Methods for repairing or reinforcing curable resin compositions, prepreg sheets, laminated sheets, and components.

Abstract

To provide a curable resin composition which can exhibit high adhesion to a member.SOLUTION: There is provided a curable resin composition. The curable resin composition contains a base resin (A) containing a radical polymerization component, and a radical generator (B). A content ratio of a skeleton represented by the following chemical formula (1) in the whole base resin (A) is 1.8 mol / kg or more.SELECTED DRAWING: None

Description

Technical Field

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[0001] The present invention relates to a curable resin composition, a prepreg sheet, a laminated sheet, and a method for repairing or reinforcing a member.

Background Art

[0002] Conventionally, in order to reinforce a member formed of polyvinyl chloride (vinyl chloride resin), a technique of combining with another resin material is known. For example, Patent Document 1 describes an unsaturated polyester resin composition suitable for bonding and reinforcing a vinyl chloride resin molded body.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, as a result of investigations by the present inventors, it has been found that there is still room for improvement in the adhesion to a member composed of polyvinyl chloride or the like, even with the resin composition described in Patent Document 1.

[0005] In view of the above circumstances, the present invention aims to provide a curable resin composition and the like that can exhibit high adhesion to a member.

Means for Solving the Problems

[0006] According to one aspect of the present invention, a curable resin composition is provided. This curable resin composition includes a base resin (A) containing a radical polymerization component and a radical generator (B). The content ratio of the skeleton represented by the following chemical formula (1) in the entire base resin (A) is 1.8 mol / kg or more.

[0007] [ka]

[0008] According to the above embodiment, a curable resin composition or the like that can exhibit high adhesion to a component is provided. [Brief explanation of the drawing]

[0009] [Figure 1] This is a cross-sectional view of a laminated sheet comprising a prepreg sheet according to this embodiment. [Modes for carrying out the invention]

[0010] Embodiments of the present invention will be described below. The various features shown in the embodiments below can be combined with each other. Furthermore, in this specification, "(meth)acrylate" refers to a concept encompassing both "acrylate" and "methacrylate." Also, unless otherwise specified, "~" in this specification represents the sequence from the above to the following.

[0011] [Curable resin composition] First, the curable resin composition of this embodiment will be described. The curable resin composition of this embodiment is shown below.

[0012] A curable resin composition, The material comprises a base resin (A) containing a radical polymerization component and a photoradical generator (B), A curable resin composition in which the content of the skeleton represented by the following chemical formula (1) in the entire base resin (A) is 1.8 mol / kg or more.

[0013] [ka]

[0014] The following describes the components that are essential or optional to be included in the curable resin composition of this embodiment.

[0015] (Base resin (A) containing a radical polymerization component) The curable resin composition of the present embodiment includes a base resin (A) containing a radical polymerization component (hereinafter, also simply referred to as "base resin (A)"). The curing component contained in this base resin (A) is typically a compound containing a radical polymerizable group (typically a carbon-carbon unsaturated bond) in its chemical structure, and it may be appropriately selected and used from known materials.

[0016] More specifically, the base resin (A) may contain resin components such as unsaturated polyester resins, urethane (meth)acrylate resins, epoxy (meth)acrylate resins, polyester (meth)acrylate resins, and polyether (meth)acrylate resins. In addition, in this specification, the base resin (A) also includes components that are incorporated as a resin matrix after curing (after polymerization). That is, the base resin (A) can include radical polymerizable monomers and multimers of these radical polymerizable monomers.

[0017] In addition, from the viewpoint of easily exhibiting the effects related to the adhesion described above, in the curable resin composition of the present embodiment, the base resin (A) is preferably a resin containing a skeleton represented by chemical formula (1), and includes one or more resins selected from the group consisting of unsaturated polyester resins, urethane (meth)acrylate resins, and epoxy (meth)acrylate resins. Similarly, from the viewpoint of easily exhibiting the effects related to the adhesion described above, in the curable resin composition of the present embodiment, the base resin (A) preferably contains neopentyl glycol di(meth)acrylate as a polymerizable monomer containing a skeleton represented by chemical formula (1). Hereinafter, the various components that can be contained in this base resin (A) will be described continuously.

[0018] · Unsaturated polyester resin In one example, the unsaturated polyester resin in this embodiment can be obtained, for example, from an unsaturated polybasic acid, a saturated polybasic acid, and glycols through a known dehydration condensation reaction, and usually has an acid value of 2 to 40 mg-KOH / g. In the production of the unsaturated polyester resin, a desired unsaturated polyester resin can be obtained by appropriately selecting the selection and combination of the acid components of the unsaturated polybasic acid and the saturated polybasic acid, the selection and combination of the glycols, and their blending ratios, etc.

[0019] Examples of the unsaturated polybasic acids include maleic acid, maleic anhydride, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, glutaconic acid, etc.

[0020] Examples of the saturated polybasic acids include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, het acid, tetrabromophthalic anhydride, etc.

[0021] Examples of the glycols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, hydrogenated bisphenol A, bisphenol A propylene oxide compound, cyclohexanedimethanol, dibromoneopentyl glycol, etc. However, from the perspective of including the skeleton represented by the aforementioned chemical formula (1) in the unsaturated polyester resin, it is desirable to include neopentyl glycol as these glycols.

[0022] In this embodiment, among unsaturated polyester resins, fumaric acid or maleic anhydride is preferred as the unsaturated polybasic acid, isophthalic acid or terephthalic acid as the saturated polybasic acid, and neopentyl glycol is preferred as the main glycol component.

[0023] • Urethane (meth)acrylate resin The urethane (meth)acrylate resin in this embodiment is a resin that can be obtained, for example, by reacting a polyalcohol and / or polyester polyol and / or polyether polyol having two or more hydroxyl groups in one molecule with a diisocyanate to obtain a terminal isocyanate, and / or an isocyanate having one or more isocyanates in one molecule, with a compound having an alcoholic hydroxyl group and one or more acrylate groups or methacrylate groups. Alternatively, the resin can be obtained by first reacting a compound having an alcoholic hydroxyl group and one or more acrylate or methacrylate groups with a diisocyanate so that an isocyanate group remains, and then reacting the remaining isocyanate group with a polyalcohol and / or polyester polyol and / or polyether polyol having two or more hydroxyl groups in one molecule. In the production of urethane (meth)acrylate, the physical properties of the resin can be adjusted by appropriately selecting a combination of isocyanate and polyalcohol and / or polyester polyol and / or polyether polyol, and a compound having an alcoholic hydroxyl group and one or more acrylate or methacrylate groups.

[0024] The above-mentioned compound having an alcoholic hydroxyl group and one or more acrylate or methacrylate groups can be hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, phenoxyhydroxypropyl (meth)acrylate, trimethylolpropanedi (meth)acrylate, dipropylene glycol mono (meth)acrylate, etc.

[0025] Furthermore, examples of polyalcohols having two or more hydroxyl groups in a single molecule include neopentyl glycol, ethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, and the like. Furthermore, as the polyester polyol having two or more hydroxyl groups in a single molecule, saturated polyester polyols with a molecular weight of 1000 to 2000 obtained by the dehydration condensation reaction of polyalcohols such as neopentyl glycol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, and bisphenol A propylene oxide adduct with polybasic acids such as adipic acid, (anhydride) phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid can be used. Furthermore, the polyether polyol having two or more hydroxyl groups in a single molecule can be polyethylene glycol, polypropylene glycols with a molecular weight of 300 to 2000 obtained by the ring-opening reaction of ethylene oxide or propylene oxide, or polycaprolactone obtained by the ring-opening reaction of caprolactone. These can be used individually or in combination of two or more types.

[0026] Examples of compounds having two or more isocyanate groups in a single molecule include aromatic and / or aliphatic polyisocyanate compounds, such as tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, trifunctional isocyanates having an isocyanurate ring formed by the triperization of a bifunctional isocyanate compound, and commercially available polyol-modified isocyanate prepolymers. These can be used individually or in combination of two or more types.

[0027] However, from the viewpoint of incorporating the skeleton represented by the aforementioned chemical formula (1) into the urethane (meth)acrylate resin, it is desirable to include neopentyl glycol or a derivative thereof as a combination of polyalcohol and / or polyester polyol and / or polyether polyol.

[0028] Epoxy (meth)acrylate resin The epoxy (meth)acrylate resin in this embodiment can be manufactured by known methods. For example, the desired epoxy (meth)epoxy acrylate resin can be obtained by appropriately selecting an epoxy resin and an unsaturated monobasic acid in the presence or absence of a known inhibitor and a known esterification catalyst, in an inert gas stream or in an air atmosphere. If necessary, other radical polymerizable monomers or organic solvents can be added to the reaction to lower the melt viscosity of the reaction system. This epoxy (meth)acrylate resin may also be referred to as "vinyl ester resin".

[0029] In this embodiment, the epoxy (meth)acrylate resin can, for example, be an epoxy (meth)acrylate resin having acrylate or methacrylate double bonds at the molecular ends, obtained by adding acrylic acid or methacrylic acid to an epoxy resin having two or more glycidyl ether groups in one molecule. The epoxy resin having two or more glycidyl ether groups in one molecule may be, for example, a bisphenol-type epoxy resin from bisphenol A, bisphenol F, bisphenol S, etc., or their derivatives; a bixylenol-type epoxy resin from bixylenol and its derivatives; a biphenol-type epoxy resin from biphenol and its derivatives; or a naphthalene-type epoxy resin from naphthalene and its derivatives; or an epoxy resin containing an aromatic ring, such as a novolac-type epoxy resin. Furthermore, epoxy resins having two or more glycidyl ether groups in one molecule may be glycidyl ether forms of polyols having fatty chains or alicyclic groups in their structure, such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, neopentyl glycol, and hydrogenated bisphenol A. These can be used individually or in combination of two or more. The epoxy equivalent (epoxy equivalent), which indicates the molecular weight of the epoxy resin, is preferably between 80 and 2000 eq / g. Furthermore, from the viewpoint of incorporating the skeleton shown in the aforementioned chemical formula (1) into the epoxy (meth)acrylate resin, it is desirable that the epoxy resin contains the glycidyl ether compound of neopentyl glycol.

[0030] • Polyester (meth)acrylate resin The polyester (meth)acrylate resin in this embodiment is, for example, a resin obtained by esterifying a polyester polyol with acrylic acid or methacrylic acid. Alternatively, the resin may be obtained by the reaction of an acid-terminated polyester with an acrylate or methacrylate having a glycidyl group. In the production of polyester (meth)acrylate resins, the properties of the polyester (meth)acrylate resin can be adjusted by appropriately selecting a polyester polyol with acrylic acid or methacrylic acid, or an acid-terminated polyester with an acrylate or methacrylate having a glycidyl group.

[0031] • Polyether (meth)acrylate resin The polyether (meth)acrylate resin in this embodiment is, for example, a resin obtained by esterifying a polyether polyol with acrylic acid or methacrylic acid. Alternatively, the resin may be obtained by the reaction of an acid-terminated polyether with an acrylate or methacrylate having a glycidyl group. In the production of polyether (meth)acrylate resins, the properties of the polyester (meth)acrylate resin can be adjusted by appropriately selecting a polyether polyol with acrylic acid or methacrylic acid, or an acid-terminated polyester with an acrylate or methacrylate having a glycidyl group.

[0032] • Radical polymerizable monomers, etc. Examples of radical polymerizable monomers in this embodiment include styrene, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, norbornene dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene oxide-added bisphenol A di(meth)acrylate, and propylene oxide-added bisphenol A di(meth)acrylate. Furthermore, the radical polymerizable monomer may be either a monomer that is solid at room temperature (25°C) or a monomer that is liquid at room temperature (25°C).

[0033] Furthermore, the curable resin composition of this embodiment may also contain a polymer of the above-mentioned radical polymerizable monomer as a base resin (A). Examples of this include diallyl phthalate prepolymer, tyke prepolymer, epoxy prepolymer, urethane prepolymer, acrylate prepolymer, and the like.

[0034] The content of the base resin (A) in the entire curable resin composition is, for example, 70% by mass or more and 99.9% by mass or less, preferably 80% by mass or more and 99.7% by mass or less, and more preferably 85% by mass or more and 99.5% by mass or less. Setting the range in this way makes it easier to balance the curability of the resin with the mechanical properties after curing.

[0035] Furthermore, if the base resin (A) contains resin components, the content of these components is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, when the total amount of base resin (A) is 100 parts by mass. Setting the content of resin components within this range improves the moldability when the prepreg sheet is formed. While the entire base resin (A) can be used as the resin component, the amount of the resin component can be 95 parts by mass or less, or 90 parts by mass or less, when the total amount of base resin (A) is 100 parts by mass.

[0036] Furthermore, if the base resin (A) contains a radical polymerizable monomer, its content is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, based on 100 parts by mass of the entire base resin (A). Setting the content of the radical polymerizable monomer within this range improves workability during application. Furthermore, the entire base resin (A) can be made of radical polymerizable monomers, but the amount of radical polymerizable monomers can be 95 parts by mass or less, or 90 parts by mass or less, when the total amount of base resin (A) is 100 parts by mass.

[0037] The curable resin composition of this embodiment is characterized in that the content of the skeleton represented by the aforementioned chemical formula (1) in the entire base resin (A) is 1.8 mol / kg or more. According to the inventors' research, they have found that by increasing the content ratio of the skeleton represented by chemical formula (1), the adhesion to the component (particularly the component made of polyvinyl chloride resin) is dramatically improved.

[0038] Here, the numerical value of the content of the skeleton represented by chemical formula (1) can be determined as follows. In other words, the total weight of the base resin (A) obtained is calculated based on the various raw materials used in synthesizing the base resin (A). The above-mentioned content ratio can be calculated by dividing this calculated weight by the number of moles used of the raw materials that can constitute chemical formula (1) (typically neopentyl glycol). Furthermore, when using an unsaturated polyester resin as the base resin (A), the proportion of this skeleton can be calculated by subtracting the amount of water produced during the esterification reaction from the weight of the base resin (A).

[0039] Even when performing similar calculations for the compositions disclosed in the examples of Patent Document 1 (e.g., Example 1 of Patent Document 1), the content of this skeleton remains at around 1.6, which is not close to the value specified in this application.

[0040] To satisfy the numerical value for the content of the skeleton shown in chemical formula (1), one can use a resin derived from neopentyl glycol as the aforementioned resin and take measures such as increasing the amount of neopentyl glycol during synthesis. Alternatively, it is also possible to satisfy the above value by using a predetermined amount of polymerizable monomer having the skeleton shown in chemical formula (1) in its structure, such as neopentyl glycol di(meth)acrylate.

[0041] The content of the skeleton represented by chemical formula (1) is preferably 1.85 mol / kg or more, more preferably 1.9 mol / kg or more, even more preferably 1.95 mol / kg or more, and even more preferably 2 mol / kg or more. There is no particular upper limit, but for example, it may be 5 mol / kg or less.

[0042] (Radical Generator (B)) The curable resin composition of this embodiment contains a radical generator (B). In other words, the curable resin composition of this embodiment hardens when the radical generator (B) generates radicals, which polymerize the aforementioned base resin (A). Examples of the radical generator (B) include a photoradical generator (B1), a thermal radical generator (B2), and a redox initiator (B3).

[0043] The photoradical generator (B1) can be appropriately selected from known materials. While the wavelength used for exposure is arbitrary, it is preferable that the photoradical generator (B1) contains a compound with an absorption peak in the ultraviolet region, as this reduces the cost of the light source and simplifies the handling of the materials.

[0044] Examples of this photoradical generator (B1) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholino Acetophenones such as phenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t- Benzophenones such as butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminonium bromide, (4-benzoylbenzyl)trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-prop Examples include thioxanthones such as xythioxanthone and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride; and acyl phosphonate oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0045] Examples of thermal radical generators (B2) include organic peroxides such as benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-n-propyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, and t-butyl peroxy-2-ethylhexanate; and azo compounds such as 2,2'-azobis-isobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile.

[0046] A redox initiator (B3) refers to a combination of agents that can generate radicals at low temperatures. Examples of redox initiators (B3) include combinations of Permec N (trade name, methyl ethyl ketone peroxide, NOF Corporation) and cobalt compounds such as cobalt naphthenate or cobalt octenoate; combinations of Permil H (trade name, cumenehydroperoxide, NOF Corporation) and vanadium compounds such as vanadium pentoxide; combinations of Niper BMT (trade name, di(3-methylbenzoyl)peroxide + benzoyl(3-methylbenzoyl)peroxide + dibenzoylperoxide, NOF Corporation) and dimethylaniline; combinations of Niper PMB (trade name, di(4-methylbenzoyl)peroxide, NOF Corporation) and dimethylaniline; and combinations of Niper BW (trade name, dibenzoylperoxide, NOF Corporation) and dimethylaniline.

[0047] The content of the photoradical generator (B) in the curable resin composition is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.2 parts by mass or more and 8 parts by mass or less, and even more preferably 0.3 parts by mass or more and 5 parts by mass or less, when the content of the base resin (A) is 100 parts by mass. Setting the range in this manner makes it easier to balance the curability of the composition with the mechanical properties after curing.

[0048] (Other ingredients) Furthermore, the curable resin composition of this embodiment may also contain additives other than those listed above, to the extent that it does not impair the objectives of the present invention, such as resins other than those listed above; thixotropes; thixotropy aids; fillers such as silica; various catalysts such as dibutylsun laurate (e.g., tin catalysts); silane coupling agents; sensitizers; colorants including one or more selected from the group consisting of dyes such as green, red, blue, yellow, and black, and pigments such as black pigment; stress reducers; defoamers; leveling agents; foaming agents; antioxidants; ion scavengers; and rubber components. These may be used individually or in combination of two or more, and the amounts blended are arbitrary.

[0049] Furthermore, both organic and inorganic oxidizers can be used as the oxidizers mentioned above. Organic oxidizers may include fatty acid amides synthesized from vegetable oil fatty acids and amines (amide waxes); hydrogenated castor oil; oxidized polyethylene; polymerized oils; surfactants; and urea-modified compounds. Inorganic oxidizers may include clay minerals such as bentonites, talc, and mica. The amount of these oxidizers added should be appropriately set according to the purpose.

[0050] The thixotrope enhancer may be, for example, a polyhydroxycarboxylic acid ester derivative, a polycarboxylic acid amide derivative, or a polyether phosphate ester derivative. As polyhydroxycarboxylic acid ester derivatives, for example, BYK-R 606 (manufactured by Bic Chemie Japan Co., Ltd., trade name) can be used. As polycarboxylic acid amide derivatives, for example, BYK-405 and BYK-R 605 (manufactured by Bic Chemie Japan Co., Ltd., trade names) can be used. As polyether phosphate ester derivatives, for example, Disparon 3500 (manufactured by Kusumoto Chemical Co., Ltd., trade name) can be used.

[0051] Other specific examples of thixotropic additives include anionic surfactants, cationic surfactants, nonionic surfactants, betaine-type surfactants, and polyethylene glycol. As anionic surfactants, alkali salts of higher fatty acids, alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, sulfosuccinate esters, etc. can be used. As cationic surfactants, higher amine halates, alkylpyridinium halides, quaternary ammonium salts, etc. can be used. As nonionic surfactants, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, etc. can be used. As betaine-type surfactants, amino acids, etc. can be used. When using polyethylene glycol as a thixotropy enhancer, the average molecular weight is arbitrary, but for example, it can be set to 200 to 1500, or to 250 to 1000.

[0052] Furthermore, the aforementioned fillers may include silica, alumina, calcium carbonate, magnesium carbonate, barium carbonate, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, magnesium oxide, zinc oxide, aluminum nitride, boron nitride, and the like. These fillers may be used individually or in combination, and their particle size and blending amounts can be set arbitrarily.

[0053] (Method for producing curable resin compositions) The curable resin composition of this embodiment can be manufactured by mixing the materials described above. For example, a predetermined curable resin composition can be obtained by mixing each material using a mixer such as a homodisperser, homomixer, universal mixer, planetary mixer, kneader, or three-roll mixer. The temperature and stirring conditions during mixing should be set appropriately according to the materials being used.

[0054] (Applications of curable resin compositions) The curable resin composition of this embodiment can be used for various applications, but for example, it can be used to repair or reinforce a component by obtaining a prepreg sheet, as described later. The type of component is not particularly limited and may be made of various materials such as metal, ceramic, resin, or mineral, but typically the curable resin composition is used to repair or reinforce a component made of polyvinyl chloride.

[0055] [Prepreg sheet] Next, the prepreg sheet of this embodiment and its manufacturing method will be described. The prepreg sheet of this embodiment is obtained by impregnating a fibrous substrate with a curable resin composition. Typically, the prepreg sheet of this embodiment is manufactured by the following process. (Sa1) Prepare a fiber substrate and a curable resin composition. (Sa2) Impregnate the fibrous substrate with a curable resin composition.

[0056] In other words, a prepreg sheet is obtained by preparing the aforementioned fiber substrate and curable resin composition in step (Sa1), and then impregnating the fiber substrate with the curable resin composition in step (Sa2). While not necessarily limited to this embodiment, typically, this impregnation involves impregnating the fiber substrate with a curable resin composition without a solvent. Furthermore, when impregnating the fiber substrate with the curable resin composition, methods such as reducing the viscosity of the curable resin composition using a roller or reducing its viscosity by heating the curable resin composition can also be employed.

[0057] <Textile base material> The fibrous base material in the prepreg sheet can be any known material, such as glass fiber, carbon fiber, aramid fiber, Zylon fiber, vinylon fiber, polyethylene fiber, boron fiber, basalt fiber, cellulose, etc. Furthermore, the surface treatment agent and shape (unidirectional, cross, NCF, nonwoven fabric, etc.) of the reinforcing fiber can be appropriately configured and used.

[0058] Among these fibrous substrates, in the prepreg sheet of this embodiment, it is preferable that the fibrous substrate is glass fiber. By adopting this configuration, the strength and transparency of the cured prepreg sheet can be made to a high level.

[0059] The fiber base material content in the entire prepreg sheet of this embodiment can be, for example, 10% to 90% by mass, and preferably 20% to 80% by mass from the viewpoint of mechanical properties and moldability.

[0060] On the other hand, the content of the curable resin composition in the entire prepreg sheet of this embodiment can be, for example, 10 to 90% by mass, and preferably 20 to 80% by weight from the viewpoint of mechanical properties and moldability.

[0061] [Laminated Sheet] Next, we will explain the more specific uses of prepreg sheets. In one embodiment, the prepreg sheet is traded as a laminated sheet and used for repairing and reinforcing components. The materials that can be used as these components are as described above.

[0062] Figure 1 is a cross-sectional view of a laminated sheet comprising a prepreg sheet according to this embodiment. The laminated sheet of this embodiment, as an example, comprises a prepreg sheet and a light-transmitting sheet disposed on at least one side of the prepreg sheet.

[0063] More specifically, the laminated sheet 10 shown in Figure 1 has a prepreg sheet 11 in the center, with a first sheet 12 on one side and a second sheet 13 on the other side. In the laminated sheet 10 of Figure 1, at least one of the first sheet 12 and the second sheet 13 is a light-transmitting sheet. Although the laminated sheet 10 shown in Figure 1 has a shape in which each sheet is flush with the surface, it is not necessary for the first sheet 12 and / or the second sheet 13 to protrude outward from the edge of the prepreg sheet 11.

[0064] As an example, a method for repairing or reinforcing a member using such a laminated sheet 10 will be described assuming that the curable resin composition is a composition that hardens with light (typically containing a photoradical generator (B1) as a radical generator (B)), and the first sheet 12 is a light-transmitting sheet. In other words, the method for repairing or reinforcing the member of this embodiment is carried out according to the following steps. (Sb1) Prepare the laminated sheet 10. (Sb2) Peel off the second sheet 13. (Sb3) The prepreg sheet 11 provided on the laminated sheet 10 is placed opposite the surface of the member to be repaired or reinforced, and the prepreg sheet 11 is laminated to the surface of the member. (Sb4) The prepreg sheet 11 is exposed through the first sheet 12 (a light-transmitting sheet). (Sb5) After exposure, peel off the first sheet 12.

[0065] First, we will explain the preparation of the laminated sheet 10 in process (Sb1). In the method for repairing or reinforcing the member of this embodiment, the first sheet 12 of the laminated sheet 10 is a light-transmitting sheet. This light-transmitting sheet can be selected from known materials, but may be a sheet or film made of polyethylene, polypropylene, polyester (PET, etc.). In this specification, the term "sheet," along with the term "film," comprehensively refers to materials that are in the form of a film or a thin plate, without any particular limitations on thickness. Although not limited to the following ranges, examples include prepreg sheet 11, first sheet 12, and second sheet 13, each having a thickness of 10 μm or more and 1 mm or less.

[0066] Furthermore, the second sheet 13 of the laminated sheet 10 may or may not be light-transmitting (i.e., it may be a light-shielding sheet or film). In addition, if the prepreg sheet 11 of this embodiment contains a photocurable resin composition, it is also possible to use a material that does not transmit light in order to prevent curing. Moreover, in one embodiment, it is also possible to construct a process in which the laminated sheet 10 does not have this second sheet 13 and the step (Sb2) described later is not performed.

[0067] Furthermore, the first sheet 12 and the second sheet 13 in the laminated sheet 10 may be surface-treated to improve their release properties. In addition, to obtain the laminated sheet 10, the aforementioned prepreg sheet 11 can be prepared and the respective films can be laminated using known methods.

[0068] In the subsequent step (Sb2), the second sheet 13 is peeled off from the laminated sheet 10 described above.

[0069] In step (Sb3), the prepreg sheet 11 provided on the laminated sheet 10 is placed opposite the surface of the member to be repaired or reinforced, and the prepreg sheet 11 is laminated to the surface of the member. The lamination method for this process can be any known technique, but it is typically performed by applying external force (such as bonding with a de-aerating roller or de-aerating operation).

[0070] Next, in step (Sb4), the prepreg sheet 11 is exposed to light through the first sheet 12. The wavelength of light used for this exposure can be appropriately selected depending on the type of photoradical generator (B1).

[0071] Finally, in step (Sb5), the first sheet 12 is peeled off to obtain the repaired or reinforced member.

[0072] Furthermore, they may be provided in the following embodiments.

[0073] (1) A curable resin composition comprising a base resin (A) containing a radical polymerization component and a radical generator (B), wherein the content of the skeleton represented by the following chemical formula (1) in the entire base resin (A) is 1.8 mol / kg or more. [ka]

[0074] (2) The curable resin composition described in (1) above, wherein the base resin (A) comprises one or more resins selected from the group consisting of unsaturated polyester resins, urethane (meth)acrylate resins and epoxy (meth)acrylate resins, as a resin containing the skeleton represented by the chemical formula (1).

[0075] (3) A curable resin composition according to (1) or (2) above, wherein the base resin (A) comprises neopentyl glycol di(meth)acrylate as a polymerizable monomer containing the skeleton represented by the chemical formula (1).

[0076] (4) A curable resin composition according to any one of the above items (1) to (3), which is used for repairing or reinforcing a member made of polyvinyl chloride.

[0077] (5) A prepreg sheet comprising a fibrous base material impregnated with a curable resin composition described in any one of items (1) to (4) above.

[0078] (6) A laminated sheet comprising a prepreg sheet as described in (5) above and a light-transmitting sheet disposed on at least one surface of the prepreg sheet, wherein the curable resin composition contains a photoradical generator (B1) as the radical generator (B).

[0079] (7) A method for repairing or reinforcing a member, comprising: preparing the laminated sheet described in (6) above; arranging the prepreg sheet provided on the laminated sheet facing the surface of the member to be repaired or reinforced; laminating the prepreg sheet to the surface of the member; and exposing the prepreg sheet through the light-transmitting sheet. Of course, this is not always the case.

[0080] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and modifications, improvements, etc., within the scope that can achieve the objectives of the present invention are included in the present invention. [Examples]

[0081] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

[0082] [Synthesis Example 1] In a reaction vessel equipped with a stirrer, fractional distillation apparatus, nitrogen inlet tube, and thermometer, 90 parts by mass of propylene glycol, 234 parts by mass of neopentyl glycol, and 213 parts by mass of isophthalic acid were added, and the temperature was raised to 215°C while stirring. When the acid value of the contents fell to 20 mg KOH / g or less at 215°C, the mixture was cooled to 100°C, 189 parts by mass of maleic anhydride were added, and the temperature was raised to 215°C. The reaction was carried out at 215°C for 8 hours to obtain an unsaturated polyester resin with an acid value of 10 mg KOH / g. In this example, the obtained resin will be abbreviated as "Resin (A-1)".

[0083] [Example 1: Preparation of a curable resin composition] In a light-shielding container equipped with a stirrer and a heating device, 63 parts by mass of resin (A-1) obtained in Synthesis Example 1, 37 parts by mass of styrene monomer as a reactive monomer, 0.25 parts by mass of 12% cobalt octenoate solution, and 1 part by mass of Permec N [trade name, methyl ethyl ketone peroxide, NOF Corporation] were added and stirred to obtain a curable resin composition. At this time, the concentration of the skeleton represented by chemical formula (1) in the base resin (A) was 2.22 [mol / kg].

[0084] [Comparative Example 1: Preparation of a Curable Resin Composition] A curable resin composition was obtained using the same method as in Example 1, except that the resin components of Example 1 (63 parts by mass of resin (A-1) and 37 parts by mass of styrene monomer) were changed to 45.8 parts by mass of resin (A-1) and 54.2 parts by mass of styrene monomer. At this time, the concentration of the skeleton represented by chemical formula (1) in the base resin (A) was 1.60 [mol / kg].

[0085] [evaluation] Each composition obtained in Example 1 and Comparative Example 1 was evaluated according to the following criteria. Specifically, a commercially available gray PVC sheet (3 mm thick) was degreased with acetone, then a #200 glass mat was placed on the surface of the PVC sheet, impregnated with the compositions of Example 1 and Comparative Example 1, and cured for 24 hours. The composite layer of the cured resin and glass mat was peeled off the PVC sheet, and the adhesion state was evaluated by observing its condition. As a result, in Example 1, resin remained almost entirely on the adhesive surface of the PVC sheet, whereas in Comparative Example 1, almost no resin remained on the adhesive surface of the PVC sheet. This confirms that the composition of Example 1 has high adhesion to polyvinyl chloride.

[0086] [Synthesis Example 2] In a reaction vessel equipped with a stirrer, condenser, nitrogen inlet tube, and thermometer, 342.3 g of bisphenol A diglycidyl ether (epoxy equivalent 188 g / eq), 156.7 g of methacrylic acid, 0.1 g of polymerization inhibitor toluhydroquinone, and 1.0 g of esterification catalyst triphenylphosphine were charged. The addition reaction was carried out at a reaction temperature of 110°C until the acid value reached 2 mg KOH / g to obtain a vinyl ester. In this example, the obtained resin will be abbreviated as "resin (A-2)".

[0087] [Example 2: Preparation of a photocurable resin composition] A photocurable resin composition was obtained by adding 60 parts by mass of resin (A-2) obtained in Synthesis Example 2, 40 parts by mass of neopentyl glycol diacrylate as a reactive monomer, and 0.4 parts by mass of Omnirad 184 (hereinafter abbreviated as "O-184") manufactured by IGM Resins BV as a photoradical generator to a light-shielding container equipped with a stirrer and a heating device, and stirring. At this time, the concentration of the skeleton shown in chemical formula (1) in the base resin (A) was 1.88 [mol / kg].

[0088] [Example 3: Preparation of a photocurable resin composition] A photocurable resin composition was obtained by adding 100 parts by mass of neopentyl glycol diacrylate and 0.4 parts by mass of O-184 to a light-shielding container equipped with a stirrer and a heating device, and stirring. At this time, the concentration of the skeleton represented by chemical formula (1) in the base resin (A) was 4.71 [mol / kg].

[0089] [Example 4: Preparation of a photocurable resin composition] A photocurable resin composition was obtained by adding 55 parts by mass of resin (A-2), 45 parts by mass of neopentyl glycol dimethacrylate, and 0.4 parts by mass of O-184 to a light-shielding container equipped with a stirrer and a heating device, and stirring. At this time, the concentration of the skeleton represented by chemical formula (1) in the base resin (A) was 1.87 [mol / kg].

[0090] [Example 5: Preparation of a photocurable resin composition] A photocurable resin composition was obtained by adding 100 parts by mass of neopentyl glycol dimethacrylate and 0.4 parts by mass of O-184 to a light-shielding container equipped with a stirrer and a heating device, and stirring. At this time, the concentration of the skeleton represented by chemical formula (1) in the base resin (A) was 4.16 [mol / kg].

[0091] [Comparative Example 2: Preparation of a Photocurable Resin Composition] A photocurable resin composition was obtained by adding 70 parts by mass of resin (A-2), 30 parts by mass of neopentyl glycol diacrylate, and 0.4 parts by mass of O-184 to a light-shielding container equipped with a stirrer and a heating device, and stirring. At this time, the concentration of the skeleton represented by chemical formula (1) in the base resin (A) was 1.41 [mol / kg].

[0092] [Comparative Example 3: Preparation of a Photocurable Resin Composition] A photocurable resin composition was obtained by adding 70 parts by mass of resin (A-2), 30 parts by mass of neopentyl glycol dimethacrylate, and 0.4 parts by mass of O-184 to a light-shielding container equipped with a stirrer and a heating device, and stirring. At this time, the concentration of the skeleton represented by chemical formula (1) in the base resin (A) was 1.25 [mol / kg].

[0093] [evaluation] Each composition obtained in Examples 2-5 and Comparative Examples 2 and 3 was evaluated according to the following criteria. Specifically, a commercially available gray PVC sheet (3 mm thick) was degreased with acetone, then a #200 glass mat was placed on the surface of the PVC sheet and impregnated with the compositions of Examples 2-5 and Comparative Examples 2 and 3. After that, a transparent polypropylene film was placed over it. Next, the resin was cured by UV exposure through the transparent polypropylene film. The composite layer of the cured resin and glass mat was peeled off the PVC sheet, and the adhesion state was evaluated by observing its condition. As a result, in Examples 2-5, resin remained almost entirely on the adhesive surface of the PVC sheet, whereas in Comparative Examples 2 and 3, almost no resin remained on the adhesive surface of the PVC sheet. This confirms the high adhesion of the compositions in Examples 2-5 to polyvinyl chloride.

[0094] From the results of the above examples, it can be said that by setting the skeleton concentration represented by chemical formula (1) to a predetermined value, a curable resin composition that exhibits high adhesion to a component can be provided. [Explanation of Symbols]

[0095] 10: Laminated sheet 11: Prepreg sheet 12: First sheet 13: Second seat

Claims

1. A curable resin composition, Used for repairing or reinforcing components made of polyvinyl chloride. The repair or reinforcement is carried out by bringing the curable resin composition into contact with the surface of the member, and then curing the curable resin composition. The material comprises a base resin (A) containing a radical polymerization component and a radical generator (B), A curable resin composition in which the content of the skeleton represented by the following chemical formula (1) in the entire base resin (A) is 1.8 mol / kg or more. 【Chemistry 1】

2. In the curable resin composition according to claim 1, The base resin (A) is a curable resin composition comprising one or more resins selected from the group consisting of unsaturated polyester resins, urethane (meth)acrylate resins, and epoxy (meth)acrylate resins, as a resin containing the skeleton represented by the chemical formula (1).

3. In the curable resin composition according to claim 1, The base resin (A) is a curable resin composition comprising neopentyl glycol di(meth)acrylate as a polymerizable monomer containing the skeleton represented by the chemical formula (1).

4. It is a prepreg sheet, A prepreg sheet comprising a fibrous base material impregnated with a curable resin composition according to any one of claims 1 to 3.

5. It is a laminated sheet, The prepreg sheet according to claim 4, A light-transmitting sheet is disposed on at least one side of the prepreg sheet, Equipped with, The curable resin composition is a laminated sheet comprising a photoradical generator (B1) as the radical generator (B).

6. A method for repairing or reinforcing a member made of polyvinyl chloride, The laminated sheet described in claim 5, The prepreg sheet provided on the laminated sheet is positioned opposite the surface of the member to be repaired or reinforced, and the prepreg sheet is laminated so that it is in contact with the surface of the member. Exposure to the prepreg sheet through the light-transmitting sheet, A method for repairing or reinforcing a component, comprising the following:

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