Thermosetting resin composition for temporary fixing, masking, or molding

Abstract

To provide a thermosetting resin composition for temporary fixation, masking or molding which is cured by heat, and has high solubility to at least one of water, ethanol, acetone and methylcyclohexane.SOLUTION: A thermosetting resin composition for temporary fixation, masking or molding contains a radical polymerization reactive component (A), a chain transfer agent (B) and a thermal polymerization initiator (C), wherein the component (A) contains one or more monofunctional radical polymerization reactive component (A1) selected from the group consisting of a monomer (A1-1) having a (meth)acrylamide group, a methacrylate monomer (A1-2) and an acrylate monomer (A1-3) having a cyclic structure, in the component (A), the content of the component (A1) is 50 wt.% or more, and in the thermosetting resin composition, the content of a bifunctional or higher radical polymerization reactive component (A2) is 0 wt.% or more and less than 15 wt.%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a thermosetting resin composition for temporary fixing, masking, or molding.

Background Art

[0002] Compositions in which the cured product dissolves in water or an organic solvent after ultraviolet (UV) curing are expected to be applied to various fields such as temporary fixing during member processing, masking agents, and molding applications such as pedestals (support materials) during 3D printer printing. Patent Document 1 discloses a photocurable resin composition that provides a cured product that dissolves in water.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, when used in such a manner that the curable composition is sandwiched between members that do not transmit UV, the photocurable resin composition as disclosed in Patent Document 1 cannot be cured with UV. Therefore, when including a mode in which the photocurable resin composition as disclosed in Patent Document 1 is sandwiched between members that do not transmit UV, it is often difficult to apply it to each use of temporary fixing, masking, or molding.

[0005] An object of the present invention is to provide a thermosetting resin composition for temporary fixing, masking, or molding that cures by heat and has high solubility in at least one of water, ethanol, acetone, and methylcyclohexane.

Means for Solving the Problems

[0006] The present invention relates to the following. [1] A thermosetting resin composition containing a radical polymerization reactive component (A), a chain transfer agent (B), and a thermal polymerization initiator (C), wherein the component (A) contains at least one monofunctional radical polymerization reactive component (A1) selected from the group consisting of a monomer (A1-1) having a (meth)acrylamide group, a methacrylate monomer (A1-2), and an acrylate monomer (A1-3) having a cyclic structure. In the component (A), the content of the component (A1) is 50% by weight or more, and in the thermosetting resin composition, the content of the difunctional or higher radical polymerization reactive component (A2) is 0% by weight or more and less than 15% by weight. A thermosetting resin composition for temporary fixing, masking, or molding, characterized by this. [2] The thermosetting resin composition according to [1], wherein the component (B) is at least one selected from the group consisting of a compound having an α-methylstyrene structure and a compound having a thiol group. [3] The thermosetting resin composition according to [1] or [2], wherein the content of the component (B) in the thermosetting resin composition is 0.5 to 10% by weight. [4] Furthermore, the thermosetting resin composition according to any one of [1] to [3], which contains a polymer component (D). [5] The thermosetting resin composition according to [4], wherein the component (D) is a water-soluble polymer. [6] The thermosetting resin composition according to [4], wherein the component (D) is a hydrogenated diene polymer. [Advantages of the Invention]

[0007] According to the present invention, it is possible to provide a thermosetting resin composition for temporary fixing, masking, or molding that cures by heat and has high solubility in at least one of water, ethanol, acetone, and methylcyclohexane. [Modes for Carrying Out the Invention]

[0008] [Definition of Terms] “(Meth)acrylate” has the meaning of at least one of acrylate and methacrylate. “(Meth)acryloyl group” has the meaning of at least one of acryloyl group and methacryloyl group. The "radical polymerization reactive component (A)" is also referred to as "component (A)". The same applies to the "chain transfer agent (B)" and the like. Regarding numerical ranges, "~" means including the values at both ends. Also, "below" means "the same as or less than", and "above" means "the same as or exceeding". That is, "0.5% by weight to 10% by weight" means "0.5% by weight or more and 10% by weight or less", and includes the meanings of "more than 0.5% by weight and 10% by weight or less", "0.5% by weight or more and less than 10% by weight", and "more than 0.5% by weight and less than 10% by weight".

[0009] [Thermosetting resin composition for temporary fixing, masking or molding] The thermosetting resin composition for temporary fixing, masking or molding (hereinafter also simply referred to as "thermosetting resin composition") contains a radical polymerization reactive component (A), a chain transfer agent (B) and a thermal polymerization initiator (C). Component (A) contains at least one monofunctional radical polymerization reactive component (A1) selected from the group consisting of a monomer (A1-1) having a (meth)acrylamide group, a methacrylate monomer (A1-2) and an acrylate monomer (A1-3) having a cyclic structure. In component (A), the content of component (A1) is 50% by weight or more, and in the thermosetting resin composition, the content of the bifunctional or higher radical polymerization reactive component (A2) is 0% by weight or more and less than 15% by weight.

[0010] The thermosetting resin composition is soluble in at least one solvent selected from water, ethanol, acetone and methylcyclohexane. Therefore, the thermosetting resin composition can be a composition for dissolving in at least one solvent selected from water, ethanol, acetone and methylcyclohexane. Here, the thermosetting resin composition may dissolve in one to three solvents selected from the group consisting of water, ethanol, acetone and methylcyclohexane, but may not dissolve in the remaining solvents. For example, the thermosetting resin composition may dissolve in both acetone and methylcyclohexane, but may not dissolve in both water and ethanol. In this specification, the "at least one solvent selected from water, ethanol, acetone and methylcyclohexane" may sometimes be referred to as the "specific solvent".

[0011] <(Radical Polymerizable Component (A))> The radical polymerizable component (A) is not particularly limited as long as it has a radical polymerizable functional group, and examples include radical polymerizable oligomers and radical polymerizable monomers. The radical polymerizable functional group is not particularly limited as long as it is an unsaturated double bond-containing group, and examples include alkenyl groups (e.g., vinyl group, allyl group, etc.), (meth)acrylamide groups, or (meth)acryloyl groups. Component (A) may consist only of the above-mentioned component (A1), or may contain a predetermined amount of a radical polymerizable oligomer and / or a radical polymerizable monomer in addition to the above-mentioned component (A1). Further, component (A) may consist only of a radical polymerizable monomer, or may be a mixture of a radical polymerizable monomer and a radical polymerizable oligomer.

[0012] In component (A), the weight average molecular weight of the radical polymerizable oligomer is preferably 1,500 or more, and particularly preferably 1,500 to 50,000. As a method for measuring the weight average molecular weight, for components with relatively high molecular weights such as oligomers and polymers, a method of converting the measurement results of gel permeation chromatography (GPC) using a calibration curve of standard polystyrene is generally known. Further, since monomers do not have a molecular weight distribution, they can be determined from the structural formula.

[0013] <<Mono-functional Radical Polymerizable Component (A1)>> Component (A1) is at least one monofunctional radical polymerizable component selected from the group consisting of a monomer (A1-1) having a (meth)acrylamide group, a methacrylate monomer (A1-2), and an acrylate monomer (A1-3) having a cyclic structure. Component (A1-1) has one (meth)acrylamide group in the molecule as a radical polymerizable functional group. Therefore, component (A1-1) does not further have a (meth)acryloyl group. Also, component (A1-2) has one methacryloyl group in the molecule as a radical polymerizable functional group. Component (A1-3) has one acryloyl group in the molecule as a radical polymerizable functional group. Therefore, component (A1-2) and component (A1-3) do not further have a (meth)acrylamide group.

[0014] <1>Monomer (A1-1) having a (meth)acrylamide group The monomer (A1-1) having a (meth)acrylamide group is not particularly limited as long as it is a compound having one (meth)acrylamide group in the molecule. Component (A1-1) is preferably a compound represented by the following formula (1).

[0015]

Chemical formula

[0016] [In the formula, R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are, independently of each other, a hydrogen atom, an alkyl group, a hydroxyalkyl group, or an aryl group substituted with one or more selected from the group consisting of an unsubstituted or hydroxyl group and an alkyl group, or R 2 and R 3 together with the N atom to which they are attached, form an alicyclic group (preferably a morpholino group) that can contain an oxygen atom. ]

[0017] In formula (1), the number of carbon atoms in the alkyl group and the alkyl moiety of the hydroxyalkyl group is preferably from 1 to 18, particularly preferably from 1 to 6. The number of carbon atoms in the aryl group is preferably from 6 to 20. The aryl group is preferably a phenyl group. The morpholino group refers to a monovalent group in which the hydrogen atom of the secondary amine part of morpholine has been removed.

[0018] Examples of component (A1-1) include (meth)acrylamide; N-alkyl(meth)acrylamides having an alkyl group with 1 to 4 carbon atoms such as N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, and N-butyl(meth)acrylamide; N,N-dialkyl(meth)acrylamides having an alkyl group with 1 to 4 carbon atoms such as N,N-dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide; N-hydroxyalkyl(meth)acrylamides having an alkyl group with 2 to 4 carbon atoms such as N-(2-hydroxyethyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide, and N-(4-hydroxybutyl)(meth)acrylamide; (meth)acrylamides having an unsubstituted or substituted aryl group such as N-phenyl(meth)acrylamide, N-(2-hydroxyphenyl)(meth)acrylamide, N-(3-hydroxyphenyl)(meth)acrylamide, N-(4-hydroxyphenyl)(meth)acrylamide, and N-(2-methylphenyl)(meth)acrylamide; (meth)acrylamides having a cyclic structure such as 4-(meth)acryloylmorpholine (preferably, a (meth)acrylamide having an alicyclic group that can contain an oxygen atom). Preferred are N-hydroxyethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and 4-(meth)acryloylmorpholine. From the viewpoint of further increasing the solubility (water solubility) of the cured product of the thermosetting resin composition in water, component (A1-1) is particularly preferably an N-hydroxyalkyl(meth)acrylamide having an alkyl group with 2 to 4 carbon atoms.

[0019] <2> Methacrylate monomer (A1-2) The methacrylate monomer (A1-2) is a monomer having one methacryloyl group in the molecule. Component (A1-2) is a compound having a methacryloyl group as a radical polymerizable group. Component (A1-2) may or may not have a cyclic structure described later.

[0020] Component (A1-2) can be appropriately selected from known methacrylate monomers. Component (A1-2) is preferably a methacrylate monomer having a hetero ring structure containing O and / or N, a hydroxyl group-containing methacrylate monomer, an alicyclic methacrylate monomer, an aromatic methacrylate monomer, an alkyl methacrylate monomer, or a methacrylate of (poly)alkylene glycol monoalkyl ether. Note that the hetero ring structure containing O and / or N is as described later for component (A1-3).

[0021] · Methacrylate monomer having a hetero ring structure containing O and / or N Specific examples of the methacrylate monomer having a hetero ring structure containing O and / or N include tetrahydrofurfuryl methacrylate, alkoxylated tetrahydrofurfuryl acrylate caprolactone-modified tetrahydrofurfuryl methacrylate, pentamethylpiperidinyl methacrylate, cyclic trimethylolpropane formal methacrylate, and the like.

[0022] · Hydroxyl group-containing methacrylate monomer The number of OH groups contained in the hydroxyl group-containing methacrylate monomer is preferably 1 to 3, and particularly preferably 1. Examples of the hydroxyl group-containing methacrylate monomer include hydroxyalkyl methacrylates such as hydroxyethyl methacrylate (e.g., 2-hydroxyethyl methacrylate), hydroxypropyl methacrylate (e.g., 2-hydroxypropyl methacrylate), hydroxybutyl methacrylate (e.g., 2-hydroxybutyl methacrylate), and diethylene glycol monoethyl ether methacrylate.

[0023] · Alicyclic methacrylate monomer Examples of the alicyclic methacrylate monomer include isobornyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyl oxyethyl methacrylate, norbornene methacrylate, cyclohexyl methacrylate, benzyl methacrylate, naphthalenyl methacrylate, phenylphenol ethyloxy methacrylate, and the like.

[0024] · Aromatic methacrylate monomer Examples of the aromatic methacrylate monomer include benzyl methacrylate, phenoxyethyl methacrylate, ethoxylated o-phenylphenol acrylate, phenoxybenzyl methacrylate, naphthalene methacrylate, ethoxylated bisphenol A dimethacrylate, modified bisphenol A dimethacrylate, and the like.

[0025] · Alkyl methacrylate monomer Examples of the alkyl methacrylate monomer include methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, isooctyl methacrylate, isomyristyl methacrylate, lauryl methacrylate, and the like.

[0026] · Methacrylate monomer of (poly)alkylene glycol monoalkyl ether Examples of the methacrylate monomer of (poly)alkylene glycol monoalkyl ether include alkoxyethyl methacrylate, alkoxypropyl methacrylate, alkoxybutyl methacrylate, and multimers of these alkylene glycols (for example, methoxytriethyleneoxyethyl methacrylate). Here, the number of carbon atoms of the alkyl group, alkoxy group, and alkylene group is preferably 1 to 6.

[0027] Component (A1-2) may be one kind or a combination of two or more kinds.

[0028] <3>Acrylate monomer (A1-3) having a cyclic structure The cyclic structure may be a monocyclic or polycyclic structure. Further, the cyclic structure may be an alicyclic structure, an aromatic ring structure, or a heterocyclic structure (i.e., a heterocyclic structure containing O and / or N).

[0029] The total number of atoms constituting one alicyclic structure is not particularly limited, but is preferably 3 to 20. The total number of atoms constituting one aromatic ring structure is not particularly limited, but is preferably 6 to 20.

[0030] The heterocyclic structure is a heterocyclic structure containing O and / or N. When the heterocyclic structure contains an oxygen atom, the number of oxygen atoms in the ring heterocyclic structure is preferably 1 to 3, and particularly preferably 1 to 2. When the heterocyclic structure contains a nitrogen atom, the number of nitrogen atoms in the heterocyclic structure is preferably 1 to 2, and particularly preferably 1. When the heterocyclic structure contains both an oxygen atom and a nitrogen atom, the total number of oxygen atoms and nitrogen atoms in the heterocyclic structure is preferably 2 to 4, and particularly preferably 2 to 3. The heterocyclic structure may be a monocyclic or polycyclic structure. The total number of atoms constituting one heterocyclic structure is not particularly limited, but is preferably 3 to 20. The heterocyclic structure is preferably a monocyclic heterocyclic structure of a 5-membered or 6-membered ring. Examples of the heterocyclic structure include morpholine, furan, tetrahydrofuran, dioxane, pyrrolidine, piperidine, piperazine, pyrrolidone, maleimide, etc. The total number of heterocyclic structures of the methacrylate monomer having a heterocyclic structure is preferably 1 to 3, and particularly preferably 1 to 2. Here, when the heterocyclic structure is a polycyclic structure, the polycyclic structure is taken as 1.

[0031] Component (A1-3) is preferably an alicyclic acrylate monomer, an acrylate monomer having a heterocyclic structure, or an aromatic acrylate monomer.

[0032] · Alicyclic acrylate monomer Examples of alicyclic acrylate monomers include isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, norbornene acrylate, cyclohexyl acrylate, benzyl acrylate, naphthalenyl acrylate, phenylphenol ethyl oxy acrylate, and the like.

[0033] ·Acrylate monomers having a heterocyclic structure containing O and / or N Specific examples of acrylate monomers having a heterocyclic structure containing O and / or N include tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, pentamethylpiperidinyl acrylate, cyclic trimethylolpropane formal acrylate, and the like.

[0034] ·Aromatic acrylate monomers Examples of aromatic acrylate monomers include benzyl acrylate, phenoxyethyl acrylate, ethoxylated o-phenylphenol acrylate, phenoxybenzyl acrylate, naphthalene acrylate, ethoxylated bisphenol A diacrylate, modified bisphenol A diacrylate, and the like.

[0035] Component (A1-3) may be one kind or a combination of two or more kinds.

[0036] <<<Mono-functional radical polymerizable component (A1') other than component (A1)>>> Component (A) may contain a monofunctional radical polymerizable reactive component other than component (A1) (hereinafter sometimes referred to as "component (A1')"). Component (A1') is not particularly limited as long as it is an oligomer and a monomer having one radical polymerizable reactive group in the molecule. Examples of component (A1') include acrylate monomers (excluding acrylate monomers having a cyclic structure). The acrylate monomer (excluding acrylate monomers having a cyclic structure) is preferably a hydroxyl group-containing acrylate monomer, an alkyl acrylate monomer, or an acrylate monomer of (poly)alkylene glycol monoalkyl ether. The acrylate monomer (excluding acrylate monomers having a cyclic structure) has one acryloyl group in the molecule as a radical polymerizable reactive functional group.

[0037] · Hydroxyl group-containing acrylate monomer The number of OH groups in the hydroxyl group-containing acrylate monomer is preferably 1 to 3, and particularly preferably 1. Examples of the hydroxyl group-containing acrylate monomer include hydroxyalkyl acrylates such as hydroxyethyl acrylate (e.g., 2-hydroxyethyl acrylate), hydroxypropyl acrylate (e.g., 2-hydroxypropyl acrylate), hydroxybutyl acrylate (e.g., 4-hydroxybutyl acrylate), and diethylene glycol monoethyl ether acrylate.

[0038] · Alkyl acrylate monomer Examples of the alkyl acrylate monomer include methyl acrylate, ethyl acrylate, tert-butyl acrylate, isooctyl acrylate, isomyristyl acrylate, and lauryl acrylate.

[0039] · Acrylate monomer of (poly)alkylene glycol monoalkyl ether Examples of the acrylate monomer of the (poly)alkylene glycol monoalkyl ether include alkoxyethyl acrylate, alkoxypropyl acrylate, alkoxybutyl acrylate, and multimers of these alkylene glycols (for example, methoxytriethyleneoxyethyl acrylate). Here, the number of carbon atoms of the alkyl group, alkoxy group, and alkylene group is preferably 1 to 6.

[0040] Component (A1') may be one kind or a combination of two or more kinds.

[0041] <<Bifunctional or higher radical polymerizable component (A2)>> The bifunctional or higher radical polymerizable component is an oligomer and a monomer having two or more radical polymerizable groups in the molecule.

[0042] Examples of the oligomer having two or more radical polymerizable groups in the molecule include (meth)acrylate oligomers having two or more (meth)acryloyl groups in the molecule. Preferred examples of the (meth)acrylate oligomer include urethane (meth)acrylate oligomers and epoxy (meth)acrylate oligomers.

[0043] Examples of the urethane (meth)acrylate oligomer include aromatic, aliphatic, polyether, polycarbonate, polyester, or a combination thereof of polyurethane (meth)acrylate oligomers. Commercially available products of urethane (meth)acrylate oligomers include, in addition to those described in the examples, EBECRYL4858 (manufactured by Daicel Allnex), UN-2301 (manufactured by Negami Chemical Co., Ltd.), EBECRYL4859 (manufactured by Daicel Allnex), EBECRYL4738 (manufactured by Daicel Allnex), and the like.

[0044] Epoxy (meth)acrylate oligomers are oligomers in which all epoxy groups in an epoxy resin have reacted with (meth)acrylic acid. Epoxy (meth)acrylate oligomers may also include oligomers in which some of the epoxy groups in an epoxy resin have reacted with (meth)acrylic acid, i.e., oligomers containing epoxy groups and (meth)acryloyl groups in the resin. Examples of epoxy resins include aromatic epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, and other epoxy resins. Commercially available epoxy (meth)acrylate oligomers include EB3700 (manufactured by Daicel-Allnex) and EB3708 (manufactured by Daicel-Allnex).

[0045] The (meth)acrylate oligomer may have 2 to 6 (meth)acryloyl groups, or may have 2 to 4 (meth)acryloyl groups.

[0046] The monomer having two or more radical polymerization reactive groups in the molecule can be appropriately selected from known components.

[0047] <Chain transfer agent (B)> The chain transfer agent (B) is a component that causes a chain transfer reaction. Here, the chain transfer reaction refers to a reaction in radical polymerization where a growing radical reacts with other chemical species in the polymerization system, accompanied by the termination of growth, the transfer of the radical, and the restart of growth. As component (B), compounds having an α-methylstyrene structure such as α-methylstyrene and α-methylstyrene dimer; alcohols such as methanol, ethanol, propanol, and butanol; aldehydes such as acetaldehyde, propionaldehyde, n-butylaldehyde, furfural, and benzaldehyde; halogens such as carbon tetrachloride and chloroform; and compounds having a thiol group such as pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, dodecyl mercaptan, lauryl mercaptan, normal mercaptan, thioglycolic acid, octyl thioglycolate, and thioglycerol are mentioned. One or more selected from the group consisting of these are mentioned, and a compound having an α-methylstyrene structure or a compound having a thiol group is preferred. Component (B) may be one kind or a combination of two or more kinds.

[0048] <Thermal polymerization initiator (C)> The thermal polymerization initiator (C) is preferably a thermal radical polymerization initiator that generates radicals upon heating. Examples of the thermal polymerization initiator (C) include organic peroxides and azo compounds.

[0049] An organic peroxide is a compound containing a peroxy group (-O-O-). An organic peroxide is a radical source. Examples of organic peroxides include diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, peroxyesters, and peroxycarbonates.

[0050] Specific examples of the organic peroxide include diacyl peroxides such as dilauroyl peroxide, dibenzoyl peroxide, and bis-3,5,5-trimethylhexanoyl peroxide; hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide (e.g., Kayaku Cumene H manufactured by Kayaku Akzo Corporation), and t-butyl hydroperoxide; dialkyl peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, t-butylcumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3; peroxyketals such as 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-di-t-butylperoxycyclohexane, and 2,2-di-t-butylperoxybutane; peroxy esters such as 1,1,3,3-tetramethylbutyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, t-amyl peroxy 2-ethylhexanoate, t-butyl peroxy 2-ethylhexanoate, di-t-butyl peroxyhexahydroterephthalate, t-amyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-amyl peroxybenzoate; peroxy carbonates such as di-2-ethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, t-butyl peroxymethyl carbonate, t-butyl peroxy 2-ethylhexyl carbonate, and 1,6-bis(t-butylperoxycarbonyloxy)hexane, etc.

[0051] Examples of the azo compound include azobisisobutyronitrile, 2,2'-azobis(2-methylisobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(isobutyrate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and the like.

[0052] As the thermal polymerization initiator, commercially available products can be used. From the viewpoints of stability and toxicity, organic peroxides are preferred as the thermal polymerization initiator, and peroxy esters are particularly preferred. Further, from the viewpoint of the balance between the stability of the composition and the curing temperature, it is preferable that the temperature at which the half-life is 1 hour, which is an index of the deactivation of the organic peroxide, is 50 to 110°C.

[0053] The component (C) may be one kind or a combination of two or more kinds.

[0054] <Further component> The thermosetting resin composition may contain further components as necessary, as long as the effects of the present invention are not impaired. Examples of the further components include a polymer component (D), a thixotropy-imparting agent containing an inorganic substance, a silane coupling agent, a surfactant, a slip agent, a polymerization inhibitor, an antioxidant, a stabilizer, a colorant, a solvent, a filler, and the like. Each of the further components may be one kind of component or a combination of two or more kinds of components.

[0055] The polymer component (D) is a component that adjusts the viscosity of the thermosetting resin composition (for example, increases the viscosity of the thermosetting resin composition). The component (D) is not particularly limited as long as it is a polymer having no radically polymerizable functional group and having a property of dissolving in the thermosetting resin composition. Examples of such a component (D) include acrylic polymers, (hydrogenated) diene polymers, and water-soluble polymers.

[0056] Examples of the acrylic polymer include poly(meth)acrylic acid, poly(meth)acrylic acid ester, or a copolymer thereof.

[0057] Examples of the (hydrogenated) diene polymer include polyisoprene, hydrogenated polyisoprene, polybutadiene, or hydrogenated polybutadiene. The (hydrogenated) diene polymer may be a homopolymer of a conjugated diene monomer such as 1,3-butadiene or isoprene, or may be a copolymer of a conjugated diene monomer and an aromatic vinyl monomer such as styrene.

[0058] Examples of the water-soluble polymer include polyoxyalkylene such as polyethylene glycol, polypropylene glycol, or a copolymer of polyethylene glycol and polypropylene glycol, polyvinyl alcohol; cellulose derivatives such as hydroxymethylcellulose, hydroxypropylcellulose, or carboxymethylcellulose; polysaccharides such as starch degradation products, hydroxypropyl etherified starch, sodium alginate, gelatin, or xanthan gum; etc.

[0059] When component (D) is other than the water-soluble polymer, the component (D) is preferably a high-viscosity liquid or solid having a viscosity of 100,000 mPa·s or more at 25°C, and particularly preferably a solid. Further, the component (D) other than the water-soluble polymer preferably has a weight-average molecular weight such that it is a high-viscosity liquid or solid having a viscosity of 100,000 mPa·s or more at 25°C. Here, the viscosity is a value measured using an E-type viscometer under atmospheric pressure at 25°C by selecting an appropriate cone plate and rotation speed.

[0060] The weight-average molecular weight of the water-soluble polymer is preferably from 300 to 100,000, more preferably from 500 to 50,000, and particularly preferably from 500 to 20,000. When the weight-average molecular weight of the water-soluble polymer is within the above range, the viscosity of the thermosetting resin composition can be efficiently increased, and the water solubility of the thermosetting resin composition after thermosetting can be enhanced. As a method for measuring the weight-average molecular weight, for components having a relatively high molecular weight such as oligomers and polymers, a method of converting the measurement results of gel permeation chromatography (GPC) using a calibration curve of standard polystyrene is generally known.

[0061] By selecting component (D), selectivity for a solvent capable of dissolving the thermosetting resin composition can be imparted. From the perspective of solubility in acetone, component (D) is preferably an acrylic polymer such as a copolymer of poly(meth)acrylate. Also, from the perspective of solubility in water, component (D) is preferably a water-soluble polymer, and particularly preferably a cellulose derivative. Further, from the perspective of solubility in methylcyclohexane, component (D) is preferably a (hydrogenated) diene-based polymer, and particularly preferably a hydrogenated diene-based polymer.

[0062] The thixotropic agent containing an inorganic substance is not particularly limited as long as it has a high thickening or thixotropic effect with a small amount of addition. Examples of the inorganic substance contained in the thixotropic agent include fumed silica, calcium carbonate, carbon black, kaolin, clay, activated clay, silica sand, silica stone, diatomaceous earth, anhydrous aluminum silicate, hydrated magnesium silicate, talc, perlite, white carbon, mica fine powder, bentonite, etc. Also, the thixotropic agent may consist only of an inorganic substance, or may be an inorganic substance surface-treated with a fatty acid and / or a resin acid.

[0063] Further components other than the above-described components are not particularly limited as long as they are components commonly used in thermosetting resin compositions, and can be appropriately selected according to the purpose.

[0064] (Content of each component) In the thermosetting resin composition, the content of each component is as follows. In component (A), the content of component (A1) is 50% by weight or more. From the perspective of thermosetting, in component (A), the content of component (A1) is preferably 60% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and particularly preferably 90% by weight or more. Also, the content of component (A1) in component (A) may be 100% by weight.

[0065] In the thermosetting resin composition, the content of component (A2) is 0 wt% or more and less than 15 wt%. From the viewpoint of solubility in a specific solvent, in the thermosetting resin composition, the content of component (A2) is preferably 0 wt% or more and 10 wt% or less, and particularly preferably 0 wt% or more and 4 wt% or less.

[0066] The content of component (A) is preferably 55 wt% or more, more preferably 70 wt% or more, and particularly preferably 80 wt% or more in the thermosetting resin composition as the main component of the thermosetting resin composition. In component (A), the component other than component (A1) and component (A2) is component (A1’).

[0067] The content of component (B) is preferably 0.5 to 10 wt%, more preferably 0.8 to 10 wt%, and particularly preferably 1.0 to 7.0 wt% in the thermosetting resin composition from the viewpoints of thermosetting and solubility in a specific solvent after thermosetting.

[0068] The content of component (C) is preferably 0.1 to 10 wt%, more preferably 0.5 to 8.0 wt%, and particularly preferably 1.0 to 7.0 wt% in the thermosetting resin composition from the viewpoints of thermosetting and solubility in a specific solvent after thermosetting.

[0069] The content of component (D) is preferably less than 50 parts by weight, more preferably 0 to 40 parts by weight, and particularly preferably 1 to 20 parts by weight with respect to 100 parts by weight of component (A) from the viewpoints of thermosetting and solubility in a specific solvent after thermosetting.

[0070] The content of further components other than component (D) is preferably 20 wt% or less, particularly preferably 10 wt% or less, and particularly preferably 5.0 wt% or less in the thermosetting resin composition.

[0071] (Further aspect of the thermosetting resin composition) Further aspects of the thermosetting resin composition are as follows. In the following aspects as well, the descriptions of the contents of the above-described respective components can be applied. In the thermosetting resin composition, when the content of monomers having a (meth)acrylamide group or the like increases, the polarity becomes higher and it tends to dissolve in water. In the above case, in component (A), the content of monomer (A1-1) having a (meth)acrylamide group may be 90% by weight or more. Further, the thermosetting resin composition may further contain a water-soluble polymer as component (D), or may not contain a polymer component (D) other than the water-soluble polymer. And in the above case, the thermosetting resin composition is preferably at least a thermosetting resin composition that dissolves in water.

[0072] In the thermosetting resin composition, when the content of a hydroxyl group-containing (meth)acrylate monomer or the like (excluding monomers having a (meth)acrylamide group) increases, the polarity becomes high and it tends to dissolve in ethanol. In the above case, component (A1) is one or more selected from the group consisting of methacrylate monomer (A1-2) and acrylate monomer (A1-3) having a cyclic structure, and in component (A), the content of the hydroxyl group-containing (meth)acrylate monomer may be 20% by weight or more. Also, in the above case, component (A1) is one or more selected from the group consisting of methacrylate monomer (A1-2) and isobornyl methacrylate, the content of the hydroxyl group-containing (meth)acrylate monomer in component (A) is 10% by weight or more, and in the thermosetting resin composition, the content of component (B) may be 3% by weight to 10% by weight. The hydroxyl group-containing (meth)acrylate monomer may be a hydroxyl group-containing methacrylate monomer contained in component (A1-2), and may also be a hydroxyl group-containing acrylate monomer that may be contained in component (A1-3) or component (A1'). And in the above case, the thermosetting resin composition is preferably at least a thermosetting resin composition that dissolves in ethanol.

[0073] In a thermosetting resin composition, when the hydrocarbon structure increases, the polarity decreases and it tends to be easily soluble in methylcyclohexane. In the above case, in component (A), the content of isobornyl acrylate is 90% by weight or more, and component (B) may be a compound having an α-methylstyrene structure or 1,4-bis(3-mercaptobutyryloxy)butane. In the above case, in component (A), the content of component (A1-3) is 80% by weight or more, component (A1') is not included, and component (B) may be pentaerythritol tetrakis(3-mercaptobutyrate). Also, in the above case, in component (A), the content of dicyclopentanyl acrylate is 90% by weight or more, and component (B) may be pentaerythritol tetrakis(3-mercaptobutyrate). And, in the above case, the thermosetting resin composition is preferably a thermosetting resin composition that is soluble in at least methylcyclohexane.

[0074] When the thermosetting composition does not contain one or more selected from N-hydroxyalkyl (meth)acrylamide, (hydrogenated) diene-based polymer, and water-soluble polymer, it tends to be easily soluble in acetone. In the above case, component (A1) is one or more selected from the group consisting of monomer (A1-1) having a (meth)acrylamide group other than N-hydroxyalkyl (meth)acrylamide, methacrylate monomer (A1-2), and acrylate monomer (A1-3) having a cyclic structure. The thermosetting resin composition may further contain an acrylic polymer as component (D), but may not contain a polymer component (D) other than the acrylic polymer. And, in the above case, the thermosetting resin composition is preferably a thermosetting resin composition that is soluble in at least acetone.

[0075] (Method for producing a thermosetting resin composition) The thermosetting resin composition is obtained by a production method including a step of mixing component (A), component (B), component (C), and a further component (component (D), etc.) which is an optional component.

[0076] (Method for curing a thermosetting resin composition) The thermosetting resin composition can be cured by heating. The heating temperature and heating time are not particularly limited as long as they are the temperature and time at which the thermosetting resin composition thermosets. The heating temperature is preferably 70 to 120 °C, and particularly preferably 80 to 110 °C. The heating time is preferably 10 minutes to 2 hours, and particularly preferably 20 minutes to 100 minutes.

[0077] [Applications] The thermosetting resin composition can be used as a thermosetting resin composition for temporary fixing (temporary fixing material), a thermosetting resin composition for masking (masking material), or a thermosetting resin composition for molding (molding material). Here, the thermosetting resin composition is dissolved in at least one of water, ethanol, acetone, and methylcyclohexane in the above applications. Therefore, the thermosetting resin composition is used to be dissolved in at least one of water, ethanol, acetone, and methylcyclohexane in the above applications. The thermosetting resin composition is applicable to temporary fixing in the processing of crystal oscillators, glass lenses, plastic lenses, and optical discs. In addition, the thermosetting resin composition is applicable to masking of printed wiring boards, electronic components, automotive parts, etc. In addition, the thermosetting resin composition is applicable to molding materials such as pedestals for 3D printer printing.

[0078] (Temporary fixing material) Temporary fixing means temporarily adhering one member to another member via a cured product of the thermosetting resin composition. The cured product of the thermosetting resin composition is later removed by dissolving in at least one of water, ethanol, acetone, and methylcyclohexane, thereby losing the adhesiveness due to the cured product of the thermosetting resin composition between one member and the other member and achieving the purpose of temporary fixing.

[0079] [Temporary fixing method] A method for temporarily fixing a member using a thermosetting resin composition for temporary fixing includes a step of bonding a base material using the thermosetting resin composition for temporary fixing, or a step of overlapping two members and applying the thermosetting resin composition to the outer peripheral portion thereof; a step of curing the thermosetting resin composition for temporary fixing to bond and temporarily fix the base material; a step of processing the temporarily fixed base material; and a step of bringing the processed base material into contact with a cleaning agent to remove the cured thermosetting resin composition for temporary fixing. Here, the cleaning agent is at least one of water, ethanol, acetone, and methylcyclohexane.

[0080] In addition, as a method for manufacturing a processed body using a thermosetting resin composition for temporary fixing, a method including the following step (A) or (B) and (C) to (E) can be mentioned. (A) (a1) A step of applying a thermosetting resin composition to one base material to form a thermosetting resin composition layer; (a2) A step of bonding the other base material on the thermosetting resin composition layer to obtain a laminate, or (B) A step of overlapping the other base material on one base material and then applying the thermosetting resin composition to the outer peripheral edge portion or the overlapping portion thereof to obtain a laminate; (C) A step of heating the laminate obtained in step (A) or step (B) to obtain an adhesive body; (D) A step of processing the adhesive body to obtain a roughly processed body; (E) A method including removing the cured product of the thermosetting resin composition from the roughly processed body to obtain a processed body.

[0081] Step (A) includes steps (a1) and (b1). Step (a1) is a step of applying a thermosetting resin composition to one base material to form a thermosetting resin composition layer. The material of the base material is not particularly limited, but a base material made of a material that does not undergo thermal deformation and is difficult to permeate oxygen is preferred.

[0082] The method of applying the thermosetting resin composition to the substrate is not particularly limited, and examples include an inkjet printing method (inkjet printing method using an inkjet 3D printer), a brush coating method, a screen printing method, a gravure printing method, a spray method, a dip method, a bar coater, a roll coater, a spin coater, a die coater, a dispenser, and other known coating means. The thickness of the curable resin composition layer formed by applying the thermosetting resin composition is not particularly limited, but is preferably 10 to 500 μm, and particularly preferably 30 to 350 μm.

[0083] Step (a2) is a step of obtaining a laminate by laminating the other substrate on the thermosetting resin composition layer. The other substrate is placed on the substrate on which the thermosetting resin composition layer is formed so as to be in contact with the cured resin layer, and the substrates are laminated together to obtain a laminate. In step (a2), a step of pressurizing the laminate may be included.

[0084] Step (B) is a step of obtaining a laminate by applying a thermosetting resin composition to the outer peripheral edge or the overlapping portion after overlapping the other substrate on one substrate. In step (B), the other substrate is placed on one substrate, and the thermosetting resin composition is applied under conditions such that the one substrate and the other substrate are fixed by the thermosetting resin composition at the outer peripheral edge or the overlapping portion of the outer peripheral portion. The method of applying the thermosetting resin composition includes the method described in step (a1).

[0085] Step (C) is a step of obtaining an adhesive by heating the laminate obtained in step (A) or step (B). By heating the laminate, the thermosetting resin composition between the one substrate and the other substrate is cured, and the substrates are adhered to each other.

[0086] The heating temperature and the heating time are not particularly limited as long as the thermosetting resin composition is thermally cured and the substrates are adhered to each other. The heating temperature and the heating time include the conditions described in the curing method of the thermosetting resin composition.

[0087] Step (D) is a step of processing the adherend to obtain a roughly processed body. Examples of the processing include cutting, grinding, polishing, drilling the temporarily fixed adherend into a desired shape, painting, etc., which are appropriately set according to the obtained processed body.

[0088] Step (E) is a method of removing the cured product of the thermosetting resin composition from the roughly processed body to obtain a processed body. Examples of the method of removing the cured product of the thermosetting resin composition include a method of bringing the roughly processed body into contact with a cleaning agent. For example, a method of spray-applying the cleaning agent to the cured product of the thermosetting resin composition, a method of immersing the roughly processed body in the cleaning agent, etc. are included. By the method of bringing the roughly processed body into contact with the cleaning agent, the cured product of the thermosetting resin composition is removed from the base material by peeling or dissolving.

[0089] The cleaning agent can be appropriately selected from at least one of water, ethanol, acetone, and methylcyclohexane according to the type of the thermosetting resin composition.

[0090] The cleaning agent may further contain, as additional components, components usually added to organic solvent-based cleaning agents such as surfactants. Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. The surfactant may be one kind or a combination of two or more kinds.

[0091] The temperature of the cleaning agent in step (E) is not particularly limited, and it is preferably 25 to 70°C. Also, the contact time between the roughly processed body and the cleaning agent in step (E) is not particularly limited as long as the cured product of the thermosetting resin composition can be removed from the roughly processed body, and can be appropriately set by those skilled in the art. From the viewpoint of accelerating the dissolution of the cured product of the thermosetting resin composition in the cleaning agent, it is preferable to vibrate the cleaning agent by ultrasonic waves or the like. The purpose of temporary fixing is achieved by step (E).

[0092] Examples of the processed body obtained by the method for manufacturing a processed body using a thermosetting resin composition for temporary fixing include a crystal oscillator, a glass lens, a plastic lens, and an optical disk.

[0093] (Masking material) Masking means protecting a substrate or the like temporarily with a cured product of a thermosetting resin composition to prevent damage, adhesion of dirt, alteration, etc. of the substrate, or preventing film formation on wiring in a film formation process. The cured product of the thermosetting resin composition is later removed to achieve the purpose of masking by the cured product of the thermosetting resin composition. The thermosetting resin composition can be used to temporarily mask a substrate or the like to be masked (for example, a printed wiring board, an electronic component).

[0094] (Masking method) As a method for masking a substrate, for example, a method of temporarily covering part or all of the surface of the substrate with a cured product of a thermosetting resin composition can be mentioned. By the masking method of the substrate, when the substrate is handled or a plurality of substrates are stacked, etc., the cured film intervening between the substrates prevents the substrates from coming into direct contact, and can suppress the occurrence of damage such as scratches on the substrate and the adhesion of foreign substances. Also, when painting automobile parts or the like, by temporarily covering the area not to be painted with a cured film of a masking material, the scattering of paint to the area not to be painted can be suppressed.

[0095] Also, as a method for manufacturing a processed body using a thermosetting resin composition for masking, a method including the following steps (F) to (I) can be mentioned. (F) A step of applying a thermosetting resin composition to a substrate to form a thermosetting resin composition layer. (G) A step of heating the thermosetting resin composition layer to obtain a substrate masked with a cured product of the thermosetting resin composition. (H) A step of processing the substrate masked with the cured product of the thermosetting resin composition to obtain a roughly processed body, and (I) A step of removing the cured product of the thermosetting resin composition from the roughly processed body to obtain a processed body.

[0096] As methods for applying a thermosetting resin composition to a substrate, curing the thermosetting resin composition, processing the substrate, and removing the cured product of the thermosetting resin composition, the methods described above are included in the method for manufacturing a processed body using a thermosetting resin composition for temporary fixing.

[0097] Examples of the processed body obtained by the method for manufacturing a processed body using a thermosetting resin composition for masking include printed wiring boards, electronic components such as displays, and automotive parts.

[0098] (Molding material) The thermosetting resin composition can be used as a molding material (support material) such as a pedestal for 3D printer printing. As a method for manufacturing a molded product using the 3D printer printing method, a method of curing 3D printer ink ejected from an inkjet nozzle of a 3D printer and stacking and stereolithographing it can be mentioned. Here, the 3D printer ink includes a model material that constitutes the molded body by photocuring such as UV, and a support material that is used as a support material when stacking the model materials three-dimensionally. By stacking the model material on the molding material, it becomes possible to manufacture a molded product having a structure such as an overhang structure or a hollow structure.

[0099] Examples of the method for manufacturing a molded product using a thermosetting resin composition for molding include a method including the following steps (J) to (L). Here, steps (J) and (K) can be performed in any order or simultaneously according to the shape of the molded product. (J) A step of forming a molding material, (K) A step of forming a model material, (L) A step of removing the molding material to obtain a molded product.

[0100] In the step of forming the molding material, after injecting and printing a thermosetting resin composition for molding from the nozzle of a 3D printer (inkjet 3D printer) and performing stereolithography, the molding material is formed by thermosetting. As the method for curing the thermosetting resin composition, the methods described above are included in the method for manufacturing a processed body using a thermosetting resin composition for temporary fixing.

[0101] In the step of forming the model material, after shaping the model material composition using a 3D printer, it is thermally cured to form the model material that constitutes the molded article. The model material composition can be appropriately set from known components, provided that it is a composition that does not dissolve in the solvent that dissolves the molding material. The curing method of the model material can be appropriately set from known photocuring conditions.

[0102] In the step of removing the molding material, the method for removing the cured product of the thermosetting resin composition described above in the method for manufacturing a processed body using a thermosetting resin composition for temporary fixing can be mentioned. Here, the type of cleaning agent used in the step of removing the molding material is at least one of water, ethanol, acetone, and methylcyclohexane, and can be appropriately selected according to the type of the thermosetting resin composition for molding.

Examples

[0103] The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited by these examples. The values in the table are parts by weight unless otherwise specified.

[0104] (Components used) <Component (A): Radical polymerization reactive component> · Component (A1-1): Monomer having a (meth)acrylamide group HEAA: Hydroxyethyl acrylamide (manufactured by KJ Chemical) ACMO: 4-Acryloylmorpholine (manufactured by KJ Chemical) · Component (A1-2): Methacrylate monomer THF-M: Tetrahydrofurfuryl methacrylate (manufactured by Showa Denko Materials) HOB: 2-Hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical) · Component (A1-3): Acrylate monomer having a cyclic structure IBOA: Isobornyl acrylate (manufactured by Nippon Shokubai) FA-513AS: Dicyclopentanyl acrylate (manufactured by Showa Denko Materials) ·Component (A'): A monofunctional radically polymerizable component other than component (A1) 4HBA: 4-Hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry) L-A: Lauryl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.) ·Component (A2): A radically polymerizable component having two or more functional groups UN-7700: A bifunctional urethane acrylate (manufactured by Negami Kogyo Co., Ltd.) <Component (B): Chain transfer agent> Karenz MT PE1: Pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko K.K.) Karenz MT BD1: 1,4-Bis(3-mercaptobutyryloxy)butane (manufactured by Showa Denko K.K.) MSD-100: α-Methylstyrene dimer (manufactured by Mitsui Chemicals, Inc.) <Component (C): Thermal polymerization initiator> Peroct O: 1,1,3,3-Tetramethylbutyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation) <Component (D): Polymer component> LA1892: Acrylic polymer (manufactured by Kuraray Co., Ltd.) (solid at 25°C) SEP2002 (hydrogenated diene polymer): Styrene hydrogenated isoprene copolymer (manufactured by Kuraray Co., Ltd.) (solid at 25°C) HPC SSL (water-soluble polymer): Hydroxypropyl cellulose (manufactured by Nippon Soda Co., Ltd.)

[0105] 〔Evaluation conditions〕 (1) Thermosetting The thermosetting resin composition was poured into a mold to form a shape of 10 mm × 5 mm × 1 mm, laminated with a PET (polyethylene terephthalate) film (manufactured by Panac Co., Ltd., product name Lumirror 100T60, thickness 100 μm), further sandwiched between slide glasses, and then heated in an oven (LC-114 manufactured by Espec) at 100°C for 30 minutes to cure the thermosetting resin composition. After peeling off the PET film, it was confirmed whether the thermosetting resin composition was cured by finger touch. ○: Cured (no liquid (thermosetting resin composition) adheres to the hand) ×: Not cured (liquid on the hand)

[0106] (2) Solvent solubility In the above “(1) Curing property”, the test piece with thermosetting property being “○” was placed in a 1 L beaker, and about 100 g of water was poured. The beaker was placed in an ultrasonic cleaner (manufactured by NDK, US-20PS), and the weakest level of ultrasonic wave was applied for 5 minutes. Then, the test piece was taken out, and it was visually confirmed whether the cured product of the thermosetting resin composition remained. The water was changed to ethanol, acetone, and methylcyclohexane respectively, and the same test was conducted. Also, the numbers of the dissolved tests were described in the table. For example, when the thermosetting resin composition dissolved in the tests of ethanol and acetone, and did not dissolve in the tests of water and methylcyclohexane, it was designated as “〇2,3”. ○1: The thermosetting resin composition dissolved in the test with water 〇2: The thermosetting resin composition dissolved in the test with ethanol 〇3: The thermosetting resin composition dissolved in the test with acetone 〇4: The thermosetting resin composition dissolved in the test with methylcyclohexane ×: The thermosetting resin composition did not dissolve in any solvent

[0107] (4) Adhesion A spacer was placed on a slide glass substrate so that the thickness became 50 μm, and about 0.05 g of the thermosetting resin composition was applied, and a PET film was pasted from above. After heating at 100 °C for 30 minutes in an oven (LC-114 manufactured by espec) to cure the thermosetting resin composition, the PET film was peeled off and left for 24 hours, and then visually observed to confirm whether it was peeled off from the slide glass substrate. ○: No peeling ×: Peeling occurred

[0108] [Manufacture of thermosetting resin composition] According to the mixing ratios shown in the table, components (A) to (C) and other components were stirred and mixed in a flask equipped with a stirrer for 30 minutes to 1 hour until uniform. Among them, for Examples 16 to 18, components (A) and (D) were stirred while heating at 80 °C to dissolve the solid components, and then at room temperature (25 °C), components (B) and (C) were added to obtain the liquid thermosetting resin compositions of the examples and comparative examples.

[0109] The results are shown in the following table. All values of the blending amounts of the respective components are in parts by weight.

[0110]

Table 1

[0111]

Table 2

[0112]

Table 3

[0113] From each table, the thermosetting resin compositions of the examples were excellent in thermosetting properties and adhesion. Further, the thermosetting resin compositions of the examples had solubility in at least one of water, ethanol, acetone, and methylcyclohexane after thermosetting. Therefore, the thermosetting resin composition can be used as a thermosetting resin composition for temporary fixing, masking, or molding.

[0114] From the results of Examples 1 to 3, when the content of component (B) increased, it had solubility not only in acetone but also in ethanol. From the results of Examples 8 to 10, when the content of the acrylate monomer having a cyclic structure in component (A) increased, the types of solvents having solubility increased. From the results of Examples 11 and 12 and Comparative Example 3, when the total content of component (A2) in component (A) was less than 15% by weight, it had solubility in a specific solvent. According to the results of Example 17 and Example 18, when component (D) was a hydrogenated diene polymer, it dissolved in methylcyclohexane, and when component (D) was a water-soluble polymer, it dissolved in water. From the results of Examples 1 to 16 and Examples 17 to 19, when the thermosetting resin composition did not contain any of (hydrogenated) diene polymer, water-soluble polymer, and N-hydroxyalkyl (meth)acrylamide, it dissolved in acetone.

[0115] On the other hand, the composition of Comparative Example 1 did not contain component (B). And the composition of Comparative Example 3 had a total content of component (A2) in component (A) of about 19% by weight. Therefore, the cured products of the thermosetting resin compositions of Comparative Examples 1 and 3 were inferior in solubility in water, ethanol, acetone, and methylcyclohexane. Also, the composition of Comparative Example 2 did not contain component (A1). And the composition of Comparative Example 4 had a total content of component (A1) in component (A) of 40% by weight. Therefore, the curable resin compositions of Comparative Examples 2 and 4 were inferior in thermosetting properties.

Claims

1. A thermosetting resin composition containing a radical polymerization reactive component (A), a chain transfer agent (B), and a thermal polymerization initiator (C), wherein component (A) contains at least one monofunctional radical polymerization reactive component (A1) selected from the group consisting of a monomer (A1-1) having a (meth)acrylamide group, a methacrylate monomer (A1-2), and an acrylate monomer (A1-3) having a cyclic structure, in component (A), the content of component (A1) is 50% by weight or more, in the thermosetting resin composition, the content of a difunctional or higher radical polymerization reactive component (A2) is 0% by weight or more and less than 15% by weight, where component (A1-1) has one (meth)acrylamide group in the molecule as a radical polymerization reactive functional group, component (A1-2) has one methacryloyl group in the molecule as a radical polymerization reactive functional group, and component (A1-2) does not have a methacrylamide group, and component (A1-3) has one acryloyl group in the molecule as a radical polymerization reactive functional group, and component (A1-3) does not have an acrylamide group, and is a thermosetting resin composition for temporary fixing, masking, or molding.

2. The thermosetting resin composition according to claim 1, wherein component (B) is at least one selected from the group consisting of a compound having an α-methylstyrene structure and a compound having a thiol group.

3. The thermosetting resin composition according to claim 1, wherein in the thermosetting resin composition, the content of component (B) is 0.5 to 10% by weight.

4. The thermosetting resin composition according to claim 2, wherein in the thermosetting resin composition, the content of component (B) is 0.5 to 10% by weight.

5. The thermosetting resin composition according to any one of claims 1 to 4, further comprising a polymer component (D).

6. The thermosetting resin composition according to claim 5, wherein component (D) is a water-soluble polymer.

7. The thermosetting resin composition according to claim 5, wherein component (D) is a hydrogenated diene-based polymer.

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