratio shown in Table 2, and stirred and mixed for 1 minute. bottom.
  • the resulting monomer mixed solution was applied in a sheet form and treated at 120° C. for 3 hours to obtain a resin sheet with a thickness of 2 mm.
  • thermoplastic resin composite was carried out.
  • fiber 10 carbon fiber (“T700SC-24000-60E” manufactured by Toray Industries, Inc.) was used.
  • the monomer mixture was supplied by the monomer supply unit 60 so that the volume content of the fibers 10 in the primary molded body 12 was 60%.
  • liquids A and B were sent from tanks 61 and 62 according to the mass ratio shown in Table 2, and stirred through a mixer 63 consisting of a static mixer to prepare a monomer mixed liquid.
  • the places where the monomer mixed liquid was dripped were divided into three places, and the flow of the monomer mixed liquid staying in the impregnation part 20 was promoted.
  • the fibers 10 supplied from the fiber supplying unit 50 were impregnated with the monomer mixed liquid in the impregnating unit 20 composed of a plurality of impregnating rollers 21 .
  • the heat forming mold 31 As the heat forming mold 31, an aluminum alloy is used, and in order to avoid a rapid hardening reaction of the monomer mixed liquid staying near the mold entrance into which the fiber 10 is sent, a water cooling pipe is provided at the mold entrance, and the temperature near the mold entrance is was kept in the range of 20-25°C. In addition, in order to prevent adhesion between the heating mold 31 and the primary molded body 12 during the curing reaction, a thin PTFE upper and lower middle is provided at the portion in contact with the primary molded body 12 inside the aluminum alloy heated molding die 31 . Set the child type.
  • a primary molding 12 having a width of 15 mm and a thickness of 0.5 mm was molded in the heating mold 31 set to a temperature lower than the dissociation temperature of the blocked diisocyanate. Specifically, the heating was controlled so that the temperature distribution from the vicinity of the entrance to the vicinity of the exit of the heating mold 31 varied continuously within the range of 20°C to 120°C.
  • the primary molded body 12 drawn out from the heating mold 31 by the drawing device 40 was further heated and cured in the heating device 32, which is a far-infrared heater.
  • the heating temperature by the heating device 32 was set to 120°C.
  • the length of the heating device 32 is variable, and the length of the heating device 32 is set to 1.0 m. Since the length of the thermoforming mold 31 was 0.5 m, the length of the thermoforming section 30 including the heating device 32 was 1.5 m.
  • the take-up speed was set to 500 mm/min so as to secure 3 minutes of polymerization time (that is, to secure 3 minutes of polymerization time from the heating mold 31 to the heating device 32).
  • the primary molded body 12 was in a glass state below the glass transition temperature at the stage when it was pulled out from the thermoforming section 30, that is, it was pseudo-cured.
  • the primary molded body 12 drawn out through the drawing device 40 was cut to a length of 30 cm. After that, in order to further complete the polymerization reaction of the primary molded body 12 , the primary molded body 12 was obtained by heating in an oven at 120° C. for 60 minutes.
  • Three sheets of the obtained primary molded body 12 were stacked and hot pressed at a pressure of 7 MPa for 60 minutes at a temperature higher than the dissociation temperature of the blocked diisocyanate to obtain a laminate as a secondary molded body.
  • the heating temperature during hot pressing was set to 220° C. in Example 6, and was set to 200° C. in other examples and comparative examples.
  • the obtained laminate was evaluated for the state of adhesion between the laminates.
  • Evaluation of the state of adhesion between laminations was carried out in accordance with JIS K7017: 1999, using a sample with a thickness of 1.5 mm, a total length of 60 mm and a width of 15 mm, and static three-point bending at a distance of 40 mm between fulcrums at 1 mm/min. A cross-section of the sample after testing was confirmed with an electron microscope. A sample with cracks between layers was evaluated as having poor interlayer adhesion and was evaluated as "X”, and a sample with no cracks was evaluated as having excellent interlayer adhesion and was evaluated as " ⁇ ". Table 2 shows the results.

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Abstract

Le but de la présente invention est d'améliorer l'adhérence entre des couches dans un corps stratifié lorsque le corps stratifié est moulé par stratification/intégration par moulage thermique.　Une composition réactive en deux parties selon un mode de réalisation est utilisée pour former une résine de matrice thermoplastique pour un matériau composite de résine thermoplastique contenant des fibres en tant que matériau de renforcement. La composition réactive en deux parties comprend un composant hydrogène actif comprenant une diamine aromatique ayant un groupe alkylthio et un composant isocyanate comprenant au moins un diisocyanate choisi dans le groupe constitué par un diisocyanate aliphatique, un diisocyanate alicyclique et des produits modifiés associés. Le diisocyanate comprend un diisocyanate bloqué dans lequel au moins l'un des groupes isocyanate est bloqué et un diisocyanate non bloqué dans lequel des groupes isocyanate ne sont pas bloqués.
PCT/JP2023/001897 2022-02-04 2023-01-23 Composition réactive en deux parties pour former une résine de matrice thermoplastique, résine de matrice pour matériau composite de résine thermoplastique, et matériau composite de résine thermoplastique et son procédé de production Ceased WO2023149258A1 (fr)

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WO2025211221A1 (fr) * 2024-04-01 2025-10-09 株式会社トクヤマ Composition durcissable permettant de former une couche de protection, stratifié, article optique, verre et lunettes
WO2026009979A1 (fr) * 2024-07-04 2026-01-08 旭化成株式会社 Composition de résine, produit durci de résine, procédé de formage de produit durci de résine, procédé de re-formage de produit durci de résine, procédé de récupération de composé contenant un groupe de blocage, et procédé de pelage de produit durci de résine

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CN118725588B (zh) * 2024-09-04 2025-01-28 浙江闪铸集团有限公司 双组分反应型3d打印蜡材及其制备方法和使用方法

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JP2018090804A (ja) * 2016-12-02 2018-06-14 エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ 貯蔵安定性の１ｋポリウレタンプリプレグ、およびこのプリプレグから製造されるポリウレタン組成物製の成形体
JP2019203113A (ja) * 2018-05-16 2019-11-28 第一工業製薬株式会社 熱可塑性マトリックス樹脂形成用二液硬化型組成物、繊維強化複合材料用マトリックス樹脂、及び繊維強化複合材料
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JPS58191745A (ja) * 1982-05-07 1983-11-09 Asahi Glass Co Ltd 繊維強化ポリウレタン成形材料
JP2018090804A (ja) * 2016-12-02 2018-06-14 エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ 貯蔵安定性の１ｋポリウレタンプリプレグ、およびこのプリプレグから製造されるポリウレタン組成物製の成形体
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WO2025211221A1 (fr) * 2024-04-01 2025-10-09 株式会社トクヤマ Composition durcissable permettant de former une couche de protection, stratifié, article optique, verre et lunettes
WO2026009979A1 (fr) * 2024-07-04 2026-01-08 旭化成株式会社 Composition de résine, produit durci de résine, procédé de formage de produit durci de résine, procédé de re-formage de produit durci de résine, procédé de récupération de composé contenant un groupe de blocage, et procédé de pelage de produit durci de résine

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