Degradable compound and curable resin composition having disassemblability

Abstract

To provide a compound that can be easily degraded by light or heat, and a curable resin composition containing the compound, the cured product thereof exhibiting superior disassemblability through substantial reduction of adhesion strength by light or acid.SOLUTION: A curable resin composition comprising the following components (A)-(C): (A) component: a compound having a structure of general formula (1) (R1 is hydrogen or an alkyl group, and R2 is a divalent organic group), (B) component: a radical initiator, (C) component: an acid generator.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound that is decomposable by light or heat, and to a dismantlable curable resin composition that contains the compound. [Background technology]

[0002] In recent years, the use of dismantling adhesives that can be dismantled after bonding has increased, with a view to reusing components. Dismantling adhesives are adhesives that can dismantle joined objects by severing chemical bonds in the cured product using various external stimuli, such as heat, light, acid, base, and oxidative stimuli. However, these dismantling stimuli have been problematic in terms of the damage they can cause to joined components and the time it takes to dismantle them. Among the dismantling stimuli, light is a relatively small source of damage to joined components. A conventional technique for dismantling adhesives that uses "light" as a dismantling stimulus utilizes an acetal group and a photoacid generator. This technique involves synthesizing a solid copolymer with an acetal structure and using it as a hot-melt adhesive for bonding. (Patent Document 1) [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-211254 Summary of the Invention [Problem to be solved by the invention]

[0004] However, hot melt adhesives generally have lower adhesive strength than other adhesives that require a curing reaction, and have the problem that they are not suitable for use in applications other than temporary fixing. [Means for solving the problem]

[0005] As a result of investigations aimed at achieving the above object, the inventors discovered a method for producing a curable resin composition that exhibits higher adhesive strength and whose cured product is easily decomposed by light or heat, thereby completing the present invention.

[0006] The gist of the present invention will now be described. [1] A curable resin composition comprising the following (A) to (C): Component (A): a compound having a structure of general formula (1) JPEG2025129584000001.jpg32127(R 1 is hydrogen or alkyl group, R 2 is a divalent organic group) Component (B): Radical initiator Component (C): Acid generator

[0007] [2] R in the general formula (1) 1 [1] or [2], wherein R is hydrogen.

[0008] [3] R in the general formula (1) 2 The curable resin composition according to [1] or [2], wherein the aromatic ring is contained.

[0009] [4] The curable resin composition according to [1] or [2], wherein the component (B) is a photoradical initiator.

[0010] [5] The curable resin composition according to [1] or [2], wherein the component (C) is a photoacid generator.

[0011] [6] A cured product obtained by curing the curable resin composition according to [1] or [2] with heat or active energy rays.

[0012] [7] A decomposition method for decomposing the cured product according to [6] above by heat or ultraviolet light.

[0013] [8] The curable resin composition according to [5], wherein the component (B) and the component (C) are activated at different wavelengths.

[0014] [9] An adhesive comprising the curable resin composition according to [1] or [2].

[0015]

[10] A sealant comprising the curable resin composition according to [1] or [2].

[0016]

[11] A coating agent comprising the curable resin composition according to [1] or [2]. [Effects of the Invention]

[0017] The present invention provides a curable resin composition that has high adhesive strength and can be reduced by light or heat, and therefore has excellent dismantling properties. [Brief explanation of the drawings]

[0018] [Figure 1] 1 shows the 1H-NMR chart of Compound 1 synthesized in the example. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention will be described in detail below. However, the present invention is not limited to the following embodiments. In this specification, "X to Y" means a range including the numerical values ​​(X and Y) before and after it as the lower and upper limits, respectively, and means "X or more and Y or less." In the present invention, a compound having a (meth)acryloyl group refers to a (meth)acrylate. The (meth)acryloyl group may have a (meth)acryloyl group in the form of a (meth)acryloyloxy group. Furthermore, the term "(meth)acryloyl" encompasses both acryloyl and methacryloyl. Thus, for example, the term "(meth)acryloyl group" encompasses both an acryloyl group (HC=CH-C(=O)-) and a methacryloyl group (HC=C(CH)-C(=O)-). Similarly, the term "(meth)acrylate" includes both acrylate and methacrylate, the term "(meth)acrylic" includes both acrylic and methacrylic, and the term "(meth)acrylamide" includes both acrylamide and methacrylamide.

[0020] The component (A) of the present invention is a compound represented by the following general formula (1). [ka] (R 1 is hydrogen or alkyl group, R 2 is a divalent organic group)

[0021] R of the component (A) 1 is hydrogen or an alkyl group. The alkyl group is not particularly limited, but examples include methyl, ethyl, and propyl groups. From the viewpoint of curability and decomposition properties, R in component (A) 1 Preferably, consists of hydrogen.

[0022] R of the component (A) 2 is a divalent organic group. There is no particular limitation as long as it is a divalent organic group, but from the viewpoint of high adhesiveness, R 2 It is preferable that the aromatic ring is contained in the alkyl group.

[0023] R of the component (A) 3 is a divalent or higher organic group. There are no particular limitations on the organic group as long as it is a divalent or higher organic group, but from the viewpoint of decomposability, it is preferably a divalent to hexavalent organic group, more preferably a divalent to tetravalent organic group, and most preferably a divalent to trivalent organic group.

[0024] The compound of general formula (1) can be obtained by acetalizing a compound having one (meth)acryloyl group and one hydroxyl group per molecule with 2-methoxypropene under acidic conditions.

[0025] The compound having one (meth)acryloyl group and one hydroxyl group per molecule used in the synthesis of the component (A) includes a hydroxyl group-containing monofunctional (meth)acrylate having only one (meth)acryloyl group per molecule.

[0026] The hydroxyl group-containing monofunctional (meth)acrylate is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, (meth)acryloxyoxyethyl acid phosphate, 2-hydroxyethyl (meth)acrylic acid phosphate, etc. Among these, from the viewpoint of high adhesiveness of a composition containing the synthesized compound, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl acrylate are preferred, 4-hydroxybutyl (meth)acrylate and 2-hydroxy-3-phenoxypropyl acrylate are more preferred, and 2-hydroxy-3-phenoxypropyl acrylate is most preferred.

[0027] The optimal functional group equivalent ratio for obtaining the component (A) is the functional group equivalent ratio (equivalent ratio of (meth)acryloyl groups to methoxy groups) between a compound having one or more (meth)acryloyl groups and one or more hydroxyl groups per molecule and 2-methoxypropene, which is preferably 1.0 to 3.0, more preferably 1.2 to 2.8, and most preferably 1.5 to 2.5. A functional group equivalent ratio of 1.0 to 3.0 can improve the yield of the component (A).

[0028] The reaction to obtain component (A) can be carried out by stirring in the presence of a solvent. Examples of solvents include, but are not limited to, formamide, sulfolane, N,N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, N-methyl-2-pyrrolidone, tetrahydrofuran, and dimethylacetamide. The yield can be increased by using a catalyst during the synthesis of component (A) of the present invention. An example of the catalyst is pyridinium p-toluenesulfonate.

[0029] The reaction temperature for obtaining the component (A) is not particularly limited as long as it is not a temperature at which the solvent evaporates, but the compound of the present invention can be reacted at room temperature or a low temperature of 20 to 50°C.

[0030] The reaction time for obtaining the component (A) is not particularly limited as long as it is 30 minutes or more, but is preferably 30 minutes to 24 hours.

[0031] The curable resin composition of the present invention has excellent curability due to the inclusion of components (A) to (C), and the cured product can be easily decomposed by light or heat. However, the curable resin composition of the present invention may also include a compound other than component (A) that has one or more (meth)acryloyl groups in one molecule as component (A'). From the viewpoint of the dismantling property of the curable resin composition, the amount of component (A') is preferably 50% by mass or less, more preferably 30% by mass or less, and most preferably 20% by mass or less, based on 100% by mass of the total of components (A) and (A'). Examples of component (A') include oligomers and monomers that have one or more (meth)acryloyl groups in one molecule. The term "oligomer" as used herein refers to a polymer in which two to several tens of monomer units (including monomer units other than (meth)acrylate monomers) are repeated. Examples of oligomers having one or more (meth)acryloyl groups in one molecule in the present invention include urethane-modified (meth)acrylates and epoxy-modified (meth)acrylates. From the viewpoint of adhesive strength, it is preferable to contain a compound having two or more (meth)acrylolyl groups, and it is more preferable to contain a urethane-modified (meth)acrylate and / or an epoxy-modified (meth)acrylate having two or more (meth)acryloyl groups.

[0032] The urethane-modified (meth)acrylate is a compound having a urethane bond in the main chain and a (meth)acryloyl group, which is formed by reacting an isocyanate group with a hydroxyl group. From the viewpoint of curability, the (meth)acryloyl group is preferably located at the end of the molecular chain. Examples of methods for producing the urethane-modified (meth)acrylate include a method of reacting a polyol compound having a hydroxyl group with a (meth)acrylate having an isocyanate group, and a method of reacting a polyol compound having a hydroxyl group, a polyisocyanate compound, and a (meth)acrylate having a hydroxyl group.

[0033] The polyol compound having a hydroxyl group is not particularly limited, but examples thereof include polyester polyols, polycarbonate polyols, and polyether polyols.

[0034] Examples of the (meth)acrylate having an isocyanate group include, but are not limited to, 2-methacryloyloxyethyl isocyanate, 2-isocyanatoethyl methacrylate, and 2-isocyanatoethyl acrylate.

[0035] Examples of the polyisocyanate compound include aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and triphenylmethane triisocyanate; isophorone diisocyanate, bis(4-isocyanate), and the like. alicyclic polyisocyanates such as 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, norbornane diisocyanate, and bicycloheptane triisocyanate; and linear or branched aliphatic polyisocyanates such as hexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and 1,6,11-undeca triisocyanate.

[0036] The (meth)acrylate having a hydroxyl group is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, (poly)ethylene glycol mono(meth)acrylate, (poly)propylene glycol mono(meth)acrylate, pentaerythritol tri(meth)acrylate, etc. These may be used alone or in combination of two or more.

[0037] The epoxy-modified (meth)acrylate is a compound that can be synthesized by ring-opening polymerization of acrylic acid or the like with the glycidyl group of a glycidyl ether compound, but is not limited to this method. The main chain of the glycidyl ether can be one of various skeletons, such as bisphenol A, bisphenol F, phenol novolac, hydrogenated bisphenol A, and hydrogenated bisphenol F. These may be used alone or in combination of two or more. Specific examples of epoxy-modified (meth)acrylates include bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, fatty acid-modified epoxy acrylate, amine-modified bisphenol epoxy acrylate, novolac epoxy acrylate, and epoxidized soybean oil acrylate.

[0038] Examples of the monomer of component (A') include a monofunctional (meth)acrylate monomer having one (meth)acryloyl group in one molecule and a polyfunctional (meth)acrylate monomer having two or more (meth)acryloyl groups in one molecule.

[0039] Examples of the monofunctional (meth)acrylate monomer include methoxydiethylene glycol mono(meth)acrylate, methoxytriethylene glycol mono(meth)acrylate, methoxytetraethylene glycol mono(meth)acrylate, methoxypentaethylene glycol mono(meth)acrylate, methoxyhexaethylene glycol mono(meth)acrylate, methoxyheptaethylene glycol mono(meth)acrylate, methoxyhexaethylene glycol mono(meth)acrylate, methoxyoctaethylene glycol mono(meth)acrylate, methoxynonaethylene glycol mono(meth)acrylate, methoxydecaethylene glycol mono(meth)acrylate, methoxytripropylene glycol mono(meth)acrylate, methoxytetrapropylene glycol mono(meth)acrylate, methoxypentapropylene glycol mono(meth)acrylate, methoxyhexapropylene glycol mono(meth)acrylate, methoxyheptapropylene glycol mono(meth)acrylate, methoxyhectapropylene glycol mono(meth)acrylate, Methoxyoctapropylene glycol mono(meth)acrylate, methoxynonapropylene glycol mono(meth)acrylate, methoxydecapropylene glycol mono(meth)acrylate, methoxytributylene glycol mono(meth)acrylate, methoxytetrabutylene glycol mono(meth)acrylate, methoxypentabtylene glycol mono(meth)acrylate, methoxyhexabtylene glycol mono(meth)acrylate, methoxyheptabtylene glycol mono(meth)acrylate, methoxyhectabtylene glycol Lithium mono(meth)acrylate, methoxyoctabutylene glycol mono(meth)acrylate, methoxynonabutylene glycol mono(meth)acrylate, methoxydecabutylene glycol mono(meth)acrylate, ethoxydiethylene glycol mono(meth)acrylate, ethoxytriethylene glycol mono(meth)acrylate, ethoxytetraethylene glycol mono(meth)acrylate, ethoxypentaethylene glycol mono(meth)acrylate, ethoxyhexaethylene glycol mono(meth)acrylate,Ethoxyheptaethylene glycol mono(meth)acrylate, ethoxyhexaethylene glycol mono(meth)acrylate, ethoxyoctaethylene glycol mono(meth)acrylate, ethoxynonaethylene glycol mono(meth)acrylate, ethoxydecaethylene glycol mono(meth)acrylate, ethoxytripropylene glycol mono(meth)acrylate, ethoxytetrapropylene glycol mono(meth)acrylate, ethoxypentapropylene glycol mono(meth)acrylate, ethoxyhexapropylene glycol mono(meth)acrylate, ethoxyheptapropylene glycol mono(meth)acrylate, ethoxyhexapropylene glycol mono(meth)acrylate, ethoxyoctapropylene glycol Examples of such acrylates include ethoxynonapropylene glycol mono(meth)acrylate, ethoxydecapropylene glycol mono(meth)acrylate, ethoxytributylene glycol mono(meth)acrylate, ethoxytetrabutylene glycol mono(meth)acrylate, ethoxypentabtylene glycol mono(meth)acrylate, ethoxyhexabtylene glycol mono(meth)acrylate, ethoxyheptabtylene glycol mono(meth)acrylate, ethoxyhexabtylene glycol mono(meth)acrylate, ethoxyoctabtylene glycol mono(meth)acrylate, ethoxynonabtylene glycol mono(meth)acrylate, and ethoxydecabutylene glycol mono(meth)acrylate. These acrylates can be used alone or in combination of two or more.

[0040] Examples of the polyfunctional (meth)acrylate monomer include bifunctional (meth)acrylates such as ethoxylated bisphenol A di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tricyclodecanol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 2-hydroxy-3-methacrylpropyl acrylate. trifunctional (meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate and trimethylolpropane trimethacrylate; tetrafunctional (meth)acrylate monomers such as ditrimethylolpropane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate; pentafunctional (meth)acrylate monomers such as dipentaerythritol monohydroxypenta(meth)acrylate and alkyl-modified dipentaerythritol penta(meth)acrylate; and hexafunctional (meth)acrylate monomers such as dipentaerythritol hexa(meth)acrylate.

[0041] The component (B) used in the present invention is a radical initiator. The component (B) is a component that cures the component (A). Examples of the component (B) include (B-1) a photoradical initiator and (B-2) a thermal radical initiator. The curable composition of the present invention can be photocured by selecting the component (B-1), and can be thermally cured by selecting the component (B-2). Note that the components (B-1) and (B-2) can be used in combination as needed.

[0042] The component (B-1) is a compound that generates radical species by decomposing a photoradical initiator when irradiated with active energy rays such as ultraviolet light or visible light. The component (B-1) is not particularly limited, but examples thereof include acetophenone-based photoinitiators, benzoin-based photoinitiators, benzophenone-based photoinitiators, thioxanthone-based photoinitiators, and acylphosphine oxide-based photoinitiators. Among these, acylphosphine oxide-based photoinitiators are preferred from the viewpoint of curability. These may be used alone or in combination of two or more.

[0043] The acetophenone-based photoinitiator is not particularly limited, but examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer.

[0044] The benzoin-based photoinitiator is not particularly limited, but examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0045] The benzophenone-based photoinitiator is not particularly limited, but examples thereof include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, and (4-benzoylbenzyl)trimethylammonium chloride.

[0046] The thioxanthone-based photoinitiator is not particularly limited, but examples thereof include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride.

[0047] The acylphosphine oxide photoinitiator is not particularly limited, but examples thereof include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide. From the viewpoint of curability, acylphosphine oxide photoinitiators are preferred, with bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide being more preferred, and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide being most preferred. These may be used alone or in combination of two or more.

[0048] The component (B-2) is a compound that decomposes upon application of heat to generate radical species. The component (B-2) is not particularly limited, but examples thereof include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; peroxyketals such as 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, and 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane; and p-menthane hydroperoxide. Hydroperoxides such as; dialkyl peroxides such as α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide; diacyl peroxides such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide, and benzoyl peroxide; peroxycarbonates such as bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and di-3-methoxybutyl peroxycarbonate;t-Butyl peroxypivalate, t-hexyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, t-butyl-2-ethylperoxyhexanoate, t-butyl peroxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butylperoxyisopropyl monocarbonate Examples of suitable peroxides include peroxyesters such as tert-butyl peroxybenzoate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, and t-butyl peroxyacetate, as well as azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile). However, from the viewpoint of the curability of the composition containing component (A), organic peroxides are preferred. These may be used alone or in combination of two or more types.

[0049] The amount of the (B) component blended is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and most preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total (meth)acrylate compound including the (A) component. When the amount is 0.05 parts by mass or more, excellent curability is obtained, and when the amount is 20 parts by mass or less, there is no risk of a decrease in storage stability.

[0050] The component (C) used in the present invention is an acid generator. The component (C) generates an acid when exposed to light or heat and can decompose the acetal group of the component (A), thereby decomposing the cured product of the curable resin composition containing the component (A). Examples of the component (C) include a photoacid generator (C-1) and a thermal acid generator (C-2). From the viewpoint of the decomposability of the component (A), it is preferable to use a photoacid generator (C-1).

[0051] The component (C-1) is a compound that generates an acid upon irradiation with active energy rays. The component (C-1) is not particularly limited, but examples thereof include aromatic iodonium-based photoacid generators and aromatic sulfonium-based photoacid generators. From the viewpoints of the decomposition of the component (A) and the dismantling of the cured product of the curable resin composition containing the component (A), it is preferable to include an aromatic sulfonium-based photoacid generator. These may be used alone or in combination of two or more.

[0052] Examples of the aromatic sulfonium photoacid generator include a photoacid generator containing a sulfonium ion in which all three groups bonded to the sulfur atom are aryl groups (e.g., phenyl groups), and examples of the aromatic iodonium photoacid generator include a photoacid generator containing an iodonium ion in which two groups bonded to the iodine atom are aryl groups (e.g., phenyl groups).

[0053] Examples of aromatic sulfonium photoacid generators include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, 4,4'-bis[diphenylsulfonio]diphenylsulfide-bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide-bishexafluoroantimonate ... Examples of suitable fluorine-containing compounds include [di(β-hydroxyethoxy)phenylsulfonio]diphenyl sulfide-bishexafluorophosphate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone hexafluoroantimonate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, and diphenyl[4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate. These compounds are not limited to these. These compounds may be used alone or in combination.

[0054] Examples of aromatic iodonium photoacid generators include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4-nonylphenyl)iodonium hexafluorophosphate, and 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate. Among these, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate is preferred. These may be used alone or in combination.

[0055] The component (C-2) is a compound that generates an acid when heated. The component (C-2) is not particularly limited, but examples thereof include aromatic sulfonium-based thermal acid generators, aromatic iodonium-based thermal acid generators, and thermal acid generators containing amine salts. From the viewpoint of decomposition properties of the cured product, aromatic sulfonium-based thermal acid generators are preferred. These may be used alone or in combination of two or more.

[0056] The component (C-2) has an anion moiety of BF4 - , PF6 - , SbF6 - , or (BX4) - (wherein X represents a phenyl group substituted with at least two fluorine atoms or trifluoromethyl groups), sulfonium salts, phosphonium salts, ammonium salts, etc. are preferred. Of these, sulfonium salts and ammonium salts are preferred.

[0057] Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, and benzyl(4-hydroxyphenyl)methylsulfonium tris(pentafluoroethyl)trifluorophosphate.

[0058] Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

[0059] Examples of the ammonium salt include dimethylphenyl(4-methoxybenzyl)ammonium hexafluorophosphate, dimethylphenyl(4-methoxybenzyl)ammonium hexafluoroantimonate, dimethylphenyl(4-methoxybenzyl)ammonium tetrakis(pentafluorophenyl)borate, dimethylphenyl(4-methylbenzyl)ammonium hexafluorophosphate, dimethylphenyl(4-methylbenzyl)ammonium hexafluoroantimonate, dimethylphenyl(4-methylbenzyl)ammonium hexafluorotetrakis(pentafluorophenyl)borate, and methylphenyldibenzylammonium hexafluorophosphate. , methylphenyldibenzylammonium hexafluoroantimonate, methylphenyldibenzylammonium tetrakis(pentafluorophenyl)borate, phenyltribenzylammonium tetrakis(pentafluorophenyl)borate, dimethylphenyl(3,4-dimethylbenzyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-N-benzylanilinium hexafluoroantimonate, N,N-diethyl-N-benzylanilinium tetrafluoroborate, N,N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N,N-diethyl-N-benzylpyridinium trifluoromethanesulfonate, and the like.

[0060] The amount of the (C) component is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and most preferably 0.5 to 5 parts by mass, per 100 parts by mass of the combined total of the (A) and (A') components. If the amount is 0.1 to 20 parts by mass, a composition containing a (meth)acrylate compound including the (A) component can be decomposed. From the viewpoint of decomposability, the amount of the (C) component is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass, per 100 parts by mass of the (A) component.

[0061] When the (B) component is a photoradical initiator (B-1), either a photoacid generator (C-1) or a thermal acid generator (C-2) can be used as the (C) component. When the (B-1) and (C-1) components are combined, the curable resin composition is cured by photocuring, and the resulting cured product is decomposed by photodecomposition. When the (B-1) and (C-1) components are combined, it is preferable that the absorption wavelength ranges activated by the (B-1) and (C-1) components are different. It is more preferable that the (B-1) component has an absorption wavelength range below 380 nm and the (B-2) component has an absorption wavelength range above 380 nm. It is most preferable that the (B-1) component has an absorption wavelength range below 380 nm and no absorption wavelength range above 380 nm. When the (B-1) and (C-2) components are combined, the curable resin composition is cured by photocuring, and the resulting cured product is decomposed by thermal decomposition. When the (B) component is an organic peroxide (B-2), it is preferable to use a photoacid generator (C-1) as the (C) component. When the (B-2) component and the (C-1) component are combined, the curable resin composition is cured by heat, and the cured product is decomposed by photodecomposition. In this way, by selecting the (B) component and the (C) component, it is possible to select the curing conditions of the curable resin composition and the decomposition conditions of the cured product.

[0062] Furthermore, the curable resin composition of the present invention may further contain an appropriate amount of additives such as an inorganic filler, an organic filler, a silane coupling agent, a stabilizer, a photosensitizer, and a polymerization inhibitor, within a range that does not impair the properties.

[0063] Examples of the inorganic filler include glass, silica, talc, alumina, mica, ceramics, silicone particles, calcium carbonate, aluminum nitride, carbon powder, kaolin clay, dried clay minerals, dried diatomaceous earth, etc. These may be used alone or in combination of two or more.

[0064] The organic filler may be an organic powder composed of rubber, elastomer, plastic, polymer (or copolymer), etc. These may be used alone or in combination of two or more. Organic fillers having a multilayer structure such as a core-shell type may also be used. The average particle size of the organic filler is preferably in the range of 0.05 to 50 μm.

[0065] Examples of the silane coupling agent include glycidyl group-containing silane coupling agents such as 3-acryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldipropyloxysilane, 3-glycidoxypropyldimethylmonomethoxysilane, 3-glycidoxypropyldimethylmonoethoxysilane, 3-glycidoxypropyldimethylmonopropyloxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane; vinyl group-containing silane coupling agents such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropylmethyldipropyloxysilane. Examples of the silane coupling agents include (meth)acrylic group-containing silane coupling agents such as propyl dimethyl monomethoxy silane, 3-methacryloxypropyl dimethyl monoethoxy silane, 3-acryloxypropyl methyl dipropyl oxy silane, 3-acryloxypropyl methyl dimethoxy silane, 3-acryloxypropyl methyl diethoxy silane, 3-acryloxypropyl methyl dipropyl oxy silane, 3-acryloxypropyl dimethyl monopropyl oxy silane, 3-acryloxypropyl dimethyl monomethoxy silane, 3-acryloxypropyl dimethyl monoethoxy silane, 3-acryloxypropyl dimethyl monopropyl oxy silane, and γ-methacryloxypropyl trimethoxy silane; amino group-containing silane coupling agents such as N-β-(aminoethyl)-γ-aminopropyl trimethoxy silane, γ-aminopropyl triethoxy silane, and N-phenyl-γ-aminopropyl trimethoxy silane; and γ-mercaptopropyl trimethoxy silane and γ-chloropropyl trimethoxy silane. It should be noted that (meth)acrylic-containing silane coupling agents are not included in the components (A) and (A') of the present invention.

[0066] Examples of the light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1-[2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methanol, and 1,2,2,6,6-pentamethyl-4-piperidinyl-methanol. Acrylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, decanedioic acid bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl) ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, N,N',N”,N”'-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazomethane Zadecane-1,10-diamine, polycondensation product of dibutylamine, 1,3,5-triazine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]], dimethyl succinate and 4-hydroxybenzoic acid Polymerization with hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20-(β-lauryloxycarbonyl)ethyl-7-oxa-3,20-diazadispiro〔5·1·11·2〕heneicosan-21-one, β-alanine-N-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester / tetradecyl ester, N-acetyl-3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20-Diazadispiro[5,1,11,2]heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo-[5,1,11,2]-heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanediol acid-[(4-methoxyphenyl)-methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2,2,6,6-tetramethyl higher fatty acid esters of 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)benzotriazole, 2-(2-hydroxy-5-methylphenyl ... Benzotriazole compounds such as 2-(3,4,5,6-tetrahydrophthalimido-methyl)-5-methylphenyl)benzotriazole, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-t-pentylphenyl)benzotriazole, reaction products of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate with polyethylene glycol, and 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol; benzoate compounds such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate; and triazine compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol.

[0067] Examples of the photosensitizer include fluorenone compounds such as 9-fluorenone, 2-hydroxy-9-fluorenone, and 2-amino-9-fluorenone; aromatic ketone compounds such as anthrone and dibenzosuberone; fluorene, 2-bromofluorene, 9-bromofluorene, 9,9-dimethylfluorene, 2-fluorofluorene, 2-iodofluorene, 2-fluoreneamine, 9-fluorenol, 2,7-dibromofluorene, 9-aminofluorene hydrochloride, 2,7-diaminofluorene, 9,9'-spirobi[9H-fluorene], 2-fluorenecarboxaldehyde, 9-fluorenylmethanol, and 2-acetylfluorene. Examples of compounds that can be used include fluorene-based compounds such as fluorene, fluoranthene-based compounds, benzil ketal-based compounds, α-hydroxyacetophenone-based compounds, benzoin-based compounds, aminoacetophenone-based compounds, oxime ketone-based compounds, and acylphosphine oxide-based compounds, which are known as radical polymerization initiators; naphthalene derivative compounds, anthracene derivative compounds, nitro group-containing compounds selected from the group consisting of nitrobenzoic acid and nitroaniline; and dye compounds selected from the group consisting of riboflavin, rose bengal, eosin, erythrosine, methylene blue, and new methylene blue rose.

[0068] Examples of the polymerization inhibitor include quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; alkylphenol-based polymerization inhibitors such as 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol (BHT), and 2,4,6-tri-tert-butylphenol; alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, phenothiazine, 4-hydroxy-2,2,6,6- Examples of polymerization inhibitors include, but are not limited to, amine-based polymerization inhibitors such as tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, and 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine; and N-oxyl-based polymerization inhibitors such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl.

[0069] <Application> The curable resin composition of the present invention can be used as an adhesive, sealant, or coating agent to impart dismantling properties and can be applied to a wide variety of applications. Specific applications include adhesion, sealing, casting, and coating of automotive switches, headlamps, engine internal parts, electrical components, drive engines, brake oil tanks, front hoods, fenders, body panels such as doors, and windows; in the electronic materials field, adhesion, sealing, casting, and coating of flat panel displays (liquid crystal displays, organic EL displays, light-emitting diode displays, field emission displays), video discs, CDs, DVDs, MDs, pickup lenses, hard disks, and the like; in the battery field, adhesion, sealing, casting, and coating of lithium batteries, lithium-ion batteries, manganese batteries, and the like; Adhesion, sealing, coating, etc. of batteries, alkaline batteries, fuel cells, silicon solar cells, dye-sensitized batteries, organic solar cells, etc.; in the optical parts field, adhesion, sealing, coating, etc. of optical fiber materials around optical switches and optical connectors, optical passive components, optical circuit components, and optoelectronic integrated circuits, etc.; in the optical equipment field, adhesion, sealing, coating, etc. of camera modules, lens materials, finder prisms, target prisms, finder covers, light-receiving sensor parts, photographic lenses, our company's lenses for projection TVs, etc.; in the infrastructure field, it can be used for adhesion, lining, sealing, coating, etc. of gas pipes, water pipes, etc.

[0070] <Curing method> The curable resin composition of the present invention can be cured by heating, ultraviolet light, or the like, depending on the selection of component (B), to give a cured product. When component (B-1) is used, the cumulative light dose is 0.1 to 50 kJ / m 2 is preferred, and 1 to 30 kJ / m 2 When component (B-2) is used, the curing temperature is preferably 50 to 150°C, more preferably 60 to 120°C, and most preferably 70 to 100°C. There are no particular restrictions on the curing time, but when the temperature is 50 to 150°C, the curing time is preferably 1 minute to 3 hours, and more preferably 2 minutes to 2 hours.

[0071] <Disassembly method> The cured product obtained by curing the curable resin composition of the present invention can be decomposed by heating, ultraviolet light, etc., depending on the selection of component (C). When component (C-1) is used, the cumulative light dose is 0.1 to 50 kJ / m 2 is preferred, and 1 to 30 kJ / m 2 When component (C-2) is used, the curing temperature is preferably 50 to 150°C, more preferably 60 to 120°C, and most preferably 70 to 100°C. There are no particular restrictions on the curing time, but when the temperature is 50 to 150°C, the curing time is preferably 1 minute to 3 hours, and more preferably 2 minutes to 2 hours. [Example]

[0072] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0073] [Examples 1 to 7, Comparative Example 1]

[0074] Examples 1 to 7 and Comparative Example 1 were prepared. Components (A) to (C) were weighed and stirred in a mixer for 60 minutes to obtain a curable resin composition. Detailed amounts prepared are shown in Table 1, and all values ​​are expressed in parts by mass.

[0075] The details of the materials used are as follows: (A-1): 47.5 g (214 mmol) of 2-hydroxy-3-phenoxypropyl acrylate and 1.34 g (5.3 mmol) of pyridinium p-toluenesulfonate were mixed in a tetrahydrofuran solution at 25°C for 30 minutes with stirring, and then dehydrated for 20 minutes at room temperature using molecular sieves 3A that had been vacuum dried at 150°C for 1 hour. While cooling in an ice bath, 10 mL (107 mmol) of 2-methoxypropene was added dropwise, and after the dropwise addition, the mixture was stirred at 60°C for 1 hour. The molecular sieves and pyridinium p-toluenesulfonate were then removed by suction filtration and using a silica gel column (solvent: acetone:hexane = 1:3), to obtain Compound 1, which has the structure of general formula (1). The resulting Compound 1 1 The H-NMR chart is shown in Figure 1. (A-2): 30.9 g (214 mol) of 4-hydroxybutyl acrylate and 1.34 g (5.3 mmol) of pyridinium p-toluenesulfonate were mixed in a tetrahydrofuran solution and stirred at 25°C for 30 minutes. The mixture was then dehydrated at room temperature for 20 minutes using molecular sieves 3A that had been vacuum-dried at 150°C for 1 hour. While cooling in an ice bath, 10 mL (107 mmol) of 2-methoxypropene was added dropwise. After stirring at room temperature for 24 hours, the molecular sieves and pyridinium p-toluenesulfonate were removed by suction filtration and a silica gel column (solvent: acetone:hexane = 1:3) to obtain Compound 2, which has the structure of general formula (1). Component (A'): a (meth)acrylate compound other than component (A). (A'-1): 2-Hydroxy-3-phenoxypropyl acrylate, product name: Epoxy Ester M-600A (Kyoeisha Chemical Co., Ltd.) (A'-2): Isononyl acrylate (Osaka Organic Chemical Industry Ltd.) (A'-3): Polyether-based urethane acrylate having acryloyl groups only at both ends Component (B): Radical initiator (B-1): Photoradical initiator Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide Product name: Omnirad819 (IGM Resin) Absorption wavelength range: 380-440 nm (B-2): t-Butyl 2-ethylperoxyhexanoate, product name: Perbutyl O (NOF Corporation) Component (C): Acid generator (C-1): Diphenyl[4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate 50% propylene carbonate solution. Product name: CPI-200K (Sanapro Co., Ltd.). Absorption wavelength: 310-370 nm. (C-2): Benzyl(4-hydroxyphenyl)methylsulfonium tris(pentafluoroethyl)trifluorophosphate, product name: TA-100 (Sanapro Co., Ltd.)

[0076] [Shear adhesive strength (initial)] Each curable resin composition was applied to a glass test piece (25 mm x 100 mm x 5 mm thick) and spread, and then two similar glass test pieces (25 mm x 100 mm x 5 mm thick) were bonded together to form a bonded area of ​​25 mm x 10 mm. After curing under curing conditions 1 or 2 while held in place with a jig, the tensile shear adhesive strength was measured at a tensile speed of 50 mm / min using a universal tensile tester. The results are shown in Table 1. The unit is [MPa]. Test details were in accordance with JIS K 6850:1999. Curing conditions 1: UV-LED irradiator wavelength 405nm irradiation 300mJ, 10 seconds Curing condition 2: 100℃, 1 hour

[0077] [Shear adhesive strength (after disassembly)] The test specimens prepared in the same manner as above were subjected to dismantling tests under dismantling conditions 1 and 2. Decomposition condition 1: UV-LED irradiator, wavelength 365nm irradiation, 300mJ, 10 seconds Decomposition condition 2: 100℃, 1 hour

[0078] [Shear adhesive strength (rate of change)] The rate of change was calculated by the following formula: Rate of change (%) = (shear adhesive strength after degradation - initial shear adhesive strength) / initial shear adhesive strength In the present invention, the rate of change is preferably -30% or less, and more preferably -40% or less.

[0079] [Table 1]

[0080] The curable resin compositions of Examples 1 to 7, which used the component (A) of the present invention, showed a significant decrease in shear adhesive strength when stimulated by light or heat, demonstrating their dismantling properties. On the other hand, Comparative Example 1, which did not use the component (A) of the present invention, showed no decrease in adhesive strength even when stimulated by light or heat, and showed an improvement in adhesive strength.

[0081] The storage modulus before and after decomposition was measured using the cured product of Example 1. The curable resin composition of Example 1 was poured into a jig set to a thickness of 0.8 mm. The cured product was then cured using a UV-LED irradiator at a wavelength of 405 nm for 10 seconds at 300 mJ, and cured. 10 mm x 50 mm x 0.8 mm strip-shaped test pieces were prepared as test pieces before decomposition. Test pieces were prepared in the same manner and further irradiated with a UV-LED irradiator at a wavelength of 365 nm for 10 seconds at an illuminance of 300 mJ, and these were used as test pieces after decomposition. The storage modulus E' at 25°C of these test pieces was measured using a dynamic viscoelasticity measuring device DMS6100 (manufactured by Seiko Instruments Inc.). Before decomposition: 1.0 x 10 6 After Pa decomposition: 1.0×10 3 A significant decrease in storage modulus was confirmed, which confirmed that the cured product itself had decomposed. [Industrial Applicability]

[0082] The adhesive strength of the curable resin composition of the present invention is significantly reduced by stimulation from light or heat, and therefore adhesives, sealants, and coating agents using the curable resin composition are easily disintegrated, making them highly useful and applicable to a variety of applications.

Claims

1. A curable resin composition comprising the following (A) to (C): Component (A): a compound having a structure of general formula (1) (R １ is hydrogen or an alkyl group, R ２ is a divalent organic group) Component (B): Radical initiator Component (C): Acid generator

2. R in the general formula (1) １ The curable resin composition according to claim 1 or 2, wherein is hydrogen.

3. R in the general formula (1) ２ The curable resin composition according to claim 1 or 2, wherein the aromatic ring is contained in the alkyl group.

4. The curable resin composition according to claim 1 or 2, wherein the component (B) is a photoradical initiator.

5. The curable resin composition according to claim 1 or 2, wherein the component (C) is a photoacid generator.

6. A cured product obtained by curing the curable resin composition according to claim 1 or 2 with heat or active energy rays.

7. A method for decomposing the cured product according to claim 6 by applying heat or active energy rays.

8. The curable resin composition according to claim 5, wherein the components (B) and (C) are activated in different absorption wavelength ranges.

9. An adhesive comprising the curable resin composition according to claim 1 or 2.

10. A sealant comprising the curable resin composition according to claim 1 or 2.

11. A coating agent comprising the curable resin composition according to claim 1 or 2.

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