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WO2025135157A1 - Composition de résine durcissable et son utilisation - Google Patents

Composition de résine durcissable et son utilisation Download PDF

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Publication number
WO2025135157A1
WO2025135157A1 PCT/JP2024/045147 JP2024045147W WO2025135157A1 WO 2025135157 A1 WO2025135157 A1 WO 2025135157A1 JP 2024045147 W JP2024045147 W JP 2024045147W WO 2025135157 A1 WO2025135157 A1 WO 2025135157A1
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Prior art keywords
component
mass
parts
composition
curable resin
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PCT/JP2024/045147
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English (en)
Japanese (ja)
Inventor
敏彦 岡本
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Kaneka Corp
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Kaneka Corp
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Classifications

    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60B—VEHICLE WHEELS; CASTORS; AXLES FOR WHEELS OR CASTORS; INCREASING WHEEL ADHESION
    • B60B5/00—Wheels, spokes, disc bodies, rims, hubs, wholly or predominantly made of non-metallic material
    • B60B5/02—Wheels, spokes, disc bodies, rims, hubs, wholly or predominantly made of non-metallic material made of synthetic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present invention relates to a curable resin composition and its use.
  • Curable resin compositions containing epoxy resins are used in the fields of fiber-reinforced composite materials and fiber-reinforced molded products, for example, as described in Patent Documents 1 to 7.
  • JP 2018-35210 A Special Publication No. 2023-502717 JP 2023-139383 A JP 2021-116404 A JP 2023-146870 A International Publication WO2023/089997 Japanese Patent Application Publication No. 8-183836
  • One embodiment of the present invention has been developed in consideration of the above problems, and its purpose is to provide a new curable resin composition that can provide a cured product with excellent toughness.
  • the inventors conducted extensive research to solve the above problems, and as a result, completed the present invention.
  • a curable resin composition includes the following components (A) and (B), and does not include the following component (D), or further includes the following component (D);
  • the content of the (B) component is 1 part by
  • the composition (M) contains the component (A), the component (C), and the component (D) which are the same as the component (A), the component (C), and the component (D) contained in the curable resin composition, the contents of the (A), (C), and (D) components in the composition (M) are the same as the contents of the (A), (C), and (D) components in the curable resin composition,
  • the cured product (M) is a cured product obtained by curing the composition (M), and has a degree of cure of 98% or more as measured by DSC,
  • a cured product (Meq) of composition (Meq) is used as a sample, and dynamic viscoelasticity measurement is performed under conditions of a tensile mode and a frequency of 1 Hz, and the temperature at which the loss tangent is maximum is designated as Ttg(Meq) (°C), E'(Meq) represents the minimum value of the storage modulus (E') of the cured product (Meq)
  • the "curable resin composition” may be referred to as the “composition”
  • the “curable resin composition according to one embodiment of the present invention” may be referred to as the “composition” hereinafter.
  • X unit contained in a polymer, copolymer, or resin refers to a "structural unit derived from an X monomer.”
  • a "butadiene unit” refers to a "structural unit derived from a butadiene monomer.”
  • a curable resin composition according to one embodiment of the present invention comprises the following components (A) and (B), and does not comprise the following component (D), or further comprises the following component (D).
  • Component (A) an epoxy group-containing substance containing at least one member selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and alicyclic epoxy resins;
  • Component (B) polymer particles having a core-shell structure including a core layer and a shell layer;
  • the curable resin composition according to one embodiment of the present invention satisfies at least any one of the following (1) to (3).
  • component (C) Component (C): an acid anhydride (c1), an aromatic amine (c2), or an alicyclic amine (c3); the total content of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, and the alicyclic epoxy resin is 60 parts by mass to 100 parts by mass, relative to 100 parts by mass of the component (A);
  • the content of the (B) component is 1 part by mass to 100 parts by mass relative to 100 parts by mass of the (A) component,
  • the content of the (C) component is 5 parts by mass to 200 parts by mass relative to 100 parts by mass of the (A) component,
  • the content of the component (D) is 0.1 parts by mass to 10.0 parts by mass relative to 100 parts by mass of the component (A)
  • the value X calculated by the following formula is When the component (C) is the acid anhydride (c1), it is 1.05 to 5.50, When the component (C) is the aromatic amine (c2) or the alicyclic amine (c3); the total
  • component (C) an epoxy curing agent containing one or more selected from the group consisting of acid anhydrides (c1), aromatic amines (c2), and alicyclic amines (c3); the total content of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, and the alicyclic epoxy resin is 5 parts by mass to 100 parts by mass, relative to 100 parts by mass of the component (A);
  • the content of the (B) component is 1 part by mass to 100 parts by mass relative to 100 parts by mass of the (A) component,
  • the content of the (C) component is 10 parts by mass to 200 parts by mass relative to 100 parts by mass of the (A) component,
  • the content of the component (D) is 0.1 parts by mass to 10.0 parts by mass relative to 100 parts by mass of the component (A)
  • the component (A) satisfies any one of the following (i), (ii), or (iii); (i) the component (A)
  • component (C) an amine-based epoxy curing agent containing an amine (c4) having one or two active hydrogen atoms in the amino group per molecule; the total content of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, and the alicyclic epoxy resin is 5 parts by mass to 100 parts by mass, relative to 100 parts by mass of the component (A);
  • the content of the (B) component is 1 part by mass to 100 parts by mass relative to 100 parts by mass of the (A) component,
  • the content of the (C) component is 10 parts by mass to 200 parts by mass relative to 100 parts by mass of the (A) component,
  • the content of the component (D) is 0.1 parts by mass to 20.0 parts by mass relative to 100 parts by mass of the component (A)
  • the content of the amine (c4) in the component (C) is 5% by mass to 100% by mass in 100% by mass of the component (C)
  • the value Y calculated by the following formula is 22 to 400
  • the cured product obtained by curing composition (M) is called “cured product (M)".
  • Cured product (M) can also be called “cured product (M) of composition (M)”.
  • Dynamic viscoelasticity measurement is performed on the cured product (M) as a sample under conditions of tensile mode and frequency of 1 Hz. The loss tangent and storage modulus are obtained by such dynamic viscoelasticity measurement.
  • the temperature at which the loss tangent of the cured product (M) is maximum is called Ttg(M) (°C).
  • Composition (M) contains components (A), (C), and (D) which are the same as (identical to) components (A), (C), and (D) contained in this composition.
  • the contents of components (A), (C), and (D) in composition (M) are the same as the contents of components (A), (C), and (D) in this composition.
  • Composition (M) does not contain component (B).
  • the composition (Meq) used to calculate the value X contains the same (A), (C) and (D) components as the (A), (C) and (D) components contained in the curable resin composition, (ii) does not contain the (B) component contained in the curable resin composition, and (iii) the contents of the (A) and (D) components in the composition (Meq) are the same as the contents of the (A) and (D) components in the curable resin composition.
  • the composition (Meq) used to calculate the value X does not contain the (D) component.
  • the degree of cure of the cured product is the curing reaction rate calculated from the total heat generation amount of the uncured curable resin composition measured using a DSC (differential scanning calorimeter) and the residual heat generation amount of the cured product obtained by curing the curable resin composition.
  • DSC differential scanning calorimeter
  • the inventor independently and surprisingly discovered that by setting the molecular weight between crosslink points of the cured product to a value within a specific range and using polymer particles, the toughness of the cured product is excellent.
  • a curable resin composition ( ⁇ ) containing an epoxy group-containing substance (component (A)), polymer particles (component (B)), a curing agent (component (C)), and a curing accelerator (component (D)) as an example.
  • a composition ( ⁇ ) i.e., not containing component (B)
  • a composition ( ⁇ ) containing the same components (A), (C), and (D) as the curable resin composition ( ⁇ ) in the same amounts as the curable resin composition ( ⁇ ) is prepared.
  • composition ( ⁇ eq) i.e., not containing component (B)
  • the amounts of the components (A) and (D) are the same as those in the curable resin composition ( ⁇ ).
  • the amount of the (C) component is an amount in which the molar amount of the functional group that reacts with the epoxy group in the (C) component (for example, an acid anhydride group when the (C) component is an acid anhydride, or an active hydrogen group of an amine when the (C) component is an aromatic amine or alicyclic amine) is equivalent to the molar amount of the epoxy group in the (A) component.
  • the molar amount of the functional group that reacts with the epoxy group in the (C) component for example, an acid anhydride group when the (C) component is an acid anhydride, or an active hydrogen group of an amine when the (C) component is an aromatic amine or alicyclic amine
  • the ratio of the crosslinking molecular weight of the cured product ( ⁇ ) obtained by curing the composition ( ⁇ ) to the crosslinking molecular weight of the cured product ( ⁇ eq) obtained by curing the composition ( ⁇ ) is set to a value within a specific range, which is referred to as "setting the crosslinking molecular weight of the cured product to a value within a specific range.”
  • ⁇ represents the Poisson's ratio of the cured product
  • ⁇ represents the specific gravity of the cured product
  • R represents the gas constant
  • T absolute temperature (K)
  • E and G represent the Young's modulus and the rigidity modulus in the rubber-like region of the cured product.
  • the rubber-like region is a region found on the higher temperature side than the transition region near the glass transition temperature when the temperature dependence of the elastic modulus (Young's modulus, rigidity modulus, etc.) is measured, and represents a region in which the temperature dependence of the elastic modulus is flat. Since crosslinked polymers such as epoxy resin cured products do not have a flow region on the higher temperature side than the rubber-like region, E and G in the formula can be expressed as the minimum values of the Young's modulus and rigidity modulus in the rubber-like region.
  • ⁇ represents the Poisson's ratio of the cured material
  • ⁇ represents the specific gravity of the cured material
  • R represents the gas constant
  • E'min represents the minimum value of the storage modulus of the cured material
  • Tmin represents the temperature (°C) at which the storage modulus of the cured material reaches its minimum value.
  • ratio ⁇ 2 x [1 + ⁇ (cured product ( ⁇ ))] x ⁇ (cured product ( ⁇ )) x R x [273 + Tmin (cured product ( ⁇ ))] / E'min (cured product ( ⁇ )) ⁇ / ⁇ 2 x [1 + ⁇ (cured product ( ⁇ eq))] x ⁇ (cured product ( ⁇ eq)) x R x [273 + Tmin (cured product ( ⁇ eq))] / E'min (cured product ( ⁇ eq)) ⁇ .
  • the only difference between the cured product ( ⁇ ) and the cured product ( ⁇ eq) is the content of the (C) component.
  • the difference in the content of the (C) component does not have a significant effect on the Poisson's ratio ( ⁇ ) and the specific gravity ( ⁇ ) of the cured product. Therefore, in the above formula, ⁇ (cured product ( ⁇ )) and ⁇ (cured product ( ⁇ eq)) can be regarded as having the same value, and ⁇ (cured product ( ⁇ )) and ⁇ (cured product ( ⁇ eq)) can be regarded as having the same value.
  • the above-mentioned ratio is designated as "X.” That is, as a result of intensive research, the present inventor independently obtained the novel finding that
  • the evaluation of the molecular weight between crosslinks must be based on the measured value of the cured product obtained by curing a composition containing only the components (A), (C), and (D). This is because the components (A) and (C) form a crosslinked structure, and the component (D) can affect the degree of progress of the crosslinking reaction. Conversely, when evaluating the molecular weight between crosslinks, components other than the components (B) and (A) to (D) (e.g., inorganic fillers) cannot be added. Although these components do not participate in the crosslinking formation, they affect the E'min of the cured product obtained by curing the composition, and the molecular weight between crosslinks cannot be evaluated correctly.
  • the component (D) is not incorporated into the crosslinked structure, but the amount added is small compared to the total amount of the components (A) and (C) because it is a curing accelerator, and the effect of the component (D) remaining unreacted after curing on the molecular weight between crosslinks is considered to be small.
  • the component (A) is an epoxy group-containing substance.
  • epoxy group-containing substance refers to a substance that has one or more epoxy groups in one molecule.
  • the epoxy group-containing substance which is component (A) contains at least one or more selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and alicyclic epoxy resins.
  • This composition has the advantages of having a relatively low viscosity and excellent processability, and furthermore, the cured product obtained by curing the composition has excellent strength, elastic modulus, and heat resistance (high Tg).
  • an "epoxy group-containing substance having two or more epoxy groups in one molecule” may be referred to as a "polyfunctional epoxy group-containing substance,” and an “epoxy group-containing substance having X epoxy groups in one molecule” may be referred to as an "X-functional epoxy group-containing substance.”
  • the bisphenol A type epoxy resin and the bisphenol F type epoxy resin in component (A) are each preferably independently a polyfunctional epoxy group-containing substance, and more preferably a difunctional epoxy group-containing substance.
  • This configuration has the advantage of a high toughness improvement effect due to control of the molecular weight between crosslinking points.
  • the alicyclic epoxy resin in component (A) is preferably a polyfunctional epoxy group-containing substance, and more preferably a difunctional epoxy group-containing substance.
  • This configuration has the advantage that the composition has a particularly low viscosity and excellent processability, and further has the advantage of a high toughness improvement effect due to control of the molecular weight between crosslinking points.
  • Examples of commercially available bisphenol A type epoxy resins include those sold under the trade name jER by Mitsubishi Chemical Corporation (e.g., jER828, jER825, jER827, jER828EL, jER828US, jER828XA, jER834, jER1001, jER1002, jER1004, jER1007, jER1009, jER1010), and those sold by Momentive Specialty Chemicals, Inc. those commercially available under the trademark EPON from Olin Epoxy Co.
  • examples of such products include, but are not limited to, those sold under the trade name DER by Epson Corporation (e.g., DER 331, DER 332, DER 336, and DER 439), those sold under the trade name ADEKA RESIN by ADEKA Corporation (e.g., EP-4100, EP-4300, EP-4400, EP-4530, EP-4504), and those sold under the trade name EPICLON by DIC Corporation (e.g., EPICLON 840, EPICLON 850).
  • Examples of commercially available bisphenol F type epoxy resins include, but are not limited to, those sold under the trade name jER by Mitsubishi Chemical Corporation (e.g., jER806, jER806H, jER807, jER4005P, jER4007P, jER4010P), those sold under the trade name DER by Olin Epoxy Co. (e.g., DER 334), those sold under the trade name ADEKA RESIN by ADEKA Corporation (e.g., EP-4901, EP-4901E), and those sold under the trade name EPICLON by DIC Corporation (e.g., EPICLON 830).
  • Alicyclic epoxy resins are compounds that contain (i) one or more saturated or unsaturated aliphatic hydrocarbon rings and (ii) one or more epoxy groups in the molecule, and also include epoxy resins that contain a cycloalkane ring.
  • alicyclic epoxy resins include 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, tetrahydroindene diepoxide, vinylcyclohexene oxide, dipentene dioxide, bis(3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene dioxide, bis(2,3-epoxycyclopentyl)ether, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxidized butanetetracarboxylic acid tetrakis, and the like.
  • epoxy resins examples include bis-(3-cyclohexenylmethyl)-modified epsilon-caprolactone, bi-7-oxabicyclo[4.1.0]heptane, dodecahydrobisphenol A diglycidyl ether, dodecahydrobisphenol F diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hexahydroterephthalic acid diglycidyl ester, and diglycidyl ether of 2,2-bis(4-hydroxycyclohexyl)propane (general name: hydrogenated bisphenol A type liquid epoxy resin).
  • the alicyclic epoxy resin preferably contains one or more selected from the group consisting of 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate, 1,2-epoxy-4-(2-oxiranyl) cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxidized butane tetracarboxylic acid tetrakis-(3-cyclohexenylmethyl) modified epsilon-caprolactone, and diglycidyl ether of 2,2-bis(4-hydroxycyclohexyl)propane, more preferably consists of only one or more selected from the group, more preferably contains 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate, and even more preferably consists of only 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohex
  • the total content of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and alicyclic epoxy resin is 60 parts by mass to 100 parts by mass, preferably 65 parts by mass to 100 parts by mass, more preferably 70 parts by mass to 100 parts by mass, more preferably 71 parts by mass to 100 parts by mass, more preferably 80 parts by mass to 100 parts by mass, even more preferably 90 parts by mass to 100 parts by mass, and particularly preferably 95 parts by mass to 100 parts by mass.
  • the upper limit of the total content of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and alicyclic epoxy resin may be less than 100 parts by mass.
  • the composition has low viscosity and excellent processability, and further, the cured product obtained by curing the composition has excellent strength, elastic modulus, and heat resistance (high Tg).
  • the total content of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, and the alicyclic epoxy resin may be 100 parts by mass.
  • the (A) component may be composed only of the bisphenol A type epoxy resin, may be composed only of the bisphenol F type epoxy resin, may be composed only of the alicyclic epoxy resin, may be composed only of the bisphenol A type epoxy resin and the alicyclic epoxy resin, may be composed only of the bisphenol F type epoxy resin and the alicyclic epoxy resin, may be composed only of the bisphenol A type epoxy resin and the bisphenol F type epoxy resin, may be composed only of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, and the alicyclic epoxy resin.
  • the (A) component may not contain other epoxy group-containing substances (e.g., glycidylamine type epoxy resin, etc.) described later.
  • Component (A) may further contain an epoxy group-containing substance other than bisphenol A epoxy resin, bisphenol F epoxy resin, and alicyclic epoxy resin, in addition to one or more selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, and alicyclic epoxy resin.
  • epoxy group-containing substances other than bisphenol A epoxy resin, bisphenol F epoxy resin, and alicyclic epoxy resin may also be referred to as "other epoxy group-containing substances”.
  • Other epoxy group-containing substances include (i) polyfunctional epoxy group-containing substances other than bisphenol A epoxy resin, bisphenol F epoxy resin, and alicyclic epoxy resin, and (ii) monofunctional epoxy group-containing substances other than alicyclic epoxy resin.
  • polyfunctional epoxy group-containing substances other than bisphenol A epoxy resin, bisphenol F epoxy resin, and alicyclic epoxy resin may also be referred to as “other polyfunctional epoxy group-containing substances”.
  • monofunctional epoxy group-containing substances other than alicyclic epoxy resin may also be referred to as “other monofunctional epoxy group-containing substances”.
  • the (A) component may be (i) composed only of bisphenol A type epoxy resin and other epoxy group-containing substances, (ii) composed only of bisphenol F type epoxy resin and other epoxy group-containing substances, (iii) composed only of alicyclic epoxy resin and other epoxy group-containing substances, (iv) composed only of bisphenol A type epoxy resin, alicyclic epoxy resin and other epoxy group-containing substances, (v) composed only of bisphenol F type epoxy resin, alicyclic epoxy resin and other epoxy group-containing substances, (vi) composed only of bisphenol A type epoxy resin, bisphenol F type epoxy resin and other epoxy group-containing substances, or (vii) composed of bisphenol A type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin and other epoxy group-containing substances.
  • polyfunctional epoxy group-containing substances are not particularly limited.
  • examples of other polyfunctional epoxy group-containing substances include commonly used epoxy resins other than bisphenol A type epoxy resins, bisphenol F type epoxy resins, and alicyclic epoxy resins, as well as the substances listed below: bisphenol AD type epoxy resins, bisphenol S type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, novolac type epoxy resins, biphenyl type epoxy resins, oxazolidone type epoxy resins, biphenyl aralkyl type epoxy resins, bisnaphthalene type epoxy resins, glycidyl ether type epoxy resins of bisphenol A propylene oxide adducts, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, fluorinated epoxy resins, glycidyl ethers of tetrabromobisphenol A, flame-retardant epoxy resins such as glycidyl ether
  • Epoxy compounds obtained by addition reaction of bisphenol A (or F) or polybasic acids to epoxy resins such as bisphenol A epoxy resins are also included in other polyfunctional epoxy group-containing substances (i.e., other epoxy group-containing substances).
  • glycidyl amine type epoxy resins include N,N,O-triglycidyl-m-aminophenol, N,N,O-triglycidyl-p-aminophenol, N,N,O-triglycidyl-4-amino-3-methylphenol, N,N,N',N'-tetraglycidyl-4,4'-methylenedianiline, N,N,N',N'-tetraglycidyl-2,2'-diethyl-4,4'-methylenedianiline, N,N,N',N'-tetraglycidyl-m-xylylenediamine, N,N-diglycidylaniline, and N,N-diglycidyl-o-toluidine.
  • polyalkylene glycol diglycidyl ethers include polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.
  • glycol diglycidyl ethers include neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and cyclohexanedimethanol diglycidyl ether.
  • examples of diglycidyl esters of aliphatic polybasic acids include dimer acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, and maleic acid diglycidyl ester.
  • epoxy group-containing substances one of the above-mentioned substances may be used alone, or two or more of them may be used in combination.
  • the total content of glycidylamine type epoxy resin, biphenyl type epoxy resin, oxazolidone type epoxy resin, biphenyl aralkyl type epoxy resin, bisnaphthalene type epoxy resin, novolac type epoxy resin and glycol diglycidyl ether in component (A) is preferably 29 parts by mass or less, more preferably 24 parts by mass or less, and particularly preferably 19 parts by mass or less.
  • the composition has a relatively low viscosity and excellent processability, and further has the advantage that the cured product obtained by curing the composition has excellent strength, elastic modulus and heat resistance (high Tg).
  • the lower limit of the total content of the glycidylamine type epoxy resin, biphenyl type epoxy resin, oxazolidone type epoxy resin, biphenyl aralkyl type epoxy resin, bisnaphthalene type epoxy resin, novolac type epoxy resin, and glycol diglycidyl ether in the (A) component is not particularly limited, but may be, for example, more than 0 parts by mass, 1 part by mass or more, 2 parts by mass or more, or 3 parts by mass or more.
  • This configuration has the advantage that the cured product obtained by curing the composition has excellent strength, elastic modulus, and heat resistance (high Tg).
  • the (A) component may or may not further contain a glycidylamine type epoxy resin.
  • the case where the (A) component contains a glycidylamine type epoxy resin will be described.
  • the content of the glycidylamine type epoxy resin in the (A) component is preferably 29 parts by mass or less, more preferably 24 parts by mass or less, even more preferably 19 parts by mass or less, and particularly preferably 14 parts by mass or less. This configuration has the advantages that the composition has a relatively low viscosity and excellent processability, and further, the cured product obtained by curing the composition has excellent strength, elastic modulus, and heat resistance (high Tg).
  • the lower limit of the content of the glycidylamine type epoxy resin in the (A) component is not particularly limited, but may be, for example, more than 0 parts by mass, 1 part by mass or more, 2 parts by mass or more, or 3 parts by mass or more.
  • This configuration has the advantages that the cured product obtained by curing the composition has excellent strength, elastic modulus, and heat resistance (high Tg).
  • polyfunctional epoxy group-containing substances having an epoxy equivalent of 300 g/eq or more and less than 3000 g/eq that is, “polyfunctional epoxy group-containing substances having an epoxy equivalent of 300 g/eq or more and less than 3000 g/eq and having two or more epoxy groups in one molecule” may be referred to as “polyfunctional epoxy group-containing substances (a1)”.
  • Epoxy equivalent can also be measured in accordance with JIS K7236.
  • Component (A) may or may not contain a polyfunctional epoxy group-containing substance (a1). It is preferable that component (A) does not contain a polyfunctional epoxy group-containing substance (a1), since this has the advantage that the composition has a relatively low viscosity and is excellent in processability.
  • the (A) component preferably contains a polyfunctional epoxy group-containing substance (a1) because the cured product obtained by curing the composition has the advantage of having excellent toughness.
  • a1 polyfunctional epoxy group-containing substance
  • bisphenol A type epoxy resins having an epoxy equivalent of 300 g/eq or more and less than 3000 g/eq and having two or more epoxy groups in one molecule (ii) bisphenol F type epoxy resins having an epoxy equivalent of 300 g/eq or more and less than 3000 g/eq and having two or more epoxy groups in one molecule, and (iii) alicyclic epoxy resins having an epoxy equivalent of 300 g/eq or more and less than 3000 g/eq and having two or more epoxy groups in one molecule are all polyfunctional epoxy group-containing substances (a1).
  • the content of polyfunctional epoxy group-containing substance (a1) is preferably 5 parts by mass to 100 parts by mass, more preferably 6 parts by mass to 50 parts by mass, even more preferably 7 parts by mass to 30 parts by mass, and particularly preferably 8 parts by mass to 20 parts by mass.
  • This configuration has the advantages that the composition has a relatively low viscosity and is excellent in processability, and further, the cured product obtained by curing the composition has excellent toughness.
  • the upper limit of the content of polyfunctional epoxy group-containing substance (a1) may be less than 100 parts by mass.
  • the "monofunctional epoxy group-containing substance” may be referred to as the “monofunctional epoxy group-containing substance (a2)."
  • the “monofunctional epoxy group-containing substance” may also be referred to as the “monoepoxide.”
  • the (A) component preferably contains a monofunctional epoxy group-containing substance (a2).
  • This configuration has the advantages that the composition has low viscosity and excellent processability, and furthermore, the cured product obtained by curing the composition has excellent toughness.
  • the content of the monofunctional epoxy group-containing substance (a2) is preferably 5 parts by mass to 40 parts by mass, more preferably 5 parts by mass to 35 parts by mass, even more preferably 5 parts by mass to 33 parts by mass, and particularly preferably 5 parts by mass to 30 parts by mass.
  • the upper limit of the content of the monofunctional epoxy group-containing substance (a2) may be less than 40 parts by mass.
  • Polyalkylene glycol diglycidyl ether, glycol diglycidyl ether, diglycidyl ester of aliphatic polybasic acid, and glycidyl ether of divalent or higher polyhydric aliphatic alcohol can be said to be epoxy resins having a relatively low viscosity.
  • epoxy resins having a relatively low viscosity are sometimes referred to as “polyepoxides" in this specification.
  • polyepoxides When polyepoxides are used in combination with epoxy resins other than polyepoxides (e.g., bisphenol A type epoxy resins and/or bisphenol F type epoxy resins, etc.), the polyepoxides function as reactive diluents in the composition, and the balance between the viscosity of the composition and the physical properties of the cured product can be improved.
  • epoxy resins other than polyepoxides e.g., bisphenol A type epoxy resins and/or bisphenol F type epoxy resins, etc.
  • epoxy resins other than polyepoxides e.g., bisphenol A type epoxy resins and/or bisphenol F type epoxy resins, etc.
  • the monofunctional epoxy group-containing substances (a2) function as reactive diluents in the composition, and the balance between the viscosity of the composition and the physical properties of the cured product can be improved.
  • the (A) component preferably contains a monofunctional epoxy group-containing substance (a2) and/or a polyepoxide as a reactive diluent.
  • the total content of the monofunctional epoxy group-containing substance (a2) and the polyepoxide in the (A) component is preferably 0.5 to 30.0 parts by mass, more preferably 2.0 to 20.0 parts by mass, and even more preferably 5.0 to 15.0 parts by mass, per 100 parts by mass of the (A) component.
  • the epoxy group-containing substance which is component (A) may contain an epoxy group-containing substance having an epoxy equivalent of less than 220 g/eq, may consist of only epoxy group-containing substances having an epoxy equivalent of less than 220 g/eq, may contain an epoxy group-containing substance having an epoxy equivalent of 90 g/eq or more and less than 210 g/eq, may consist of only epoxy group-containing substances having an epoxy equivalent of 90 g/eq or more and less than 210 g/eq, or may consist of only epoxy group-containing substances having an epoxy equivalent of 135 g/eq or more and less than 200 g/eq.
  • This configuration has the advantage that a cured product having a high elastic modulus and heat resistance can be obtained.
  • component (A) preferably contains bisphenol A type epoxy resin and/or bisphenol F type epoxy resin, and more preferably is composed only of bisphenol A type epoxy resin and/or bisphenol F type epoxy resin. Furthermore, since a curable resin composition capable of providing a cured product with excellent heat resistance can be obtained at a low price, component (A) further preferably contains bisphenol A type epoxy resin, and is particularly preferably composed only of bisphenol A type epoxy resin.
  • the total content of bisphenol A type epoxy resin and bisphenol F type epoxy resin is preferably 60 parts by mass or more, more preferably 80 parts by mass or more, and even more preferably 90 parts by mass or more.
  • This configuration has the advantage that the obtained cured product has excellent toughness, impact resistance, heat resistance, and strength.
  • the total content of bisphenol A type epoxy resin and bisphenol F type epoxy resin may be 100 parts by mass.
  • component (A) may be composed of (i) only bisphenol A type epoxy resin, or (ii) only a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin.
  • component (A) contains a bisphenol A type epoxy resin with an epoxy equivalent of less than 220 g/eq and/or a bisphenol F type epoxy resin with an epoxy equivalent of less than 220 g/eq, and it is particularly preferable that component (A) contains a mixture of a bisphenol A type epoxy resin with an epoxy equivalent of less than 220 g/eq and a bisphenol F type epoxy resin with an epoxy equivalent of less than 220 g/eq.
  • the composition preferably contains, as the (A) component, (i) an alicyclic epoxy resin, more preferably (ii) a polyfunctional alicyclic epoxy resin having two or more epoxy groups in one molecule, and even more preferably (iii) a polyfunctional alicyclic epoxy resin having an epoxy equivalent of less than 220 g/eq (or 90 g/eq or more and less than 220 g/eq) and two or more epoxy groups in one molecule.
  • an alicyclic epoxy resin more preferably (ii) a polyfunctional alicyclic epoxy resin having two or more epoxy groups in one molecule, and even more preferably (iii) a polyfunctional alicyclic epoxy resin having an epoxy equivalent of less than 220 g/eq (or 90 g/eq or more and less than 220 g/eq) and two or more epoxy groups in one molecule.
  • the (i) content of the alicyclic epoxy resin is preferably 60 parts by mass to 100 parts by mass (or 60 parts by mass or more and less than 100 parts by mass), (ii) the content of the polyfunctional alicyclic epoxy resin having two or more epoxy groups in one molecule is more preferably 60 parts by mass to 100 parts by mass (or 60 parts by mass or more and less than 100 parts by mass), and (iii) the content of the polyfunctional alicyclic epoxy resin having an epoxy equivalent of less than 220 g/eq (or 90 g/eq or more and less than 220 g/eq) and two or more epoxy groups in one molecule is even more preferably 60 parts by mass to 100 parts by mass (or 60 parts by mass or more and less than 100 parts by mass).
  • a curable resin composition comprising: The composition comprises the following components (A), (B) and (C), does not contain the following component (D), or further contains the following component (D);
  • the content of the alicyclic epoxy resin in 100 parts by mass of the component (A) is 60 parts by mass to 100 parts by mass (or 60 parts by mass or more and less than 100 parts by mass),
  • the composition preferably contains, as the (A) component, (i) a bisphenol A type epoxy resin, more preferably (ii) a polyfunctional bisphenol A type epoxy resin having two or more epoxy groups in one molecule, and even more preferably (iii) a polyfunctional bisphenol A type epoxy resin having an epoxy equivalent of less than 220 g/eq (or 90 g/eq or more and less than 220 g/eq) and having two or more epoxy groups in one molecule.
  • a bisphenol A type epoxy resin more preferably (ii) a polyfunctional bisphenol A type epoxy resin having two or more epoxy groups in one molecule, and even more preferably (iii) a polyfunctional bisphenol A type epoxy resin having an epoxy equivalent of less than 220 g/eq (or 90 g/eq or more and less than 220 g/eq) and having two or more epoxy groups in one molecule.
  • the (i) content of the bisphenol A type epoxy resin is preferably 60 parts by mass to 100 parts by mass (or 60 parts by mass or more and less than 100 parts by mass), (ii) the content of the polyfunctional bisphenol A type epoxy resin having two or more epoxy groups in one molecule is more preferably 60 parts by mass to 100 parts by mass (or 60 parts by mass or more and less than 100 parts by mass), and (iii) the content of the polyfunctional bisphenol A type epoxy resin having an epoxy equivalent of less than 220 g/eq (or 90 g/eq or more and less than 220 g/eq) and two or more epoxy groups in one molecule is even more preferably 60 parts by mass to 100 parts by mass (or 60 parts by mass or more and less than 100 parts by mass).
  • a curable resin composition comprising: The composition comprises the following components (A), (B) and (C), does not contain the following component (D), or further contains the following component (D);
  • the content of the bisphenol A type epoxy resin in 100 parts by mass of the component (A) is 60 parts by mass to 100 parts by mass (or 60 parts by mass or more and less than 100 parts by mass),
  • a curable resin composition comprising: The composition comprises the following components (A), (B) and (C), does not contain the following component (D), or further contains the following component (D);
  • the content of the bisphenol A type epoxy resin in 100 parts by mass of the component (A) is 60 parts by mass to 100 parts by mass (or 60 parts by mass or more and less than 100 parts
  • the component (B) is a polymer particle having a core-shell structure including a core layer and a shell layer.
  • the term "polymer particle having a core-shell structure including a core layer and a shell layer” refers to a particle in which a core layer made of a core polymer and a shell layer made of a shell polymer form a layer structure.
  • the "polymer particle having a core-shell structure including a core layer and a shell layer” may be referred to as a "core-shell polymer particle” or simply as a "polymer particle”.
  • the (B) component (polymer particles) can exhibit a toughness improving effect in the composition.
  • the composition has the advantage of being able to provide a cured product with excellent toughness.
  • the composition tends to provide a cured product with excellent strength.
  • the polymer particles can be obtained by forming a shell layer by graft polymerizing a graft copolymerizable monomer (a monomer for forming a shell layer) in the presence of a core layer. More specifically, this polymerization operation can be carried out by adding a monomer for forming a shell layer (shell polymer) to a latex of a core polymer prepared in an aqueous polymer latex state and polymerizing it. In the polymer particles, it is preferable that the core polymer and the shell polymer are substantially chemically bonded. Note that in the polymer particles, the core layer and the shell layer do not have to form a complete layer structure. The shell layer (shell polymer) needs only to cover at least a part of the core layer (core polymer), and does not have to cover the entire core layer. Also, a part of the shell layer may penetrate into the inside of the core layer.
  • the core layer is preferably an elastic core layer having rubber properties in order to enhance the toughness of the cured product of the composition.
  • the core layer preferably contains a diene-based rubber, and more preferably is a diene-based rubber (e.g., composed only of a diene-based rubber), because this provides a high toughness-improving effect on the resulting cured product, provides a high impact resistance-improving effect on the resulting cured product, and has low affinity with component (A) so that the viscosity increase over time due to swelling of the core layer is unlikely to occur. Since a wide range of polymer compositions can be designed by combining a variety of monomers, the core layer preferably contains a (meth)acrylate-based rubber.
  • an intermediate layer such as that described in paragraphs [0046] to [0049] of WO2016-163491, can be provided between the core layer and the shell layer.
  • the alicyclic amine (c3) is not particularly limited.
  • Examples of the alicyclic amine (c3) include isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), aminoethylpiperazine, piperazine, and menthenediamine.
  • the ratio (molar amount of active hydrogen of the amine in the (C) component / molar amount of epoxy groups in the (A) component) is preferably 0.67 to 0.87, more preferably 0.67 to 0.85, even more preferably 0.67 to 0.83, and particularly preferably 0.68 to 0.82.
  • the ratio (molar amount of active hydrogen of the amine in the (C) component/molar amount of epoxy groups in the (A) component) is preferably 1.10 to 2.40, more preferably 1.25 to 2.30, more preferably 1.45 to 2.20, even more preferably 1.55 to 2.15, and particularly preferably 1.85 to 2.10.
  • This configuration has the advantage that the value X of the composition is highly likely to be 1.30 to 9.00. As a result, the obtained composition has the advantage of being able to provide a cured product with excellent toughness. In addition, this configuration also has the advantage that the composition can provide a cured product with excellent heat resistance, i.e., a cured product with a high Tg.
  • the component (D) is a curing accelerator.
  • the term "curing accelerator” refers to a substance that can accelerate the curing of the composition.
  • the curing accelerator can function as a catalyst for accelerating, for example, the reaction between epoxy groups contained in the component (A) or the reaction between the epoxy groups contained in the component (A) and the epoxy groups contained in the component (C) or other components.
  • tertiary amines such as C1-C12 alkylene imidazole, N-arylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, N-butylimidazole, 2-undecylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and addition products of epoxy resins and imidazole; (d) Lewis acid amine complexes such as boron trifluoride amine complex and boron trichloride amine complex; and (e) 6-caprolactam.
  • tertiary amines such as C1-C12 alkylene imidazole, N-arylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, N-
  • Component (D) may be encapsulated in a microcapsule or the like, or may be a substance that can function as a latent catalyst that becomes active only when the temperature is raised.
  • a latent curing accelerator in which imidazoles or tertiary amines are microencapsulated can also be used.
  • commercially available products e.g., Novacure HX-3722, Novacure HX-3742, Novacure HX-3088, etc., manufactured by Asahi Kasei Corporation
  • component (D) one of these may be used alone, or two or more may be used in combination.
  • the (D) component preferably contains one or more selected from the group consisting of (i) (b) tertiary amines such as 2,4,6-tris(dimethylaminomethyl)phenol, triethylenediamine, and N,N-dimethylpiperazine, and (c) imidazoles such as 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, among others, and more preferably consists of only one or more selected from said group; and (ii) it is even more preferable that the (D) component contains one or more selected from the group consisting of 2,4,6-tris(dimethylaminomethyl)phenol and 2-ethyl-4-methylimidazole, and particularly preferably consists of only one or more selected from said group.
  • tertiary amines such as 2,4,6-tris(dimethyla
  • component (C) is an acid anhydride (c1)
  • the composition preferably contains component (D).
  • component (C) is an aromatic amine (c2) or an alicyclic amine (c3)
  • the composition may or may not contain component (D).
  • the content of component (D) in the composition is 0.1 to 20.0 parts by mass, preferably 0.2 to 16.0 parts by mass, more preferably 0.5 to 13.0 parts by mass, even more preferably 1.0 to 10.0 parts by mass, and particularly preferably 2.0 to 8.0 parts by mass, per 100 parts by mass of component (A).
  • This configuration has the advantage of being able to sufficiently promote curing of the composition.
  • the composition may contain other components as necessary.
  • the other components are not particularly limited, but include, for example, reinforcing agents such as epoxy unmodified rubber polymers, inorganic fillers such as silicic acid and/or silicate salts, calcium oxide, radical curing resins, photopolymerization initiators, azo-type chemical foaming agents and/or thermally expandable microballoons, colorants such as pigments and/or dyes, extender pigments, ultraviolet absorbers, antioxidants, stabilizers (gelling inhibitors), plasticizers, leveling agents, defoamers, silane coupling agents, antistatic agents, flame retardants, lubricants, viscosity reducing agents, low shrinkage agents, organic fillers, thermoplastic resins, desiccants, dispersants, etc.
  • reinforcing agents such as epoxy unmodified rubber polymers, inorganic fillers such as silicic acid and/or silicate salts, calcium oxide, radical curing resins, photopolymerization initiators, azo-type chemical
  • Value X> The value X of the composition varies depending on the component (C).
  • the value X is 1.05 to 5.50. This configuration allows the composition to provide a cured product with excellent toughness.
  • the value X is preferably 1.05 to 5.00, more preferably 1.05 to 4.50, even more preferably 1.06 to 4.25, and particularly preferably 1.07 to 4.00, since the cured product has better toughness.
  • component (C) is an aromatic amine (c2) or an alicyclic amine (c3)
  • the value X is 1.30 to 9.00. This configuration allows the composition to provide a cured product with excellent toughness. Since the cured product has better toughness, when component (C) is an aromatic amine (c2) or an alicyclic amine (c3), the value X is preferably 1.35 to 8.75, more preferably 1.40 to 8.50, even more preferably 1.45 to 8.25, and particularly preferably 1.50 to 8.00.
  • the value X of the composition is (i) the ratio of the molar amount of acid anhydride groups in component (C) to the molar amount of epoxy groups in component (A) contained in the composition (molar amount of acid anhydride groups in component (C)/molar amount of epoxy groups in component (A)), (ii) the ratio of the molar amount of active hydrogen of the amine in component (C) to the molar amount of epoxy groups in component (A) contained in the composition (molar amount of active hydrogen of the amine in component (C)/molar amount of epoxy groups in component (A)), (iii) the average epoxy equivalent of the epoxy group-containing material (A) contained in the composition, (iv) the average acid anhydride equivalent of the acid anhydride (c1) contained in the composition, the average active hydrogen equivalent of the amine of the aromatic amine (c2) contained in the composition, or the average active hydrogen equivalent of the amine of the alicyclic amine (c3) contained in the composition, (v) the average epoxy equivalent of the
  • the amount of the polyfunctional epoxy group-containing substance (a1) having an epoxy equivalent of 300 g/eq or more and less than 3000 g/eq and having two or more epoxy groups per molecule, (vi) the amount of the monofunctional epoxy group-containing substance (a2) having one epoxy group per molecule contained in the composition, (vii) the average number of epoxy groups per molecule of the epoxy group-containing substance (A) contained in the composition, (viii) the average number of acid anhydride groups per molecule of the acid anhydride (c1) contained in the composition, the average number of active hydrogen atoms per molecule of the amine of the aromatic amine (c2) contained in the composition, or the average number of active hydrogen atoms per molecule of the amine of the alicyclic amine (c3) contained in the composition, and (ix) the type and amount of the curing accelerator (D) contained in the composition can be adjusted by changing the amount of the polyfunctional epoxy group-containing substance (a1) having an epoxy equivalent of 300 g/eq or more and less than 3000
  • the curing conditions e.g., curing temperature, curing time, thickness of the composition before curing, etc.
  • the curing conditions e.g., curing temperature, curing time, thickness of the composition before curing, etc.
  • the value Y of the composition may reflect the molecular weight between crosslink points of the composition.
  • the value Y of the composition is preferably 22 to 400, more preferably 25 to 360, more preferably 30 to 320, even more preferably 35 to 280, and particularly preferably 40 to 200.
  • the larger the value Y the more advantageously the cured product obtained will have excellent elongation properties.
  • the smaller the value Y the more advantageously the cured product obtained will have excellent strength and heat resistance.
  • the value Y of the composition is (i) the average epoxy equivalent of the epoxy group-containing substance (A) contained in the composition, (ii) the average acid anhydride equivalent of the acid anhydride (c1) contained in the composition, the average active hydrogen equivalent of the aromatic amine (c2) contained in the composition, or the average active hydrogen equivalent of the alicyclic amine (c3) contained in the composition, (iii) the amount of the polyfunctional epoxy group-containing substance (a1) contained in the composition having an epoxy equivalent of 300 g/eq or more and less than 3000 g/eq and having two or more epoxy groups in one molecule, (iv) the amount of the monofunctional epoxy group-containing substance (a2) contained in the composition having one epoxy group in one molecule, (v) the amount of the polyfunctional epoxy group-containing substance (a2) contained in the composition having one epoxy group in one molecule, (vi) the amount of the polyfunctional epoxy group-containing substance (a3) contained in the composition having one epoxy group in one molecule, (vii) the amount of the polyfunctional epoxy
  • Viscosity of curable resin composition Since the composition has excellent fiber impregnation ability, the viscosity at 25° C. is preferably 5000 mPa ⁇ s or less, more preferably 4000 mPa ⁇ s or less, more preferably 3000 mPa ⁇ s or less, more preferably 2500 mPa ⁇ s or less, more preferably 2000 mPa ⁇ s or less, even more preferably 1000 mPa ⁇ s or less, and particularly preferably 800 mPa ⁇ s or less. Similarly, since the composition has excellent fiber impregnation ability, the viscosity at 50° C.
  • mPa ⁇ s or less is preferably 1000 mPa ⁇ s or less, more preferably 800 mPa ⁇ s or less, more preferably 500 mPa ⁇ s or less, even more preferably 300 mPa ⁇ s or less, and particularly preferably 200 mPa ⁇ s or less.
  • the composition can also be used after heating to a temperature of, for example, 40°C to 100°C, preferably 40°C to 90°C, and more preferably 50°C to 80°C, within a range that balances sufficient viscosity reduction (preferably 200 mPa ⁇ s or less) and sufficient working time until curing.
  • a curable resin composition containing an epoxy group-containing substance e.g., epoxy resin
  • the more epoxy groups contained in one molecule of the epoxy group-containing substance the higher the crosslink density of the cured product.
  • the smaller the molecular weight of the epoxy group-containing substance, the higher the crosslink density of the cured product, and the larger the molecular weight of the epoxy group-containing substance the lower the crosslink density of the cured product.
  • the higher the crosslink density of the cured product the smaller the molecular weight between crosslink points of the cured product.
  • a curable resin composition that contains a large amount of a polyfunctional epoxy group-containing substance as the epoxy group-containing substance has a high crosslink density of the cured product, in other words, a low molecular weight between crosslink points of the cured product.
  • the inventor independently and surprisingly discovered that by setting the molecular weight between crosslink points of the cured product to a value within a specific range and using polymer particles, the toughness of the cured product is excellent.
  • ⁇ represents the Poisson's ratio of the cured product
  • ⁇ represents the specific gravity of the cured product
  • R represents the gas constant
  • T absolute temperature (K)
  • E and G represent the Young's modulus and the rigidity modulus in the rubber-like region of the cured product.
  • the rubber-like region is a region found on the higher temperature side than the transition region near the glass transition temperature when the temperature dependence of the elastic modulus (Young's modulus, rigidity modulus, etc.) is measured, and represents a region in which the temperature dependence of the elastic modulus is flat. Since crosslinked polymers such as epoxy resin cured products do not have a flow region on the higher temperature side than the rubber-like region, E and G in the formula can be expressed as the minimum values of the Young's modulus and rigidity modulus in the rubber-like region.
  • ⁇ represents the Poisson's ratio of the cured material
  • ⁇ represents the specific gravity of the cured material
  • R represents the gas constant
  • E'min represents the minimum value of the storage modulus of the cured material
  • Tmin represents the temperature (°C) at which the storage modulus of the cured material reaches its minimum value.
  • variable portion in the molecular weight between crosslink points of the cured product ( ⁇ ) [273+Tmin(M)]/[E'(M)].
  • the evaluation of the molecular weight between crosslinks must be based on the measured value of the cured product obtained by curing a composition containing only the components (A), (C), and (D). This is because the components (A) and (C) form a crosslinked structure, and the component (D) can affect the degree of progress of the crosslinking reaction. Conversely, when evaluating the molecular weight between crosslinks, components other than the components (B) and (A), (C), and (D) (e.g., inorganic fillers) cannot be added. Although these components do not participate in the crosslinking formation, they affect the E'min of the cured product obtained by curing the composition, and the molecular weight between crosslinks cannot be evaluated correctly.
  • an epoxy curing agent with a large number of active hydrogens per molecule in the amino group e.g., 4 or more
  • an epoxy curing agent with a small number of active hydrogens per molecule in the amino group it is usually used in combination with an epoxy curing agent with a large number of active hydrogens per molecule in the amino group, and the average number of active hydrogens per molecule in the amino group is large for the epoxy curing agent as a whole.
  • the present inventor first focused on the use of a large amount of an epoxy curing agent with a small number of active hydrogens per molecule in the amino group, which had hardly been used in the past, and thereby set the molecular weight between crosslink points within a specified range, and further used polymer particles, thereby solving the above problem and completing the present invention.
  • component (A) e.g., epoxy resin
  • dispersing polymer particles (B) in component (A) e.g., epoxy resin
  • component (B) e.g., epoxy resin
  • the cured product becomes more susceptible to plastic deformation, and toughness is significantly improved.
  • the technical idea of setting the molecular weight between crosslinks to a value within a specified range can be said to be a technical idea that could never have been conceived of in the prior art.
  • the total content of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin and the alicyclic epoxy resin is 5 parts by mass to 100 parts by mass, preferably 10 parts by mass to 100 parts by mass, more preferably 20 parts by mass to 100 parts by mass, more preferably 30 parts by mass to 100 parts by mass, more preferably 40 parts by mass to 100 parts by mass, more preferably 50 parts by mass to 100 parts by mass, more preferably 60 parts by mass to 100 parts by mass, more preferably 70 parts by mass to 100 parts by mass, more preferably 80 parts by mass to 100 parts by mass, even more preferably 90 parts by mass to 100 parts by mass, and particularly preferably 95 parts by mass to 100 parts by mass.
  • the upper limit of the total content of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin and the alicyclic epoxy resin in 100 parts by mass of the (A) component may be less than 100 parts by mass. According to this configuration, the composition has low viscosity and excellent processability, and further, the cured product obtained by curing the composition has excellent strength, elastic modulus, and heat resistance (high Tg).
  • the total content of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and alicyclic epoxy resin may be 100 parts by mass in 100 parts by mass of component (A).
  • component (A) may be composed of only bisphenol A type epoxy resin, only bisphenol F type epoxy resin, only alicyclic epoxy resin, only bisphenol A type epoxy resin and alicyclic epoxy resin, only bisphenol F type epoxy resin and alicyclic epoxy resin, only bisphenol A type epoxy resin and bisphenol F type epoxy resin, or only bisphenol A type epoxy resin, bisphenol F type epoxy resin, and alicyclic epoxy resin.
  • the component (A) may not contain other epoxy group-containing substances (such as glycidylamine-type epoxy resins) described below.
  • component (A) contains a polyfunctional epoxy group-containing substance (a1) and a monofunctional epoxy group-containing substance (a2), since the cured product obtained by curing the composition has the advantage of being more tough.
  • component (A) contains a polyfunctional epoxy group-containing substance (a1) and a monofunctional epoxy group-containing substance (a2) in a curable resin composition that satisfies at least the above (3) (hereinafter also referred to as "Case E").
  • the content of the polyfunctional epoxy group-containing substance (a1) is preferably 5 parts by mass to 95 parts by mass, and the content of the monofunctional epoxy group-containing substance (a2) is preferably 5 parts by mass to 95 parts by mass
  • the content of the polyfunctional epoxy group-containing substance (a1) is more preferably 6 parts by mass to 50 parts by mass, and the content of the monofunctional epoxy group-containing substance (a2) is more preferably 6 parts by mass to 50 parts by mass
  • the content of the polyfunctional epoxy group-containing substance (a1) is more preferably 7 parts by mass to 40 parts by mass
  • the content of the monofunctional epoxy group-containing substance (a2) is more preferably 7 parts by mass to 40 parts by mass
  • the content of the polyfunctional epoxy group-containing substance (a1) is 7 parts by mass to 35 parts by mass
  • the content of the monofunctional epoxy group-containing substance (a2) is more preferably 7 parts by mass to 35 parts by mass.
  • the content of the polyfunctional epoxy group-containing substance (a1) is 8 parts by mass to 33 parts by mass, and the content of the monofunctional epoxy group-containing substance (a2) is 7 parts by mass to 33 parts by mass, it is more preferable that (vi) the content of the polyfunctional epoxy group-containing substance (a1) is 9 parts by mass to 30 parts by mass, and the content of the monofunctional epoxy group-containing substance (a2) is 7 parts by mass to 30 parts by mass, it is even more preferable that (vii) the content of the polyfunctional epoxy group-containing substance (a1) is 10 parts by mass to 25 parts by mass, and the content of the monofunctional epoxy group-containing substance (a2) is 7 parts by mass to 30 parts by mass, it is even more preferable that (viii) the content of the polyfunctional epoxy group-containing substance (a1) is 15 parts by mass to 20 parts by mass, and the content of the monofunctional epoxy group-containing substance (a2) is 8 parts by mass to 30 parts by mass.
  • the composition has low viscosity and excellent processability, and furthermore, the cured product obtained by curing the composition has excellent strength and/or toughness.
  • the content of (i) the polyfunctional epoxy group-containing substance (a1) may be less than 95 parts by mass, and/or the content of (ii) the monofunctional epoxy group-containing substance (a2) may be less than 95 parts by mass or less than 40 parts by mass, per 100 parts by mass of component (A).
  • a curable resin composition that satisfies at least (3) above
  • specific aspects of the component (A) other than those described above are the same as those explained in the section ⁇ 1-1-2. Component (A)> above, so the explanation is omitted here by incorporating that description.
  • the preferred aspects in a curable resin composition that satisfies at least (1) above are also preferred aspects in a curable resin composition that satisfies at least (3) above.
  • the component (C) is an amine-based epoxy curing agent.
  • the component (C) can function as a curing agent for the component (A).
  • the amine-based epoxy curing agent that is the component (C) includes at least an amine (c4) having one or two active hydrogen atoms in the amino group per molecule.
  • the "amine (c4) having one or two active hydrogen atoms in the amino group per molecule” may be referred to as "amine (c4)".
  • the component (C) contains at least the amine (c4), which has the advantages of (i) being able to obtain a cured product having excellent toughness and elongation characteristics, and (ii) being able to obtain a composition having a low viscosity and excellent handleability.
  • the amine (c4) there is no particular limitation on the amine (c4), so long as the number of active hydrogen atoms in the amino group is one or two per molecule.
  • the amine (c4) include aliphatic amines in which the number of active hydrogen atoms in the amino group is two per molecule, such as 3-diethylaminopropylamine, 3-dimethylaminopropylamine, 2-diethylaminoethylamine, 2-dimethylaminoethylamine, piperazine, 2-methylpiperazine, N,N'-dimethylethylenediamine, ethanolamine, n-octylamine, 2-ethylhexylamine, n-dodecylamine, hexylamine, and cyclohexylamine; aromatic amines in which the number of active hydrogen atoms in the amino group is two per molecule, such as aniline, o-toluidine, 4-chloro-o-toluidine
  • aliphatic amines in which the number of active hydrogen atoms in the amino group is one per molecule, such as N-hydroxyethyl)piperazine, 1-methylpiperazine, piperidine, 4-methylpiperidine, diethanolamine, di-n-octylamine, di(2-ethylhexyl)amine, di-n-dodecylamine, dihexylamine, dicyclohexylamine, N-methylcyclohexylamine, N-methyl-n-octylamine, and diallylamine; aromatic amines in which the number of active hydrogen atoms in the amino group is one per molecule, such as N-methylaniline, diphenylamine, N-methyl-p-toluidine, N-phenyl-p-toluidine, N-methyl-m-toluidine, N-methyl-2-naphthaleneamine, N-phenyl-2-naphthaleneamine, and N-methyl-1-naphthalene
  • component (C) contains 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 100% by mass.
  • component (C) is composed of only one or more selected from the group consisting of 3-diethylaminopropylamine, 3-dimethylaminopropylamine, 2-diethylaminoethylamine, 2-dimethylaminoethylamine, piperazine, 2-methylpiperazine, N,N'-dimethylethylenediamine, 1-(2-hydroxyethyl)piperazine, and 1-methylpiperazine.
  • This configuration has the advantage that a cured product with excellent toughness can be obtained.
  • the composition can also be produced by directly mixing the powder (powder, granules, or particulate) of the core-shell polymer particles, which is component (B), with component (A) to disperse the core-shell polymer particles in component (A).
  • component (B) component (B)
  • component (A) component (A)
  • component (A) component (A)
  • the specific production method is a method in which the following first, second, and third steps are carried out in order:
  • First step mixing an aqueous latex containing core-shell polymer particles (e.g., a reaction mixture obtained after producing core-shell polymer particles by emulsion polymerization) with an organic solvent having a solubility in water of 5% by weight to 40% by weight at 20°C, and then mixing the resulting mixture with an excess of water to agglomerate the polymer particles;
  • a second step a step of separating and recovering the aggregated core-shell polymer particles from the liquid phase, and then mixing the core-shell polymer particles with an organic solvent again to obtain an organic solvent solution of the core-shell polymer particles;
  • the third step is to mix the obtained organic solvent solution with the component (A), and then distill off the organic solvent from the obtained mixture.
  • component (A) is liquid at 23°C.
  • component (A) is liquid at 23°C, the third step is facilitated.
  • “Liquid at 23°C” means that the softening point is 23°C or lower and that the component exhibits fluidity at 23°C.
  • the fiber-reinforced composite material can be suitably used to form wheels (particularly vehicle wheels).
  • the fiber-reinforced composite material can also be suitably used to form pressure vessels (e.g., high-pressure vessels) by coating the outer surface of a tank liner.
  • the fiber-reinforced composite material is not limited to these applications, and can also be suitably used as structural members and/or outer panels for aircraft, spacecraft (spacecraft), automobiles, industrial machinery, railroad cars, ships, etc.
  • the obtained pressure vessel can be suitably used as a high pressure vessel (e.g., a high-pressure hydrogen tank).
  • a high pressure vessel e.g., a high-pressure hydrogen tank.
  • the curing temperature is preferably about 50°C to 250°C, more preferably 80°C to 200°C, and particularly preferably 100°C to 150°C.
  • One embodiment of the present invention may have the following configuration.
  • the composition (M) contains the component (A), the component (C), and the component (D) which are the same as the component (A), the component (C), and the component (D) contained in the curable resin composition, the contents of the (A), (C), and (D) components in the composition (M) are the same as the contents of the (A), (C), and (D) components in the curable resin composition,
  • the cured product (M) is a cured product obtained by curing the composition (M), and has a degree of cure of 98% or more as measured by DSC,
  • a cured product (Meq) of composition (Meq) is used as a sample, and dynamic viscoelasticity measurement is performed under conditions of a tensile mode and a frequency of 1 Hz, and the temperature at which the loss tangent is maximum is designated as Ttg(Meq) (°C), E'(Meq) represents the minimum value of the storage modulus (E') of the cured product (Meq)
  • the polymer particles (B-2); the core layer comprises: (b1) 50.00% by mass to 99.99% by mass of a conjugated diene monomer; (b2) 0.00% by mass to 49.99% by mass of a vinyl monomer copolymerizable with the conjugated diene monomer; and (b3) 0.01% by mass to 3.00% by mass of a chain transfer agent, wherein the total of the (b1) conjugated diene monomer, the (b2) vinyl monomer copolymerizable with the conjugated diene monomer
  • the curable resin composition satisfies the above (1)
  • the component (A) satisfies any one of the following (i), (ii) or (iii):
  • the component (A) contains a polyfunctional epoxy group-containing substance (a1) having an epoxy equivalent of 300 g/eq or more and less than 3,000 g/eq and having two or more epoxy groups in one molecule, and the content of the polyfunctional epoxy group-containing substance (a1) is 5 parts by mass to 100 parts by mass per 100 parts by mass of the component (A);
  • the component (A) contains a monofunctional epoxy group-containing substance (a2) having one epoxy group in one molecule, and the content of the monofunctional epoxy group-containing substance (a2) in 100 parts by mass of the component (A) is 5 parts by mass to 40 parts by mass;
  • the component (A) contains the polyfunctional epoxy group-containing substance (a1) and the monofunctional epoxy group-
  • a laminate comprising at least two substrates and an adhesive layer formed by curing an adhesive containing the curable resin composition described in any one of [1] to [10], which bonds the at least two substrates.
  • a fiber-reinforced composite material comprising the curable resin composition described in any one of [1] to [10] and fibers.
  • a high-pressure vessel comprising the fiber-reinforced composite material described in [13].
  • One embodiment of the present invention may have the following configuration.
  • a curable resin composition comprising the following components (A), (B) and (C), and not including the following component (D) or further comprising the following component (D);
  • the content of the component (C) in the composition (Meq) is an amount such that the ratio of the molar amount of the acid anhydride groups in the component (C) to the molar amount of the epoxy groups in the component (A) contained in the component (A) (molar amount of the acid anhydride groups in the component (C)/molar amount of the epoxy groups in the component (A)) is 1, and when the component (C) in the composition (Meq) is the aromatic amine (c2), the content of the component (C) in the composition (Meq) is an amount such that the ratio of the molar amount of the active hydrogen of the amine in the component (C) to the molar amount of the epoxy groups in the component (A) contained in the composition (Meq) (molar amount of the active hydrogen of the amine in the component (C)/molar amount of the epoxy groups in the component (A)) is 1.
  • the core layer is a diene rubber obtained by polymerizing a monomer mixture containing 50% by mass to 99.99% by mass of a conjugated diene monomer (b1), 0% by mass to 49.99% by mass of a vinyl monomer copolymerizable with the conjugated diene monomer (b2), and 0.01% by mass to 3.00% by mass of a chain transfer agent (b3), the total of the conjugated diene monomer (b1), the vinyl monomer copolymerizable with the conjugated diene monomer (b2), and the chain transfer agent (b3) being 100% by mass, the shell layer having epoxy groups, and a content of the epoxy groups in the shell layer relative to the total mass of the shell layer being 0.2 mmol/g to 5.0 mmol/g.
  • the component (A) further contains a glycidylamine type epoxy resin,
  • the curable resin composition according to any one of [A1] to [A5], wherein the content of the glycidyl amine type epoxy resin is 29 parts by mass or less in 100 parts by mass of the component (A).
  • [A7] The curable resin composition according to any one of [A1] to [A6], wherein the component (A) satisfies any one of the following (i), (ii), or (iii): (i) the component (A) contains a polyfunctional epoxy group-containing substance (a1) having an epoxy equivalent of 300 g/eq or more and less than 3000 g/eq and having two or more epoxy groups in one molecule, and the content of the polyfunctional epoxy group-containing substance (a1) in 100 parts by mass of the component (A) is 5 parts by mass to 100 parts by mass; (ii) the component (A) contains a monofunctional epoxy group-containing substance (a2) having one epoxy group in one molecule, and the content of the monofunctional epoxy group-containing substance (a2) in 100 parts by mass of the component (A) is The content of the monofunctional epoxy group-containing substance (a2) is 5 parts by mass to 40 parts by mass; (iii) the component (A) contains the polyfunctional epoxy group-containing substance (a1) and the
  • a fiber-reinforced composite material comprising a curable resin composition according to any one of [A1] to [A8] and fibers.
  • a wheel comprising the fiber-reinforced composite material described in [A10] or [A11].
  • a vehicle wheel comprising the fiber-reinforced composite material described in [A10] or [A11].
  • a cured product (Meq) of composition (Meq) is used as a sample, and dynamic viscoelasticity measurement is performed under conditions of a tensile mode and a frequency of 1 Hz, and the temperature at which the loss tangent is maximum is designated as Ttg(Meq) (°C), E'(Meq) represents the minimum value of the storage modulus (E') of the cured product (Meq) in the temperature range of [Ttg(Meq) (°C)] to [Ttg(Meq)+25(°C)], and Tmin(Meq) (°C) is the temperature (°C) at which the value of E'(Meq) is obtained, the composition (M) contains the component (A), the component (C), and the component (D) which are the same as the component (A), the component (C), and the component (D) contained in the curable resin composition, the contents of the component (A), the component (C), and the component (D) in the composition (M)
  • the core layer is a diene rubber obtained by polymerizing a monomer mixture containing 50% by mass to 99.99% by mass of a conjugated diene monomer (b1), 0% by mass to 49.99% by mass of a vinyl monomer copolymerizable with the conjugated diene monomer (b2), and 0.01% by mass to 3.00% by mass of a chain transfer agent (b3), the total of the conjugated diene monomer (b1), the vinyl monomer copolymerizable with the conjugated diene monomer (b2), and the chain transfer agent (b3) being 100% by mass, the shell layer having epoxy groups, and a content of the epoxy groups in the shell layer relative to the total mass of the shell layer being 0.2 mmol/g to 5.0 mmol/g.
  • the component (A) further contains a glycidylamine type epoxy resin,
  • a curable resin composition comprising the following components (A), (B) and (C), and not including the following component (D) or further including the following component (D);
  • Component (A) an epoxy group-containing substance containing at least one member selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and alicyclic epoxy resins;
  • Component (B) polymer particles having a core-shell structure including a core layer and a shell layer;
  • Component (D) curing accelerator; the total content of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, and the alicyclic epoxy resin is 5 parts by mass to 100 parts by mass, the content of the component (B) is 1 part by mass to 100 parts by mass, relative to 100 parts by mass of the component (A), the content of the
  • the composition (M) contains the component (A), the component (C), and the component (D) which are the same as the component (A), the component (C), and the component (D) contained in the curable resin composition, the contents of the component (A), the component (C), and the component (D) in the composition (M) are the same as the contents of the component (A), the component (C), and the component (D) in the curable resin composition,
  • the cured product (M) is obtained by curing the composition (M) under the following curing conditions: When the component (C) is the acid anhydride (c1), the curing temperature is 175° C. and the curing time is 2 hours; When the component (C) is the aromatic amine (c2), the curing temperature is 175° C. and the curing time is 2 hours; When the component (C) is the alicyclic amine (c3), the curing temperature is 120° C. and the curing time is 2 hours.
  • a fiber-reinforced composite material comprising a curable resin composition according to any one of [C1] to [C6] and fibers.
  • a wheel comprising a fiber-reinforced composite material according to [C10], [C8] or [C9].
  • a vehicle wheel comprising the fiber-reinforced composite material described in [C11], [C8] or [C9].
  • a high-pressure vessel comprising the fiber-reinforced composite material described in [C12], [C8] or [C9].
  • One embodiment of the present invention may have the following configuration.
  • a curable resin composition comprising the following components (A), (B) and (C), does not contain the following component (D), or further contains the following component (D);
  • the content of the (B) component is 1 part by mass to 100 parts by mass relative to 100 parts by mass of the (A) component, The
  • Ttg(M) (°C) is the temperature at which the loss tangent is maximum when dynamic viscoelasticity is measured using a cured product (M) of composition (M) as a sample under conditions of a tensile mode and a frequency of 1 Hz
  • E'(M) represents the minimum value of the storage modulus (E') of the cured product (M) in the temperature range of [Ttg(M) (°C)] to [Ttg(M)+25 (°C)]
  • Tmin(M) (°C) is the temperature (°C) at which the value of E'(M) is obtained.
  • the composition (M) contains the component (A), the component (C), and the component (D) which are the same as the component (A), the component (C), and the component (D) contained in the curable resin composition, the contents of the (A), (C), and (D) components in the composition (M) are the same as the contents of the (A), (C), and (D) components in the curable resin composition,
  • the cured product (M) is a cured product obtained by curing the composition (M) at a curing temperature of 120° C. for a curing time of 2 hours.
  • a two-component or multi-component curable resin composition comprising a first component and a second component,
  • the first component includes the following component (A):
  • the second component includes the following component (C) and does not include the following component (D) or further includes the following component (D)
  • the curable resin composition further contains the following component (B):
  • Component (C) an amine-based epoxy curing agent containing an amine (c1) having one or two active hydrogen atoms in the amino group per molecule;
  • Ttg(M) (°C) is the temperature at which the loss tangent is maximum when dynamic viscoelasticity is measured using a cured product (M) of composition (M) as a sample under conditions of a tensile mode and a frequency of 1 Hz
  • E'(M) represents the minimum value of the storage modulus (E') of the cured product (M) in the temperature range of [Ttg(M) (°C)] to [Ttg(M)+25 (°C)]
  • Tmin(M) (°C) is the temperature (°C) at which the value of E'(M) is obtained.
  • the composition (M) contains the component (A), the component (C), and the component (D) which are the same as the component (A), the component (C), and the component (D) contained in the curable resin composition, the contents of the (A), (C), and (D) components in the composition (M) are the same as the contents of the (A), (C), and (D) components in the curable resin composition,
  • the cured product (M) is a cured product obtained by curing the composition (M) at a curing temperature of 120° C. for a curing time of 2 hours.
  • [D4] The curable resin composition according to any one of [D1] to [D3], wherein the (C) component further contains an alicyclic amine (c2) having four active hydrogen atoms in the amino group per molecule, and the content of the amine (c2) in the (C) component is 0.1% by mass to 95.0% by mass in 100% by mass of the (C) component.
  • the (C) component further contains an alicyclic amine (c2) having four active hydrogen atoms in the amino group per molecule, and the content of the amine (c2) in the (C) component is 0.1% by mass to 95.0% by mass in 100% by mass of the (C) component.
  • [D11] A laminate comprising at least two substrates and an adhesive layer formed by curing the adhesive described in [D10], which bonds the at least two substrates.
  • [D12] A fiber-reinforced composite material comprising a curable resin composition according to any one of [D1] to [D8] and fibers.
  • [D13] A fiber-reinforced composite material according to [D12], in which the fibers are carbon fibers.
  • [D14] A wheel comprising the fiber-reinforced composite material described in [D12] or [D13].
  • [D15] A vehicle wheel comprising the fiber-reinforced composite material described in [D12] or [D13].
  • a high-pressure vessel comprising the fiber-reinforced composite material described in [D12] or [D13].
  • the polymerization was terminated by volatilizing under reduced pressure to remove the remaining monomers that were not used in the polymerization.
  • each of PHP, EDTA, and FE was added to the pressure-resistant polymerization vessel in an arbitrary amount and at an arbitrary time.
  • a latex (R-1) containing a core layer (polybutadiene rubber particles) mainly composed of polybutadiene rubber was obtained.
  • the volume average particle diameter of the polybutadiene rubber particles contained in the obtained latex was 0.10 ⁇ m.
  • Production Example 1-2 Preparation of polybutadiene rubber latex (R-2) Into a pressure-resistant polymerization reactor having a volume of 100 L, 21 parts by mass of the polybutadiene rubber latex (R-1) obtained in Production Example 1-1 (including 7 parts by mass of polybutadiene rubber particles), 200 parts by mass of deionized water, 0.03 parts by mass of tripotassium phosphate, 0.002 parts by mass of EDTA, and 0.001 parts by mass of FE were charged. Next, oxygen was sufficiently removed from inside the pressure-resistant polymerization reactor by replacing the gas inside the pressure-resistant polymerization reactor with nitrogen while stirring the charged raw materials.
  • a latex (R-2) containing a core layer (polybutadiene rubber particles) mainly composed of polybutadiene rubber was obtained.
  • the volume average particle diameter of the polybutadiene rubber particles contained in the obtained latex was 0.20 ⁇ m.
  • Production Example 1-3 Preparation of polybutadiene rubber latex (R-3) 200 parts by mass of deionized water, 0.03 parts by mass of tripotassium phosphate, 0.002 parts by mass of EDTA, 0.001 parts by mass of FE, and 0.5 parts by mass of SDS as an emulsifier were charged into a pressure-resistant polymerization vessel having a volume of 100 L. Next, the gas inside the pressure-resistant polymerization vessel was replaced with nitrogen while stirring the charged raw materials, thereby sufficiently removing oxygen from inside the pressure-resistant polymerization vessel.
  • R-3 Preparation of polybutadiene rubber latex (R-3) 200 parts by mass of deionized water, 0.03 parts by mass of tripotassium phosphate, 0.002 parts by mass of EDTA, 0.001 parts by mass of FE, and 0.5 parts by mass of SDS as an emulsifier were charged into a pressure-resistant polymerization vessel having a volume of 100 L. Next, the gas inside the pressure
  • a latex (R-3) containing a core layer (polybutadiene rubber particles) mainly composed of polybutadiene rubber was obtained.
  • the volume average particle diameter of the polybutadiene rubber particles contained in the obtained latex was 0.13 ⁇ m.
  • component (B) (polymer particles) (formation of shell layer) Production Example 2-1; Preparation of aqueous latex (L-1) containing polymer particles 262 parts by mass of the polybutadiene rubber latex (R-2) prepared in Production Example 1-2 (containing 87 parts by mass of polybutadiene rubber particles) and 57 parts by mass of deionized water were charged into a glass reactor.
  • the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the raw materials charged at 60°C were stirred while performing the nitrogen replacement.
  • EDTA 0.004 parts by mass of EDTA, 0.001 parts by mass of FE, and 0.2 parts by mass of SFS were added into the glass reactor.
  • a mixture of the shell layer forming monomers (8 parts by mass of methyl acrylate (MA), 3.5 parts by mass of butyl acrylate (BA), and 1.5 parts by mass of glycidyl methacrylate (GMA)) and 0.04 parts by mass of cumene hydroperoxide (CHP) was continuously added to the glass reactor over 120 minutes.
  • 0.04 parts by mass of CHP was added to the glass reactor, and the mixture in the glass reactor was further stirred for 2 hours to complete the polymerization.
  • an aqueous latex (L-1) containing component (B) (polymer particles) was obtained.
  • the polymerization conversion rate of the monomer components was 99% or more.
  • the volume average particle diameter of the polymer particles contained in the obtained aqueous latex (L-1) was 0.21 ⁇ m.
  • the content of the epoxy group relative to the total amount of the shell layer of the polymer particles was 0.8 mmol/g.
  • Production Example 2-2 Preparation of aqueous latex (L-2) containing polymer particles 271 parts by mass of the polybutadiene rubber latex (R-2) prepared in Production Example 1-2 (containing 90 parts by mass of polybutadiene rubber particles) and 51 parts by mass of deionized water were charged into a glass reactor.
  • the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device.
  • the gas in the glass reactor was replaced with nitrogen, and the raw materials charged at 60°C were stirred while performing the nitrogen replacement.
  • 0.004 parts by mass of EDTA, 0.001 parts by mass of FE, and 0.2 parts by mass of SFS were added into the glass reactor.
  • a mixture of the shell layer forming monomers (9.25 parts by mass of methyl methacrylate (MMA) and 0.75 parts by mass of GMA) and 0.14 parts by mass of CHP was continuously added into the glass reactor over 120 minutes. After the addition was completed, 0.04 parts by mass of CHP was added to the glass reactor, and the mixture in the glass reactor was further stirred for 2 hours to complete the polymerization.
  • an aqueous latex (L-2) containing component (B) (polymer particles) was obtained.
  • the polymerization conversion rate of the monomer components was 99% or more.
  • the volume average particle diameter of the polymer particles contained in the obtained aqueous latex (L-2) was 0.21 ⁇ m.
  • the content of epoxy groups relative to the total amount of the shell layer of the polymer particles was 0.5 mmol/g.
  • Production Example 2-3 Preparation of aqueous latex (L-3) containing polymer particles
  • An aqueous latex (L-3) containing component (B) (polymer particles) was obtained in the same manner as in Production Example 2-2, except that 10 parts by mass of MMA was used instead of 9.25 parts by mass of MMA and 0.75 parts by mass of GMA as the monomer for forming the shell layer in Production Example 2-2.
  • the volume average particle diameter of the polymer particles (B) contained in the obtained aqueous latex (L-3) was 0.21 ⁇ m.
  • the content of epoxy groups relative to the total mass of the shell layer of the polymer particles (B) was 0 mmol/g.
  • Production Example 2-4 Preparation of aqueous latex (L-4) containing polymer particles 250 parts by mass of the polybutadiene rubber latex (R-3) prepared in Production Example 1-3 (containing 83 parts by mass of polybutadiene rubber particles) and 65 parts by mass of deionized water were charged into a glass reactor.
  • the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device.
  • the gas in the glass reactor was replaced with nitrogen, and the raw materials charged at 60°C were stirred while performing the nitrogen replacement.
  • 0.0048 parts by mass of EDTA, 0.0012 parts by mass of FE, and 0.15 parts by mass of SFS were added into the glass reactor.
  • Production Example 2-8 Preparation of aqueous latex (L-8) containing polymer particles
  • aqueous latex (L-8) containing polymer particles In Production Example 2-6, except that ⁇ 1 part by mass of MMA, 6 parts by mass of ST, 2 parts by mass of AN and 4 parts by mass of GMA> was used instead of ⁇ 4 parts by mass of MMA, 6 parts by mass of ST, 2 parts by mass of AN and 1 part by mass of GMA> as the monomer for forming the shell layer, an aqueous latex (L-8) containing component (B) (polymer particles) was obtained in the same manner as in Production Example 2-6.
  • the volume average particle diameter of the polymer particles (B) contained in the obtained aqueous latex (L-8) was 0.21 ⁇ m.
  • the content of epoxy groups relative to the total mass of the shell layer of the polymer particles (B) was 2.2 mmol/g.
  • Production Example 2-9 Preparation of aqueous latex (L-9) containing polymer particles
  • An aqueous latex (L-9) containing component (B) (polymer particles) was obtained in the same manner as in Production Example 2-6, except that ⁇ 5 parts by mass of MMA, 6 parts by mass of ST, 2 parts by mass of AN, and 1 part by mass of GMA> was used instead of ⁇ 4 parts by mass of MMA, 6 parts by mass of ST, 2 parts by mass of AN, and 1 part by mass of GMA> as the monomer for forming the shell layer in Production Example 2-6.
  • the volume average particle diameter of the polymer particles (B) contained in the obtained aqueous latex (L-9) was 0.21 ⁇ m.
  • the content of epoxy groups relative to the total mass of the shell layer of the polymer particles (B) was 0 mmol/g.
  • Production Example 2-10 Preparation of aqueous latex (L-10) containing polymer particles
  • An aqueous latex (L-10) containing component (B) (polymer particles) was obtained in the same manner as in Production Example 2-6, except that ⁇ 3 parts by mass of MMA and 10 parts by mass of GMA> were used instead of ⁇ 4 parts by mass of MMA, 6 parts by mass of ST, 2 parts by mass of AN, and 1 part by mass of GMA> as the monomers for forming the shell layer in Production Example 2-6.
  • the volume average particle diameter of the polymer particles (B) contained in the obtained aqueous latex (L-10) was 0.21 ⁇ m.
  • the content of epoxy groups relative to the total mass of the shell layer of the polymer particles (B) was 5.4 mmol/g.
  • Production Example 2-11 Preparation of aqueous latex (L-11) containing polymer particles
  • An aqueous latex (L-11) containing component (B) (polymer particles) was obtained in the same manner as in Production Example 2-6, except that in Production Example 2-6, 12.5 parts by mass of MMA and 0.5 parts by mass of ST were used instead of 4 parts by mass of MMA, 6 parts by mass of ST, 2 parts by mass of AN, and 1 part by mass of GMA as the monomers for forming the shell layer.
  • the volume average particle diameter of the polymer particles (B) contained in the obtained aqueous latex (L-11) was 0.21 ⁇ m.
  • the content of epoxy groups relative to the total mass of the shell layer of the polymer particles (B) was 0 mmol/g.
  • Production Example 3-2 Preparation of Dispersion (M-2) A dispersion (M-(2)) in which component (B) (polymer particles) was dispersed in component (A) was obtained in the same manner as in Production Example 3-1, except that (L-2) obtained in Production Example 2-2 was used instead of (L-1) as the aqueous latex containing polymer particles, and that A-(2) (bisphenol A type epoxy resin that is liquid at room temperature) was used instead of A-(1) as component (A).
  • Production Examples 3-3 to 11 Preparation of Dispersions (M-(3) to (11)) Dispersions (M-(3) to (11)) in which component (B) (polymer particles) was dispersed in component (A) were obtained in the same manner as in Production Example 3-2, except that (L-3 to 11) obtained in Production Examples 2-3 to 11 were used instead of (L-2) as the aqueous latex containing polymer particles in Production Example 3-2.
  • ⁇ (C) component> (Acid anhydride (c1)) c1-(1): 4-methylcyclohexane-1,2-dicarboxylic anhydride (mixture of isomers) (Tokyo Chemical Industry Co., Ltd., acid anhydride group equivalent: 168 g/eq) c1-(2): Methyltetrahydrophthalic anhydride (DIC, "EPICLON B-570-H", acid anhydride group equivalent: 166 g/eq) (Aromatic amine (c2)) c2-(1): Diethyltoluenediamine (manufactured by Mitsubishi Chemical, "jER Cure WA", active hydrogen equivalent: 44.6 g/eq) (Alicyclic amine (c3)) c3-(1): Isophoronediamine (manufactured by BASF, active hydrogen equivalent: 42.6 g/eq) c3-(2): 1,3-bis(aminomethyl)cyclohexane (mixture of is
  • c-(2) Condensation product of dimer acid or fatty acid with polyamine (Tsukuno Foods, "Vegichem Green V140", an amidoamine having 3 or more active hydrogens in the amino group per molecule, active hydrogen equivalent: 97 g/eq)
  • D-(1) 2-ethyl-4-methylimidazole (Tokyo Chemical Industry Co., Ltd.)
  • D-(2) 2,4,6-tris(dimethylaminomethyl)phenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • D-(3) N-benzyldimethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • the volume average particle diameter (Mv) of the polymer particles (B) dispersed in the aqueous latex was measured using a Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.).
  • the aqueous latex was diluted with deionized water and used as a measurement sample. The measurement was performed by inputting the refractive index of water and the refractive index of each polymer particle, adjusting the sample concentration so that the measurement time was 600 seconds and the signal level was within the range of 0.6 to 0.8.
  • a V-notch was made in the test piece, and a crack was made from the tip of the V-notch to the center of the test piece using a razor blade.
  • the test piece thus obtained was subjected to a three-point bending test under the conditions of a support distance of 50 mm, a test speed of 1 mm/min, and 23°C. From the bending test results, the fracture toughness values (K1c and G1c) were evaluated in accordance with ASTM D-5045.
  • composition (M) contains the same (identical) components (A), (C), and (D) as the components (A), (C), and (D) contained in the curable resin compositions of each of the Examples and Comparative Examples, and the contents of each of the components (A), (C), and (D) in composition (M) are the same as the contents of the components (A), (C), and (D) in the curable resin compositions of each of the Examples and Comparative Examples.

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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

Le problème abordé par la présente invention est de fournir une composition de résine durcissable permettant de fournir un produit durci présentant une excellente ténacité. L'invention concerne une composition de résine durcissable qui contient des quantités spécifiques du composant (A) : une substance contenant un groupe époxy spécifique, un composant (B) : des particules polymères ayant une structure spécifique, et un composant (C) : un agent de durcissement époxyde spécifique, dans lequel le composant (D) : un accélérateur de durcissement n'est pas présent ou est présent à une proportion spécifique, et les valeurs X ou Y sont comprises dans des plages spécifiques.
PCT/JP2024/045147 2023-12-20 2024-12-20 Composition de résine durcissable et son utilisation Pending WO2025135157A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0656966A (ja) * 1992-06-25 1994-03-01 Ciba Geigy Ag エポキシ樹脂硬化剤の貯蔵安定性懸濁物
JPH06157715A (ja) * 1992-07-09 1994-06-07 Ciba Geigy Ag エポキシ樹脂の硬化性懸濁物
JP2015532354A (ja) * 2012-10-19 2015-11-09 ダウ グローバル テクノロジーズ エルエルシー ポリオールを用いたポリマー粒子分散液
JP2018035210A (ja) * 2016-08-29 2018-03-08 株式会社カネカ 繊維強化複合材料用エポキシ樹脂組成物
FR3097550A1 (fr) * 2019-06-18 2020-12-25 Axon Cable Utilisation d’une résine époxyde pour l’encapsulation/enrobage des contacts pour connecteurs électriques
WO2022025234A1 (fr) * 2020-07-31 2022-02-03 セメダイン株式会社 Adhésif à deux composants
WO2022239471A1 (fr) * 2021-05-13 2022-11-17 Dic株式会社 Composition durcissable, objet durci, matériau composite renforcé par des fibres, et article moulé en résine renforcée par des fibres
CN116376229A (zh) * 2023-04-21 2023-07-04 四川东树新材料有限公司 一种长适用期碳纤维缠绕用环氧树脂及其制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0656966A (ja) * 1992-06-25 1994-03-01 Ciba Geigy Ag エポキシ樹脂硬化剤の貯蔵安定性懸濁物
JPH06157715A (ja) * 1992-07-09 1994-06-07 Ciba Geigy Ag エポキシ樹脂の硬化性懸濁物
JP2015532354A (ja) * 2012-10-19 2015-11-09 ダウ グローバル テクノロジーズ エルエルシー ポリオールを用いたポリマー粒子分散液
JP2018035210A (ja) * 2016-08-29 2018-03-08 株式会社カネカ 繊維強化複合材料用エポキシ樹脂組成物
FR3097550A1 (fr) * 2019-06-18 2020-12-25 Axon Cable Utilisation d’une résine époxyde pour l’encapsulation/enrobage des contacts pour connecteurs électriques
WO2022025234A1 (fr) * 2020-07-31 2022-02-03 セメダイン株式会社 Adhésif à deux composants
WO2022239471A1 (fr) * 2021-05-13 2022-11-17 Dic株式会社 Composition durcissable, objet durci, matériau composite renforcé par des fibres, et article moulé en résine renforcée par des fibres
CN116376229A (zh) * 2023-04-21 2023-07-04 四川东树新材料有限公司 一种长适用期碳纤维缠绕用环氧树脂及其制备方法

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