WO2022210246A1 - Composition de résine époxy, produit de résine époxy durcie, et article moulé en résine renforcée par des fibres revêtu obtenu à l'aide de ceux-ci - Google Patents

Composition de résine époxy, produit de résine époxy durcie, et article moulé en résine renforcée par des fibres revêtu obtenu à l'aide de ceux-ci Download PDF

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Publication number
WO2022210246A1
WO2022210246A1 PCT/JP2022/013895 JP2022013895W WO2022210246A1 WO 2022210246 A1 WO2022210246 A1 WO 2022210246A1 JP 2022013895 W JP2022013895 W JP 2022013895W WO 2022210246 A1 WO2022210246 A1 WO 2022210246A1
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Prior art keywords
epoxy resin
epoxy
fiber
resin composition
reinforced
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PCT/JP2022/013895
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English (en)
Japanese (ja)
Inventor
宮川裕司
山本航
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東レ株式会社
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Priority to JP2022520872A priority Critical patent/JPWO2022210246A1/ja
Publication of WO2022210246A1 publication Critical patent/WO2022210246A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08G59/66—Mercaptans
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material

Definitions

  • the present invention relates to an epoxy resin composition, a cured epoxy resin, and a coated fiber-reinforced resin molded product using the same.
  • FRP fiber reinforced plastic
  • Sheet molding compound (SMC) molding methods and bulk molding compound (BMC) molding methods are often used as manufacturing methods for fiber-reinforced resin molded products.
  • the resin transfer molding (RTM) method has attracted attention and is being applied.
  • the resin transfer molding (RTM) method can use reinforcing fibers in the form of continuous fibers, has very high mechanical properties, and is excellent in productivity because it can be molded in a short cycle time.
  • fiber-reinforced resin molded products obtained by these molding methods have defects due to insufficient resin filling on the surface, and surface unevenness occurs due to the shape of the reinforcing fiber and the shrinkage of the resin.
  • the surface smoothness is inferior to that of metal members that are often used from the ground up.
  • the surface of the fiber-reinforced resin molded article needs to be repaired and polished before being painted, which sometimes requires a great deal of labor.
  • the surface may not be sufficiently smooth in some cases.
  • the fiber-reinforced resin molded product is transferred to a mold having a molding temperature lower than the curing temperature.
  • a composition (a resin different from the matrix resin) for covering the fiber-reinforced resin molded product is injected and cured between the surface of the fiber-reinforced resin molded product and the surface of the mold, thereby reducing the fibers on the surface of the molded product.
  • a coated fiber-reinforced resin molded article with hidden eyes and pinholes was obtained.
  • the composition used for coating the fiber-reinforced resin molding used in this case includes, for example, a combination of an aliphatic epoxy resin having an alicyclic skeleton, a thiol compound, and phosphines, and low-temperature fast-curing properties, weather resistance, Tg
  • a coating resin composition (Patent Document 2) that aims to improve the transparency, and an epoxy resin composition that combines a quaternary phosphonium salt, a secondary or tertiary thiol compound, and a polyepoxy compound and has excellent transparency
  • Patent Document 3 a curable epoxy resin composition for optical semiconductor encapsulation, which is obtained by combining an epoxy resin having an epoxy group having an alicyclic structure, that is, an alicyclic epoxy resin, a monoallyl diglycidyl isocyanurate compound, and an acid anhydride-based curing agent.
  • Patent Document 4 an epoxy resin composition for light-emitting diodes having excellent light transmittance and refractive index, which is obtained by combining an epoxy resin having no carbon-carbon double bond and a polythiol-based curing agent (Patent Document 5).
  • JP 2017-109502 A Japanese Patent Application No. 2018-539446 JP 2013-221091 A JP 2015-034297 A JP 2007-109915 A
  • composition for coating the fiber-reinforced resin molded article described in Patent Document 1 has excellent transparency as a coating, shortens the occupancy time in the mold, and improves productivity, so it has a low viscosity. Curing in a short time at low temperature, high weather resistance and Tg are required, respectively, thiol-based curing agent excellent in low-temperature fast curing, epoxy resin with an epoxy group having an alicyclic structure with excellent weather resistance and Tg, Thus, a combination of cycloaliphatic epoxies is preferred.
  • the reaction between an alicyclic epoxy and a thiol-based curing agent has a slow reaction rate from the viewpoint of steric hindrance, and is not suitable for low-temperature rapid curing.
  • the epoxy resin described in the epoxy resin composition described in Patent Document 2 has an alicyclic skeleton and has fast curing properties. In comparison, the Tg improving effect is not sufficient.
  • Patent Document 3 if an epoxy resin containing an aromatic ring is used, both Tg and fast curability can be achieved, but the weather resistance is poor because it absorbs ultraviolet rays.
  • Patent Document 4 is excellent in terms of Tg and weather resistance, but is insufficient in low-temperature rapid curability due to the use of an acid anhydride.
  • Patent Document 5 there is no description of forming a film of a fiber-reinforced composite material, and the composition is based on the premise of high-temperature curing.
  • the object of the present invention is to provide an epoxy resin that can reduce the surface unevenness caused by the temperature difference between the molding temperature (curing temperature) and normal temperature when molding a fiber reinforced resin, and has high surface quality and excellent weather resistance.
  • An object of the present invention is to provide a composition, a cured epoxy resin product, and a coated fiber-reinforced resin molded product using the same.
  • the epoxy resin composition of the present invention comprises an epoxy resin (A) comprising a single or multiple epoxy resins, a thiol group-containing curing agent (B), a catalyst
  • the epoxy resin (A1) which accounts for 50% or more by weight of the epoxy resins constituting the epoxy resin (A), has a difunctional epoxy group having a glycidyl structure. above and one or more epoxy groups having an alicyclic structure.
  • the ratio of the functional group number [AG] of the epoxy group having a glycidyl structure contained in the epoxy resin (A) to the functional group number [AF] of the epoxy group having an alicyclic structure is has a relationship of [AG]/[AF]>0.7.
  • neither the epoxy resin (A) nor the thiol group-containing curing agent (B) contain carbon-carbon unsaturated bonds.
  • the epoxy resin cured product of the present invention is an epoxy resin cured product obtained by curing the epoxy resin composition of the present invention, and has a glass transition temperature (Tg) of 40°C or higher.
  • the coated fiber-reinforced resin molded article of the present invention is obtained by coating at least part of the surface of the fiber-reinforced resin molded article with the cured epoxy resin of the present invention as a coating layer.
  • the fiber-reinforced resin molded article is carbon fiber-reinforced plastic.
  • a coating film is further formed by clear coating on the surface of the coating layer.
  • the present invention when a fiber-reinforced resin is molded, it is possible to greatly reduce the surface unevenness caused by the temperature difference between the molding temperature (curing temperature) and normal temperature, and the epoxy resin composition has excellent weather resistance. It becomes possible to provide epoxy resin cured products and coated fiber-reinforced resin molded products.
  • the epoxy resin composition of the present invention is an epoxy resin composition containing at least an epoxy resin (A) consisting of a single or multiple epoxy resins, a thiol group-containing curing agent (B), and a catalyst (C), wherein the epoxy resin Among the epoxy resins constituting (A), the epoxy resin (A1), which accounts for 50% or more by weight, has two or more functional epoxy groups having a glycidyl structure and one or more functional epoxy groups having an alicyclic structure.
  • the term “epoxy group having a glycidyl structure” refers to a glycidyl group ((C 2 H 3 O)—CH 2 ) in which methylene is bonded to oxirane.
  • the term “epoxy group having an alicyclic structure” refers to a compound in which an epoxy group is partly contained in a compound in which carbon atoms are cyclically bonded (alicyclic compound).
  • Epoxy groups with a glycidyl structure react quickly with thiols even at low temperatures. Therefore, since the epoxy group having a glycidyl structure has two or more functionalities, the epoxy resin can be incorporated into the network structure of the cured product even if it is cured at a low temperature in a short time, reducing the amount of epoxy resin that remains as a low molecular weight. and have sufficient adhesion to remove from the mold.
  • neither the epoxy resin (A) nor the thiol group-containing curing agent (B) contain a carbon-carbon unsaturated bond.
  • a carbon-carbon unsaturated bond By not containing a carbon-carbon unsaturated bond, discoloration of the resin due to ultraviolet rays can be prevented, and it can be used outdoors for a long period of time.
  • the fiber-reinforced resin molded product is coated with the epoxy resin composition used in the present invention and then coated with a paint containing an ultraviolet absorber
  • the shape of the fiber-reinforced resin molded product to be coated includes an upright surface, Dripping of the paint occurs during painting, and the coating film thickness becomes uneven due to work variations, and the effect of the ultraviolet absorber is reduced in areas where the film thickness is thin. It is important to keep it.
  • the expression "including standing surfaces” means that adjacent surfaces in the fiber-reinforced resin molded article have surfaces in which the other surface is inclined by 30° or more with respect to the tangential direction of one surface.
  • the coating film thickness is preferably 100 ⁇ m or less, more preferably 60 ⁇ m, and still more preferably 40 ⁇ m or less.
  • the epoxy equivalent and active hydrogen equivalent of the epoxy resin (A) and thiol group-containing curing agent (B) used in the present invention are preferably 170 g/eq or less. By keeping the epoxy equivalent low, it is possible to have a dense three-dimensional structure, which increases the Tg of the cured product. It also has good adhesion to plastic products with small surface free energy such as fiber reinforced resin molded products containing
  • the viscosity of each of the epoxy resin (A) and the thiol group-containing curing agent (B) is preferably 80 Pa ⁇ s or less at 25°C.
  • the viscosity of each of the epoxy resin (A) and the thiol group-containing curing agent (B) is preferably 80 Pa ⁇ s or less at 25°C.
  • the epoxy resin (A) and the thiol group-containing curing agent (B) can be mixed with a static mixer. , more preferred.
  • the viscosity after mixing the epoxy resin (A) and the thiol group-containing curing agent (B) is 10 Pa s or less at 25 ° C., it can be sufficiently flowed into the mold even at a low temperature. preferable.
  • the epoxy resin composition is composed only of non-volatile matter.
  • the epoxy resin composition of the present invention preferably has a vapor pressure of 0.5 kPa or less in a mold temperature environment.
  • the epoxy resin (A1) which accounts for 50% or more by weight, has an epoxy group having a glycidyl structure with at least two functionalities and an alicyclic It has one or more functional epoxy groups having a structure.
  • the epoxy resin (A1) may be any epoxy resin having two or more functional epoxy groups having a glycidyl structure and one or more functional epoxy groups having an alicyclic structure. Diglycidyl 4,5-epoxyhexahydrophthalate is preferred because it has high weather resistance and low viscosity because it does not contain any.
  • epoxy resin (A1) when two or more types of epoxy resins having two or more functional epoxy groups having a glycidyl structure and one or more functional epoxy groups having an alicyclic structure are included, the total content of these epoxy resins is 50 by weight. % or more, these epoxy resins are combined to be the epoxy resin (A1).
  • the epoxy resin (A) may contain an epoxy resin (A2) as an epoxy resin other than the epoxy resin (A1).
  • epoxy resins (A2) include 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 1-epoxyethyl-3,4- Those having an alicyclic structure such as epoxycyclohexane, limonene diepoxide, dicyclopentadiene diepoxide, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, sorbitol Liquid epoxy resins having an epoxy group having a glycidyl structure such as polyglycidyl ether, glycerol polyglycidyl ether, polyglyce
  • the thiol group-containing curing agent (B) used in the present invention more specifically refers to a compound having two or more thiol groups in one molecule capable of reacting with the epoxy group of the epoxy resin (A). acts as a curing agent for
  • a thiol compound as a curing agent, it is expected that even when forming a cured film at a temperature lower than the temperature at which the fiber-reinforced composite material is molded, it will be possible to cure at a sufficiently high speed and increase productivity. be done.
  • thiol group-containing curing agents (B) include pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate ), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine- 2,4,6(1H,3H,5H)-trione, bisphenol A-type thiol,
  • the thiol group-containing curing agent (B) preferably has a secondary thiol structure or a tertiary thiol structure, and more preferably has two or more thiol structures represented by the following chemical formula (1).
  • R 7 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • R 8 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • n a natural number of 1 or more.
  • the resin composition for coating is highly stable when prepared, does not easily thicken in a short period of time, and is easy to mold.
  • n represents a natural number of 1 or more and 10 or less, and more preferably, n represents a natural number of 1 or more and 5 or less.
  • Examples of thiol compounds having two or more thiol structures represented by Chemical Formula 1 include 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5 -tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.
  • the contents of the epoxy resin (A) and the thiol group-containing curing agent (B) in the epoxy resin composition of the present invention are determined by the number of thiol groups (H) in the component thiol group-containing curing agent (B) and the epoxy resin (A) It is a preferred embodiment that the ratio of the total number of epoxy groups (E) in the compound, the H/E ratio, satisfies the range of 0.8 to 1.3. If the H/E ratio is less than 0.8, excessive polymerization of the epoxy resin may proceed, resulting in deterioration of the physical properties of the cured product. If the H/E ratio exceeds 1.3, the concentration of reaction sites in the system decreases due to excessive curing agent components, and the reaction rate decreases, resulting in a failure to exhibit sufficient high-speed curability.
  • the catalyst (C) used in the present invention is preferably a quaternary phosphonium salt.
  • the quaternary phosphonium salt acts as a curing accelerator for rapid curing.
  • quaternary phosphonium salts used as the catalyst (C) in the present invention include tetraethylphosphonium bromide, tributylmethylphosphonium iodide, tetraethylphosphonium hexafluorophosphate, tetraethylphosphonium tetrafluoroborate, tributyl(cyanomethyl)phosphonium chloride, Tetrakis(hydroxymethyl)phosphonium chloride, tetrabutylphosphonium hydroxide, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrakis(hydroxymethyl)phosphonium sulfate, tributyl-n-octylphosphonium bromide, tetra-n-octylphosphonium bromide, tetra Butylphosphonium tetrafluoroborate, tetrabutylphosphonium
  • the compound represented by the chemical formula (2) is preferred.
  • Specific examples of the compound represented by Chemical Formula 2 include methyltributylphosphonium dimethylphosphate and tetrabutylphosphonium o,o-diethylphosphorodithioate.
  • R 1 to R 4 each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. .
  • R 5 and R 6 each independently represent an alkyl group having 1 to 20 carbon atoms.
  • M 1 and M 2 each independently represent an element selected from Group 16 of the periodic table, and oxygen and sulfur are particularly preferred.
  • the content of the catalyst (C) used in the present invention is preferably 0.1 parts by mass or more and less than 15 parts by mass, more preferably 0.1 parts by mass or more and 12 parts by mass based on 100 parts by mass of the epoxy resin (A). or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less. If the amount of the catalyst (C) is less than 0.1 parts by mass, the time required for curing may become longer and sufficient high-speed curability may not be exhibited. On the other hand, when the amount of the catalyst (C) is 15 parts by mass or more, the time to maintain the low viscosity is shortened, and it may become difficult to pour the resin composition into the cavity in the mold.
  • the epoxy resin composition of the present invention comprises, for example, a main component liquid containing an epoxy resin (A) and a thiol group-containing curing agent (B) as main components (the main component herein means the mass of the curing agent liquid). It means that it is the component with the maximum amount as a standard.) and the curing agent liquid contained in each of the above-mentioned amounts, and just before use, mix the main liquid and the curing agent so that the above-mentioned amounts are obtained. Obtained by mixing liquids.
  • the catalyst (C) described above can be blended in either the main liquid or the curing agent liquid, it is more preferably contained in the curing agent liquid.
  • compounding ingredients can be blended into either the main liquid or the hardener liquid, and can be used by mixing with either or both in advance.
  • the main component liquid and the curing agent liquid are preferably heated separately before mixing, and are mixed using a mixer immediately before use such as injection into a mold to obtain a two-component epoxy resin composition. is preferable from the standpoint of the pot life of the resin.
  • the epoxy resin cured product of the present invention is an epoxy resin cured product obtained by curing the epoxy resin composition of the present invention, and has a glass transition temperature (Tg) of 40°C or higher.
  • Tg glass transition temperature
  • This Tg means that a cured resin plate is prepared by the method described in ⁇ Preparation of cured resin plate> below, and DMA (dynamic viscoelasticity) is measured by the method described in ⁇ Measurement of glass transition temperature Tg of cured resin> below.
  • DMA dynamic viscoelasticity
  • the Tg of the cured epoxy resin is more preferably 50°C or higher.
  • Epoxy resin cured products that have a low Tg and are in a rubbery state at room temperature are susceptible to side reactions, even if they are cured products of epoxy resins that do not have unsaturated bonds and thiol group-containing curing agents. and discoloration due to ultraviolet light is likely to occur.
  • the epoxy resin cured product of the present invention since the epoxy resin cured product of the present invention has a Tg higher than room temperature, it has sufficient hardness, and the coated molded product is less likely to be damaged during handling.
  • Machinability at normal temperature is also good, so when polishing the surface of the coated fiber reinforced resin molded article as a pretreatment for coating the fiber reinforced resin molded article coated with the epoxy resin cured product of the present invention, Because it does not soften even when heat is trapped, it can be polished in a short time even with fine-grained paper. It is more preferable that the hardness of the coating resin of the coated fiber-reinforced resin molded product is H or higher than the pencil hardness under standard conditions of temperature of 23° C. and humidity of 50%.
  • Weather resistance of the epoxy resin cured product of the present invention is preferably such that discoloration is slight even when exposed to an ultraviolet dose (308 MJ/m 2 ) equivalent to one year exposure to Florida in a high temperature environment (47°C).
  • the color difference ( ⁇ E) of a cured epoxy resin product having a thickness of 2 mm is preferably 30 or less, more preferably 20 or less. With this plate thickness and this color difference, if the film thickness of the paint containing the ultraviolet absorber applied to the fiber-reinforced resin molded product coated with the epoxy resin cured product is 10 ⁇ m or more, the discoloration will be slight. Further, if the color difference ( ⁇ E) of the epoxy resin cured product having a thickness of 2 mm is 4 or less, discoloration is slight even without a coating containing an ultraviolet absorber.
  • the coated fiber-reinforced resin molded product of the present invention is obtained by coating at least part of the surface of the fiber-reinforced resin molded product with the cured epoxy resin of the present invention as a coating layer.
  • the fiber-reinforced resin molded product to be coated is preferably carbon fiber-reinforced plastic.
  • Carbon fiber reinforced plastics are lightweight, have high rigidity and strength, and can be used in automobiles, railways, aircraft, drones, etc. to reduce their weight, thereby increasing fuel efficiency and cruising range.
  • carbon fiber reinforced resin molded articles using fabrics such as plain weave, twill weave, and satin weave for the surface layer are also required to be aesthetically pleasing, and are suitable as objects to be coated with the epoxy resin composition of the present invention.
  • the fabric used has a carbon fiber basis weight of preferably 180 g/m 2 or more, more preferably 215 g/m 2 or more.
  • the commercial value of the molded article is particularly high in the case of a product in which the fabric itself is visible from the outside by applying a clear coating without applying a colored coating in whole or in part.
  • the carbon fiber used in the coated fiber-reinforced resin molded article of the present invention is not particularly limited, polyacrylonitrile-based carbon fiber, rayon-based carbon fiber, pitch-based carbon fiber, and the like are preferably used. Among them, polyacrylonitrile-based carbon fibers having high tensile strength are particularly preferably used. Twisted yarn, untwisted yarn, non-twisted yarn, and the like can be used as the form of the carbon fiber.
  • Such carbon fibers preferably have a tensile modulus in the range of 180 to 600 GPa. If the tensile modulus is within this range, the obtained fiber-reinforced composite material can be given rigidity, so that the obtained molded article can be reduced in weight. In general, carbon fibers tend to have a lower strength as the modulus of elasticity increases, but within this range the strength of the carbon fibers themselves can be maintained.
  • a more preferable elastic modulus is in the range of 200 to 440 GPa, more preferably in the range of 220 to 300 GPa. The range may be a combination of any of the above upper and lower limits.
  • the tensile modulus of carbon fiber is a value measured according to JIS R7601-2006.
  • Carbon fibers include "Torayca (registered trademark)" T300 (tensile strength: 3.5 GPa, tensile modulus: 230 GPa), “Torayca (registered trademark)” T300B (tensile strength: 3.5 GPa, tensile modulus : 230 GPa), “Torayca (registered trademark)” T400HB (tensile strength: 4.4 GPa, tensile modulus: 250 GPa), “Torayca (registered trademark)” T700SC (tensile strength: 4.9 GPa, tensile modulus: 230 GPa), “Torayca (registered trademark)” T800HB (tensile strength: 5.5 GPa, tensile modulus: 294 GPa), “Torayca (registered trademark)” T800SC (tensile strength: 5.9 GPa, tensile modulus: 294 GPa), “Torayca (registered trademark)” Trademark) “
  • the number of filaments of the carbon fiber is not particularly limited, but when the woven fabric described later is used for the coated fiber-reinforced resin molded product of the present invention, the weaving productivity, the required tensile strength of the coated fiber-reinforced resin molded product, From the viewpoint of flexural modulus, strength, and plate design, the carbon fiber bundle preferably has a range of 1,000 to 70,000 filaments, more preferably 1,000 to 60,000 filaments. It is.
  • the form of the reinforcing fibers used in the coated fiber-reinforced resin molded product of the present invention is not particularly limited, but the above reinforcing fibers are aligned in one direction and combined with the matrix resin described later. It is preferable to adopt a directional fiber reinforced plastic or a fabric reinforced plastic in which the above-mentioned reinforcing fibers are processed into a fabric and then combined with a matrix resin to be described later.
  • the weave structure of the woven fabric is not particularly limited, but plain weave, twill weave, satin weave, ridge weave, satin weave, nest weave, huck weave, imitation weave, and pear weave are preferably used. .
  • the ridge weave can be exemplified by warp ridge weave, weft ridge weave, and variable ridge weave, and can be selected according to the design properties required for the coated fiber-reinforced resin molded product.
  • the nanako weave includes regular nanako weave, variable nanako weave, irregular nanako weave, variable nanako weave, and counter nanako weave. can do.
  • the reinforcing fiber constituting the woven fabric a single glass fiber, a single carbon fiber, or a plurality of different types of glass fibers and carbon fibers may be used. Alternatively, at least one type of glass fiber and at least one type of carbon fiber may be combined and woven together because of their excellent performance, cost and design.
  • the fiber-reinforced resin plastic to be coated may be molded by any method for molding fiber-reinforced plastic, but the reinforcing fiber bundle cut to an appropriate length is pre-impregnated with a thermosetting resin and formed into a sheet.
  • the SMC molding method in which an intermediate base material is pressurized and heated in a molding die to mold it into a predetermined shape, and the intermediate material that is bulk-shaped by mixing reinforcing fiber bundles cut to an appropriate length, thermosetting resin, and filler.
  • a BMC molding method in which a material is pressurized and heated in a molding die to mold it into a predetermined shape.
  • An intermediate base material in which reinforcing fiber bundles that are arranged in parallel or woven into a sheet are impregnated with a matrix resin is impregnated with a matrix resin.
  • a prepreg molding method in which a certain prepreg is laminated and arranged in a mold and heated and pressed with a press, laminated and arranged in a mold and vacuum bagged and heated, or molded by pressurizing and heating in an autoclave.
  • Liquid compression method, RTM method (resin transfer molding method), etc. in which a liquid matrix resin is supplied onto a reinforcing fiber base material such as a fabric or NCF placed on one mold, and the double-sided mold is closed and pressurized and heated. is.
  • the prepreg molding method using prepreg and the RTM molding method are suitable as molding methods for coated fiber-reinforced resin molded products that require less disturbance of the texture of the fabric and are required to be aesthetically pleasing.
  • thermoplastic resin and a thermosetting resin can be appropriately applied as the matrix resin of the fiber-reinforced resin plastic to be coated.
  • Thermosetting resins such as unsaturated polyester resins, epoxy resins, phenolic resins, and polyurethane resins are preferably used as the matrix resin because they provide coated fiber-reinforced resin moldings with excellent mechanical properties.
  • epoxy resins of the same type as the epoxy resin composition of the present invention are more preferable because covalent bonds can be formed with each other and adhesion is further improved.
  • the glass transition temperature of the matrix resin is preferably 100° C. or higher.
  • the epoxy resin composition of the present invention can coat a fiber reinforced resin molded article at a low temperature in a short time with a large film thickness
  • a coated fiber reinforced resin molded article obtained by coating a fiber reinforced resin molded article with the epoxy resin composition of the present invention can be obtained.
  • the surface roughness of the fiber-reinforced resin molded product to be coated is more effective if the undulation curve (Wt) is 3 ⁇ m or more, because the unevenness does not disappear unless the coated surface is polished after coating by the conventional coating method. .
  • a method of coating a fiber-reinforced resin molded product with the epoxy resin composition of the present invention there is a method described in Patent Document 1, or a single-sided mold is coated with the epoxy resin composition of the present invention, and a fiber-reinforced resin molded product is coated thereon. It is also possible to use a method of covering the design surface of , and curing while drawing a vacuum.
  • the fiber-reinforced resin molded product may have a release material applied to the mold that is transferred to the surface so that it can be easily released from the mold, or an internal mold release material added to the matrix resin.
  • the adhesion of the fiber-reinforced resin molded product may not be sufficiently exhibited, so the surface on which the coating layer is formed may be polished with an abrasive or the like to remove the matrix resin and mold release agent on the surface of the fiber-reinforced resin molded product.
  • surface treatment may be applied to chemically improve adhesion.
  • the surface of the fiber reinforced resin layer that has been pretreated to improve adhesion to the coating layer is polished with sandpaper or the like to remove the outermost layer or to form polishing marks. Therefore, the epoxy resin composition of the present invention may be coated. By performing these treatments, irregularities that may occur in the molded article can be made smaller than irregularities caused by fibers.
  • the post-heating temperature may be higher than the temperature at which the epoxy resin composition of the present invention is coated.
  • the coated epoxy resin cured product has a higher elastic modulus than the liquid epoxy resin composition, so it is difficult to follow the heat shrinkage of the surface irregularities of the fiber reinforced resin molded product caused by post-heating. This is because even if the resin composition is post-cured at a temperature higher than the temperature at which the resin composition is cured, deterioration in surface quality is slight.
  • the post-heating temperature is preferably +70°C or lower, more preferably +60°C or lower with respect to the complete curing Tg of the epoxy resin composition of the present invention.
  • the post-heating temperature is preferably +70°C or lower, more preferably +60°C or lower with respect to the complete curing Tg of the epoxy resin composition of the present invention.
  • the thickness of the coating layer of the coated fiber-reinforced resin molded product of the present invention is preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more.
  • the thickness of the coating layer of the coated fiber-reinforced resin molded product of the present invention is preferably 600 ⁇ m or less, more preferably 500 ⁇ m or less.
  • the effect of the present invention can be evaluated by quantifying surface unevenness.
  • typical means for this are a method of measuring using a surface roughness meter, or a cross section of the coated fiber reinforced resin using a microscope or the like.
  • it may be obtained from the waviness curve (Wt) using a contact-type surface roughness meter, or may be obtained from a cross section using a microscope. If it is difficult to see the interface between the coating agent and the fiber-reinforced resin molded product, X-ray fluorescence analysis, SEM, or the like may be used.
  • the evaluation of the present invention uses WaveScan, which can quantify the clarity of the image and the phenomenon that waviness appears on the painted surface (also called orange peel) when a certain level of glossiness is obtained. can also be measured.
  • the best surface condition is called "Class A”.
  • SW short wave
  • LW long wave
  • SW is 20 or less
  • LW is 4 or less.
  • the waviness curve (Wt) is preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less. If the thickness is 2 ⁇ m or less, class A can be achieved with only one coating.
  • the molded product has a particularly high commercial value.
  • the unique pattern expressed by the woven structure is excellent in design, plain weave, twill weave, satin weave, and the like are often preferred.
  • the basis weight of the base material also affects the design. When used for a product whose woven structure is visible from the outside, it is preferable to use a base material of approximately 100 g/m 2 to 300 g/m 2 .
  • Epoxy resin Syna Epoxy 186 (manufactured by SYNASIA): diglycidyl 4,5-epoxyhexahydrophthalate, epoxy equivalent 110 - "Celoxide” (registered trademark) 2021P (manufactured by Daicel Corporation): 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, epoxy equivalent 130 EHPE3150 (manufactured by Daicel Corporation): 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxy equivalent 180 ⁇ HBE-100 (manufactured by Shin Nippon Rika Co., Ltd.): Hydrogenated bisphenol A type epoxy resin, epoxy equivalent 215 ⁇ RD 129 (manufactured by epotec): pentaerythritol polyglycidyl ether, epoxy equivalent 160 2.
  • the component (B) (thiol compound), the component (C) (quaternary phosphonium salt) and other substances were blended at the blending ratio shown in Table 1 to prepare a curing agent liquid.
  • An epoxy resin composition was prepared by using these base liquids and curing agent liquids and mixing them at the compounding ratios shown in Table 1.
  • Tg of cured resin A test piece of 40 mm ⁇ 10 mm was cut out from the cured resin plate, and Tg was measured using a DMA (dynamic viscoelasticity measurement) device (ARES-G2 manufactured by TA Instruments). The measurement conditions are a temperature increase rate of 5° C./min. Measurement was performed in the temperature range of -50°C to 130°C, and the point at which the storage modulus changed (On set) was defined as the glass transition point.
  • DMA dynamic viscoelasticity measurement
  • ⁇ Coloring of cured product The presence or absence of coloration was determined for the resin-cured plate. Specifically, a test piece of 30 mm square and 2 mm in thickness cut out from a cured resin plate is used, and a spectrophotometer (CM-700d, manufactured by Konica Minolta Co., Ltd.) is used to set the color tone of the cured product to L. *a*b* color system.
  • the L*a*b* color system is used to represent the color of a substance, where L* represents lightness and a* and b* represent chromaticity.
  • a* indicates the red direction
  • -a* indicates the green direction
  • b* indicates the yellow direction
  • -b* indicates the blue direction.
  • Spectral transmittance was measured in a wavelength range of 380 to 780 nm, with a D65 light source and a 10° field of view, and without specular reflection. At this time, the case where
  • the fiber-reinforced composite material used was produced by the following RTM molding method.
  • Carbon fiber fabric CO6343B (carbon fiber: T300-3K, texture: plain weave, basis weight: 198 g / m 2 , manufactured by Toray Industries, Inc.) was placed in the cavity of a mold having a plate-shaped cavity of 350 mm ⁇ 700 mm ⁇ 1.6 mm as a reinforcing fiber. ) and a glass fiber fabric M340 (Unitika Ltd.) as an intermediate layer were placed, and the mold was clamped with a press. Next, the inside of the mold held at a temperature of 120° C.
  • molding temperature is evacuated to atmospheric pressure ⁇ 0.1 MPa by a vacuum pump, and 100 parts by mass of an epoxy resin composition (TR-C38 manufactured by Toray Industries, Inc.)
  • TR-C38 manufactured by Toray Industries, Inc.
  • a mixed resin containing 1 part by mass of IC-35 was injected using a resin injection machine.
  • the surface smoothness of the obtained fiber-reinforced composite material was measured by SURF COM 480A (manufactured by ACCRETECH) in the "wave undulation curve" mode, measuring length 10 mm, cutoff 0.25 mm, resin made at the intersection of the warp and weft of the fabric. Measurements were taken 10 times so as to pass through the chisel, and the maximum value was 7.5 ⁇ m.
  • ⁇ Coating molding> The temperature of the cavity coating mold of a mold having a plate-shaped cavity of 350 mm ⁇ 350 mm ⁇ 1.9 mm is adjusted to 50 ° C., a fiber reinforced composite material cut into 350 mm ⁇ 350 mm is placed on the lower mold, and the fiber reinforced resin is produced. Two spacers of 350 mm ⁇ 10 mm ⁇ 0.3 mmt were placed on both ends of the upper surface, and after the upper mold was closed, the inside of the mold was evacuated. Then, according to the compounding ratio of Table 1, the epoxy resin composition was injected using a resin injection machine. The resin was poured into the mold, and after 10 minutes, the upper mold was opened and the fiber-reinforced resin molded product with the film formed on the surface was taken out.
  • a fiber reinforced composite material cut to 350 mm ⁇ 350 mm is placed on a hot plate, and the temperature of the hot plate is adjusted so that the surface temperature of the fiber reinforced composite material is 50 ° C., and then the fiber reinforced composite material on the hot plate is coated with a thickness
  • Two spacers of 50 mm x 20 mm x 0.2 mm wrapped in 0.05 mm paper were arranged with a 10 mm separation between them so that the longitudinal direction was horizontal.
  • the surface smoothness of the coated coated fiber-reinforced resin molded product was evaluated by wave scan (WS) value of the surface of the molded product.
  • the WS value is called “class A” when the surface is the best in automobile applications.
  • SW short wave
  • LW long wave
  • the LW value of the surface of the coated fiber-reinforced resin molded product on which the coating layer was formed was measured five times using a wave scan device (Wave Scan Dual), and the average value is shown in Table 1.
  • Weather resistance was evaluated by placing a 2 mm thick resin cured plate in a metering weather meter (M6T manufactured by Suga Test Instruments Co., Ltd.), temperature 47° C., humidity 50%, irradiation amount 1250 W/m 2 , cumulative irradiation amount 308 MJ/. Tests were performed on m2 . Before and after standing, the color difference ( ⁇ E) was measured with a spectrophotometer (CM-700d, manufactured by Konica Minolta, Inc.).
  • Example 1 As shown in Table 1, a main agent liquid consisting of 100 parts by mass of "Syna Epoxy 186" having two functional epoxy groups having a glycidyl structure in one molecule and one functional epoxy group having an alicyclic structure was added to the main agent tank.
  • An epoxy resin composition was prepared using a resin injection machine in which a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET” was dissolved in 124 parts by mass of a thiol compound "Karenzu MT PE1" was placed in a curing agent tank. was prepared by mixing.
  • the temperature of the main agent tank and the curing agent tank was controlled to 25° C., respectively, and mixing was performed via a static mixer.
  • This epoxy resin composition had a low viscosity even at a temperature of 25° C., and could be injected into the entire mold with sufficient margin in the method described in ⁇ Coating Molding> above.
  • the mixing state of the main component liquid and the curing agent liquid was also good.
  • Even after curing at 50°C for 10 minutes, the adhesiveness to the fiber-reinforced composite material was good, and the mold could be demolded without any problems.
  • the cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance.
  • a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
  • Example 2 To 100 parts by mass of "Syna Epoxy 186", 50 parts of "Celoxide 2021P” having a bifunctional epoxy group having an alicyclic structure was added to prepare a main liquid, and 117 parts by mass of the thiol compound "Karenz MT PE1" was added to the fourth.
  • the procedure was carried out in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of a grade phosphonium salt "Hishikorin PX-4ET” was dissolved was put into a curing agent tank. Compared with Example 1, it had a lower viscosity and could be quickly injected into the entire mold in the method described in ⁇ Coating Molding> above.
  • Example 1 Although the adhesive strength at demolding was lower than that of Example 1, the mold could be demolded without any problems.
  • the cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance.
  • a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
  • Example 3 To 100 parts by mass of "Syna Epoxy 186", 12.5 parts of “Celoxide 2021P” having an epoxy group having an alicyclic structure and 12.5 parts of “EHPE3150” having an epoxy group having a glycidyl structure were added to prepare a main component liquid. was mixed. At the time of preparation, the mixture was heated to 120° C. to dissolve “EHPE3150”, returned to room temperature, and transferred to the main agent tank of the resin injector.
  • Example 1 was carried out in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET” was dissolved in 117 parts by mass of the thiol compound "Karenzu MT PE1" was added to the curing agent tank. did.
  • Example 1 As with Example 1, it had a low viscosity and could be quickly injected into the entire mold by the method described in ⁇ Coating molding> above.
  • the adhesive strength at the time of demolding was the same, and the mold could be demolded without any problem.
  • the cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance.
  • a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
  • Example 4 25 parts of "EHPE3150” having an epoxy group having a glycidyl structure was added to 100 parts by mass of "Syna Epoxy 186" to prepare a main component liquid. At the time of preparation, the mixture was heated to 120° C. to dissolve “EHPE3150”, returned to room temperature, and transferred to the main agent tank of the resin injector. Performed in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt “Hishikorin PX-4ET” was dissolved in 113 parts by mass of the thiol compound "Karenzu MT PE1" was added to the curing agent tank. did.
  • Example 1 As with Example 1, it had a low viscosity, and could be injected into the entire mold without any problems in the method described in ⁇ Coating molding> above.
  • the adhesive strength at the time of demolding was high, and the mold could be demolded without any problem.
  • the cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance.
  • a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
  • Example 5 Example 5 was repeated except that the post-curing temperature was 80°C for Example 5 and 125°C for Example 6. Even when the post-curing temperature was changed, the cured product of the epoxy resin composition showed no coloration, slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance. A fiber-reinforced composite material having a cured film prepared using this epoxy resin composition exhibits better surface smoothness when the post-curing temperature is lower, but sufficiently good surface smoothness is exhibited even at a high temperature. had. The surface smoothness after coating was also very good. Table 1 shows the results.
  • Example 7 To 100 parts by mass of “Syna Epoxy 186" was added 50 parts of "EHPE3150” having an epoxy group having a glycidyl structure to prepare a main component liquid. At the time of preparation, the mixture was heated to 120° C. to dissolve “EHPE3150”, returned to room temperature, and transferred to the main agent tank of the resin injector.
  • Example 4 was carried out in the same manner as in Example 4, except that a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET” was dissolved in 108 parts by mass of the thiol compound "Karenzu MT PE1" was added to the curing agent tank. did.
  • Example 1 Although the viscosity was slightly higher than that of Example 1, it could be injected into the entire mold without any problems in the method described in ⁇ Coating Molding> above.
  • the adhesive strength at the time of demolding was very high, and the mold could be demolded without any problem.
  • the cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance.
  • a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
  • the cured product of the epoxy resin composition was not colored, but had a Tg much lower than the temperature of the test environment, was greatly discolored due to being exposed to ultraviolet rays in a rubber state, and did not have sufficient weather resistance.
  • the cured film prepared using this epoxy resin composition was soft, and when polishing was performed before painting, the cured film was missing and clogging occurred on the surface of the Scotchbride. Compared to 1, the time and number of scotch brides required increased.
  • a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and although the surface smoothness after coating was inferior to that of Example 1, it was good. Table 2 shows the results.
  • the coating was peeled off when the mold was demolded, and the adhesion was low when the mold was demolded.
  • the cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance.
  • a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 2 shows the results.
  • the cured product of the epoxy resin composition was not colored, but had a Tg much lower than the temperature of the test environment, was greatly discolored due to being exposed to ultraviolet rays in a rubber state, and did not have sufficient weather resistance.
  • the cured film prepared using this epoxy resin composition was soft, and when polishing was performed before painting, the cured film was missing and clogging occurred on the surface of the Scotchbride. Compared to 1, the time and number of scotch brides required increased.
  • a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibits good surface smoothness, and although the surface smoothness after coating is inferior to that of Example 1, it is durable for use. rice field. Table 2 shows the results.
  • the epoxy resin composition of the present invention significantly reduces the surface unevenness that occurs on the surface due to the shape of the reinforcing fibers caused by the temperature difference between the molding temperature (curing temperature) and normal temperature when the fiber reinforced resin is molded. and excellent weather resistance, it is suitable for use as a fiber-reinforced composite material for automobile applications, which particularly require high appearance quality. As a result, it can be expected to contribute to the improvement of fuel efficiency by further reducing the weight of automobiles and the reduction of greenhouse gas emissions.

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Abstract

Le but de la présente invention est de fournir : une composition de résine époxy qui, lorsqu'une résine renforcée par des fibres est moulée, peut réduire une irrégularité de surface provoquée par une différence de température entre une température de moulage (une température de durcissement) et une température normale et présente une qualité de surface élevée et une excellente résistance aux intempéries ; un produit de résine époxy durcie ; et un article moulé en résine renforcée par des fibres revêtu obtenu à l'aide de ceux-ci.　Pour atteindre le but précédent, ladite composition de résine époxy contient au moins : une résine époxy (A) comprenant une ou plusieurs résines époxy ; un agent de durcissement contenant un groupe thiol ; et un catalyseur (C). Une résine époxy (A1), qui représente 50 % ou plus en termes de rapport en poids des résines époxy qui constituent la résine époxy (A), comprend deux groupes époxy, ou plus, ayant une structure glycidyle et un ou plusieurs groupes époxy ayant une structure alicyclique.
PCT/JP2022/013895 2021-03-29 2022-03-24 Composition de résine époxy, produit de résine époxy durcie, et article moulé en résine renforcée par des fibres revêtu obtenu à l'aide de ceux-ci WO2022210246A1 (fr)

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JPS56131619A (en) * 1980-03-18 1981-10-15 Hitachi Chem Co Ltd Epoxy resin composition for electrical insulation
WO2012017896A1 (fr) * 2010-08-05 2012-02-09 日産化学工業株式会社 Composition de résine époxy possédant un cycle hydrocarbure aliphatique monocyclique
CN108192285A (zh) * 2017-12-23 2018-06-22 汕头市骏码凯撒有限公司 一种光学led封装用高粘结环氧塑封料及其制备方法
JP2018530628A (ja) * 2015-07-02 2018-10-18 ハンツマン・アドヴァンスト・マテリアルズ・ライセンシング・（スイッツランド）・ゲーエムベーハー 屋外製品の製造のための熱硬化性エポキシ樹脂組成物およびそれから得られる製品
JP2019522002A (ja) * 2016-07-13 2019-08-08 常州強力先端電子材料有限公司Ｃｈａｎｇｚｈｏｕ Ｔｒｏｎｌｙ Ａｄｖａｎｃｅｄ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． ハイブリッド型感光性樹脂およびその製造方法
JP2019156952A (ja) * 2018-03-12 2019-09-19 三井化学株式会社 光学材料用組成物およびその用途
CN110628178A (zh) * 2019-08-23 2019-12-31 上海卫星装备研究所 一种自修复型纤维增强复合材料及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56131619A (en) * 1980-03-18 1981-10-15 Hitachi Chem Co Ltd Epoxy resin composition for electrical insulation
WO2012017896A1 (fr) * 2010-08-05 2012-02-09 日産化学工業株式会社 Composition de résine époxy possédant un cycle hydrocarbure aliphatique monocyclique
JP2018530628A (ja) * 2015-07-02 2018-10-18 ハンツマン・アドヴァンスト・マテリアルズ・ライセンシング・（スイッツランド）・ゲーエムベーハー 屋外製品の製造のための熱硬化性エポキシ樹脂組成物およびそれから得られる製品
JP2019522002A (ja) * 2016-07-13 2019-08-08 常州強力先端電子材料有限公司Ｃｈａｎｇｚｈｏｕ Ｔｒｏｎｌｙ Ａｄｖａｎｃｅｄ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． ハイブリッド型感光性樹脂およびその製造方法
CN108192285A (zh) * 2017-12-23 2018-06-22 汕头市骏码凯撒有限公司 一种光学led封装用高粘结环氧塑封料及其制备方法
JP2019156952A (ja) * 2018-03-12 2019-09-19 三井化学株式会社 光学材料用組成物およびその用途
CN110628178A (zh) * 2019-08-23 2019-12-31 上海卫星装备研究所 一种自修复型纤维增强复合材料及其制备方法

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