JP6539488B2 - Method for producing cured product, cured product, curable composition and adhesive - Google Patents

Description

  In the present invention, it is essential to carry out two or more kinds of polymerization reactions using a specific curable composition, and a second curing is performed after passing through the first curing to be a cured product having a specific elastic modulus, and the second The present invention relates to a method for producing a cured product which becomes a cured product having a specific elastic modulus after curing, a cured product obtained by the production method, a curable composition used for the production method, and an adhesive comprising the curable composition.

  Conventionally, a curable composition used as an adhesive contains a polymerizable resin and an initiator, is cured by causing a polymerization reaction by heat, light or the like, and is widely used in various applications. Such adhesives include, in addition to adhesion to various adherends, thin film molding, flexibility, transparency, moisture resistance, conductivity, heat resistance, transparency, refractive index and curability control, etc. Functionalization is desired.

  As a curing means of the adhesive, curing by heat or light is generally used. Thermosetting adhesives have problems in productivity because they require a long curing process at high temperature. Therefore, in many cases, a photocurable adhesive that can be polymerized in a short time and is excellent in productivity is used. However, the photocurable adhesive has a problem that it is difficult to use it as an adhesive when the adherend is opaque, since the portion which is not irradiated with light is not cured.

  As a means for solving the above problems, Patent Document 1 discloses a pressure-sensitive adhesive sheet for an intermediate film which is cured by light curing to exhibit adhesiveness. Further, Patent Document 2 discloses a cationically curable curable adhesive composition using an epoxy compound. Furthermore, Patent Document 3 discloses a semiconductor adhesive composition having two different polymerization reaction steps using an epoxy compound and an acrylic compound. However, a curable composition is obtained which gives a cured product excellent in thin film formation of the cured product, elastic modulus stability of the cured product after the first curing, and strong adhesion and low moisture permeability in the cured product after the second curing. It is not done.

JP 2002-348150 A JP, 2006-210297, A Unexamined-Japanese-Patent No. 2012-188463

  A cured product prepared by a conventionally known production method can be applied to an opaque adherend, and can form a thin film of the cured product, and the cured product after the first curing develops tackiness and develops adhesion There is a problem that a cured product which is excellent in the stability of the properties and which is a cured product after the second curing is excellent in strong adhesion and low moisture permeability can not be obtained.

The inventors of the present invention have intensively studied the above problems, and it is essential to carry out two or more kinds of polymerization reactions using the curable composition, and the second curing is carried out via the first curing having a specific elastic modulus. It discovered that the said subject could be solved by the manufacturing method of the hardened | cured material which will become hardened | cured material which has a specific elasticity modulus later, and reached | attained this invention.
That is, in the method for producing a cured product using a curable composition, the present invention essentially requires two or more kinds of polymerization reactions to be carried out, and in the process of converting the curable composition into a cured product, the elastic modulus is 10 It is essential to pass the first curing to ³ to 10 ⁶ Pa, and the elastic modulus of the second cured cured product is 10 ⁷ Pa or more, and the curable composition is a cationically polymerizable compound (A), A radically polymerizable compound (B), a photopolymerization initiator (C) and a thermal polymerization initiator (D) are contained, and the content of the cationically polymerizable compound (A) is a cationically polymerizable compound (A), radically polymerizable The manufacturing method of hardened | cured material which is a curable composition which is 50-95 mass parts with respect to a total of 100 mass parts of a mass of a compound (B), a photoinitiator (C), and a thermal-polymerization initiator (D) To provide.

  The present invention provides a method for producing the above-mentioned cured product, a cured product obtained by the method for producing the above-mentioned cured product, an adhesive comprising the above-mentioned cured composition and the above-mentioned curable composition.

  According to the present invention, the elastic modulus does not significantly change depending on the curing conditions after the first curing, and the stability of the elastic modulus is good, and after the second curing, high transparency, low moisture permeability, strong adhesiveness It is possible to provide a cured product, a curable composition and an adhesive that simultaneously satisfy the above and flexibility.

  In the method for producing a cured product of the present invention, it is essential to carry out two or more kinds of polymerization reactions. When the above-mentioned polymerization reaction is classified according to the chemical reaction species, for example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and ring-opening polymerization can be mentioned. In the method for producing a cured product of the present invention, at least radical polymerization and cationic polymerization are preferably performed because of high reactivity.

  The first curing in the present invention means a polymerization reaction in which the cured product exhibits adhesiveness, and, for example, photopolymerization reaction such as photo radical polymerization reaction, photo cation polymerization reaction, heat radical polymerization reaction, heat cation polymerization reaction, etc. Thermal polymerization reaction is mentioned. It is preferable to raise the reaction rate of the reaction as much as possible, since the first curing develops highly reliable tackiness.

  The second curing in the present invention means a polymerization reaction in which the cured product exhibits strong adhesive strength and low moisture permeability, and a polymerization reaction different from the first curing is selected, for example, photo radical polymerization reaction, photo cationic polymerization A photopolymerization reaction such as a reaction, a thermal radical polymerization reaction, and a thermal polymerization reaction such as a thermal cationic polymerization reaction can be mentioned. The second curing may be performed in one step or may be performed in a plurality of steps. For example, when performing a photopolymerization reaction, curing may be performed first with a low dose, and then curing may be performed with a high dose. For example, when performing a thermal polymerization reaction, curing may be performed at a low temperature or a short time, and then curing may be performed at a high temperature or a long time. In order to obtain a cured product excellent in strong adhesion and low moisture permeability, it is preferable to mention the reaction rate of the reaction as much as possible.

According to the method for producing a cured product of the present invention, it is essential to go through the first curing in which the elastic modulus is 10 ³ to 10 ⁶ Pa. The cured product after the first curing is preferable because it has high adequate tack and high tack stability.

According to the method for producing a cured product of the present invention, the elastic modulus of the cured product after the second curing is 10 ⁷ Pa or more. The cured product after the second curing is preferable because it is excellent in strong adhesive strength and low moisture permeability. The second curing means the last polymerization reaction carried out in the method for producing a cured product of the present invention.

  The curable composition used in the method for producing a cured product of the present invention contains a cationically polymerizable compound (A), a radically polymerizable compound (B), a photopolymerization initiator (C) and a thermal polymerization initiator (D). Do. In the curable composition used in the present invention, the content of the cationically polymerizable compound (A) is the cationically polymerizable compound (A), the radically polymerizable compound (B), the photopolymerization initiator (C) and the thermal polymerization initiation It is 50 to 95 parts by mass with respect to 100 parts by mass of the mass of the agent (D). The curable composition used in the present invention may further contain a cationic curing retarder (E). Hereinafter, each component will be described in order.

<Cationically Polymerizable Compound (A)>
The said cationically polymerizable compound (A) will not be specifically limited if it shows cationic polymerization property. Examples of compounds exhibiting cationic polymerization include epoxy compounds, oxetane compounds, and vinyl ether compounds, but the cured product exhibits high adhesion to various adherends, and exhibits high heat resistance, high strength and low moisture permeability. Particularly, epoxy compounds are preferred.

As the above-mentioned epoxy compound, diglycidyl ether compounds, polyfunctional epoxy compounds and alicyclic epoxy compounds are preferable.
The diglycidyl ether compound is preferable because the cured product exhibits high adhesion to various adherends. Examples of diglycidyl ether compounds include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, glycerin diglycidyl ether, 1,4-butanediol diglycidyl ether, 5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, etc. may be mentioned.
The alicyclic epoxy compound is preferable because the cured product after the second curing has high heat resistance and high strength. Examples of alicyclic epoxy compounds include 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, methylene bis (3,4-epoxycyclohexane), propane-2 , 2-Diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, ethylene bis (3,4-epoxycyclohexane carboxylate), bis (3,4-epoxy Cyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl 3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3, 4-Epoxycyclohexylmethyl 6- Ethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl 3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl 3,4- Epoxy-5-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, dicyclopentadiene diepoxide, 3,4-epoxy-6-methylcyclohexyl carboxy Rate, α-pinene oxide, cyclohexene oxide, cyclopentene oxide and the like.
The polyfunctional epoxy compound is preferable because the cured product after the second curing has low moisture permeability. Examples of polyfunctional epoxy compounds include 1- (2,3-bis (oxiran-2-ylmethoxy) propoxy) -3- (oxiran-2-ylmethoxy) propan-2-ol, trimethylolpropane triglycidyl ether, tris Examples thereof include (2,3-epoxypropyl) isocyanurate, 1,1,2,2-tetrakis (glycidyloxyphenyl) ethane and pentaerythritol tetraglycidyl ether.
As other epoxy compounds, those shown below may be mentioned. That is, for example, methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, mixed alkyl glycidyl ether having 12 to 13 carbon atoms, phenyl-2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, p -Sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl glycidyl Ether, 4-phenylphenol glycidyl ether, cresyl glycidyl ether, dib Monoglycidyl ether compounds such as mocresyl glycidyl ether, decyl glycidyl ether, methoxypolyethylene glycol monoglycidyl ether, ethoxy polyethylene glycol monoglycidyl ether, butoxy polyethylene glycol monoglycidyl ether, phenoxy polyethylene glycol monoglycidyl ether, dibromophenyl glycidyl ether; glycidyl And glycidyl esters such as acetate and glycidyl stearate.

  An epoxidized polyolefin can also be used as said epoxy compound. The epoxidized polyolefin is a polyolefin in which an epoxy group is introduced by modifying the polyolefin with an epoxy group-containing monomer. Epoxidized polyolefin is obtained by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and, if necessary, another monomer, by either a copolymerization method or a graft method. It can be manufactured. Ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer and another monomer may be polymerized alone or in combination with other monomers. Also, the double bond of a non-conjugated polybutadiene having a hydroxyl group at the end can be obtained by epoxidation by the peracetic acid method, and one having a hydroxyl group in the molecule may be used. Moreover, a hydroxyl group can be urethane-ized with isocyanate, and a primary hydroxyl group-containing epoxy compound can be made to react here, and an epoxy group can be introduce | transduced.

  As said ethylene or C3-C20 alpha-olefin, ethylene, propylene, butylene, isobutylene, 1,3-butadiene, 1,4-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3 -Butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and the like can be mentioned.

  Examples of the epoxy group-containing monomer include glycidyl esters of α, β-unsaturated acids, vinyl benzyl glycidyl ether and allyl glycidyl ether. Specific examples of glycidyl esters of α, β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylic acid, with glycidyl methacrylate being particularly preferred.

  Examples of the other monomers include unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, Fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (metha] phthalic acid ) Acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) ) Acrylate malate, dicyclopentadiene · And unsaturated polybasic acids such as polyfunctional (meth) acrylates having one carboxyl group and two or more (meth) acryloyl groups; 2-hydroxyethyl (meth) acrylate, (meth) acrylate -2-hydroxypropyl, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n (meth) acrylate -Octyl, isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, (meth ) Dimethylaminoethyl acrylate, aminopropyl (meth) acrylate, (meth) acrylic Dimethylaminopropyl methacrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) acrylate ) Tetrahydrofuryl acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethane Tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tri Unsaturated monobasic acids and esters of polyhydric alcohols or polyhydric phenols such as cyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloyl ethyl] isocyanurate and polyester (meth) acrylate oligomers; (meth) acrylic acid Metal salts of unsaturated polybasic acids such as zinc and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetratetra Durophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-anhydride Acid anhydride of unsaturated polybasic acid such as maleic acid adduct, dodecenyl succinic anhydride and methyl hymic acid; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylene triamine tris (meth) acrylamide, xylylene bis (meth) Amides of unsaturated monobasic acids such as acrylamide, α-chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide and amines of polyhydric amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanation Unsaturated nitriles such as nylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol Unsaturated aromatic compounds such as vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether and vinyl naphthalene; unsaturated ketones such as methyl vinyl ketone; vinyl amines such as allylamine, N-vinyl pyrrolidone and vinyl piperidine Saturated amine compounds; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether and isobutyl vinyl ether; Unsaturated imides such as maleimide, N-phenyl maleimide and N-cyclohexyl maleimide; Indens such as indene and 1-methyl indene; polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane etc Macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain; vinyl urethane compounds of hydroxyl group-containing vinyl monomers and polyisocyanate compounds; vinyl epoxy compounds of hydroxyl group-containing vinyl monomers and polyepoxy compounds; pentaerythritol triacrylate A reaction product of a hydroxyl group-containing polyfunctional acrylate such as dipentaerythritol pentaacrylate with a polyfunctional isocyanate such as tolylene diisocyanate or hexamethylene diisocyanate; Hydroxyl group-containing polyfunctional acrylates such as lysitol triacrylate and dipentaerythritol pentaacrylate; polyfunctional acrylates having an acid value which is a reactant of a dibasic acid anhydride such as succinic anhydride, phthalic anhydride and tetrahydrophthalic anhydride; Can be mentioned.

  A commercial item can also be used as said epoxidized polyolefin, For example, Epolide PB3600, PB4700 (made by Daicel), Adekasizer BF-1000, Adekastab FC-3000 (made by Adeka), Bond first 2B, 7B, 2C , E, 7B, 7L, 7M, VC40, CG5001, CG5004 (manufactured by Sumitomo Chemical Co., Ltd.), JP-100, JP-200 (manufactured by Nippon Soda Co., Ltd.) Poly bd R-45 HT, Poly bd R-15 HT (manufactured by Idemitsu Kosan Co., Ltd.) And Ricon 657 (manufactured by Arkema) and the like.

  Examples of the oxetane compounds include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and 1,2-bis [(3-Ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1 , 6-Bis (3-ethyl-3-oxetanylmethoxy) hexane, 3-ethyl-3- [ Phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane and 3-ethyl And 3- (chloromethyl) oxetane and the like.

  Examples of the vinyl ether compounds include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, Examples thereof include hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether and 1,6-cyclohexane dimethanol divinyl ether.

  As said cationically polymerizable compound (A), a commercial item can be used, For example, Epolight 40E, 1500NP, 1600, 80MF, 4000, 3002, M-1230, 100F (made by Kyoeisha Chemical Co., Ltd.), Adeka Glycic Roll ED-503, ED-503D, ED-503G, ED-505, ED-523T, ED-513, ED-501, ED-502, ED-509, ED-518, ED-529, Adeka resin EP-4000S, EP-4005, EP-4080, EP-4085, EP-4088 (made by Adeka), EP-4100 E, Denacol EX-201, EX-203, EX-211, EX-212, EX-221, EX-251, EX-251, EX-252, EX-711, EX-721, Denacol EX-111, EX 121, EX-141, EX-142, EX-145, EX-146, EX-147, EX-171, EX-192, EX-731 (manufactured by Nagase ChemteX Corp.), Celoxide 2021 P, 2081, 2000, 3000 ( Daicel Corporation), Epiol M, EH, L-41, SK, SB, TB, OH (manufactured by NOF Corporation), Aron oxetane EXOH, POX, OXA, OXT-101, OXT-121, OXT-211, OXT- 212, OXT-221 (manufactured by Toagosei Co., Ltd.), Etanacol OXBP, OXTP (manufactured by Ube Industries, Ltd.), 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemicals), ogsol PG-100 , EG-200, EG-210, EG-250. Osaka Gas Chemical Co., Ltd., ESN- 475 V (made by Tohto Kasei Co., Ltd.), Epikote YX 8800 (made by Mitsubishi Chemical Co., Ltd.), Epiclon N-665, HP-7200 (made by DIC), EOCN-1020, EOCN-102 S, EOCN- 103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H and NC-7000L (manufactured by Nippon Kayaku Co., Ltd.) and the like.

In the curable composition used in the method for producing a cured product of the present invention, the content of the cationically polymerizable compound (A) is the cationically polymerizable compound (A), the radically polymerizable compound (B), the photopolymerization initiator (C) And 50 to 95 parts by mass, preferably 70 to 95 parts by mass, per 100 parts by mass of the sum of the mass of the thermal polymerization initiator (D). When the content of the cationically polymerizable compound (A) is smaller than 50 parts by mass, the cured product after the second curing may not have an appropriate elastic modulus, adhesiveness and low moisture permeability, and 95 parts by mass If it is larger, the cured product after the first curing may not have an appropriate modulus of elasticity and tackiness.
For example, in the case of forming a cured product with a film thickness of 1 to 100 μm, the content of the cationically polymerizable compound (A) is the cationically polymerizable compound (A), the radically polymerizable compound (B), the photopolymerization initiator (C) And 50 parts by mass to 100 parts by mass of the sum of the mass of the thermal polymerization initiator (D). Preferably, it is 70 to 95 parts by mass. When the content of the cationically polymerizable compound (A) is smaller than 50 parts by mass, the cured product after the second curing may not have an appropriate elastic modulus, adhesiveness and low moisture permeability, and 95 parts by mass If it is larger, the cured product after the first curing may not have appropriate modulus of elasticity and tackiness.

<Radical polymerizable compound (B)>
The radically polymerizable compound (B) is not particularly limited as long as it exhibits radical polymerizability, but is preferably acrylate and methacrylate from the viewpoint of curability and the presence of compounds of various structures.

The radically polymerizable compound (B) is not particularly limited, and those conventionally used for curable compositions can be used, but the structure contains a monofunctional (meth) acrylic compound and a saturated aliphatic ring in the structure ( The meta) acrylic compounds, polyfunctional (meth) acrylic compounds, epoxy (meth) acrylic compounds, etc. are preferred.
The monofunctional (meth) acrylic compound is preferable because the viscosity of the curable composition can be reduced, and the cured product after the second curing exhibits good flexibility. Examples of monofunctional (meth) acrylic compounds include: (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, glycidyl (meth) acrylic acid, the following compound No. B1-No. B4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate ( Meta) Isononyl acrylate, Stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylic Aminopropyl acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, (meth) ) Phenoxyethyl acrylate, (meth) acrylic Tetrahydrofuryl, vinyl (meth) acrylate, and (meth) allyl acrylate and benzyl (meth) acrylate.
The (meth) acrylic compound having a saturated aliphatic ring in the structure is preferable because the cured product after the second curing has low moisture permeability. Examples of (meth) acrylic compounds containing a saturated aliphatic ring in the structure include tricyclodecanedimethanol di (meth) acrylate, isoboronyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid and the like. Be
The polyfunctional (meth) acrylic compound is preferable because the cured product after the second curing has a high elastic modulus. As a polyfunctional (meth) acrylic compound, for example, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol And tetra (meth) acrylate and pentaerythritol tri (meth) acrylate.
Epoxy (meth) acrylic compounds are preferable because of high radical polymerizability. As an epoxy (meth) acrylic compound, for example, 2-hydroxy-3-phenoxypropyl (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylic acid adduct, (meth) acrylic acid adduct of ethylene glycol diglycidyl ether And (meth) acrylic acid adducts of propylene glycol diglycidyl ether and (meth) acrylic acid adducts of diethylene glycol diglycidyl ether.
As other radically polymerizable compounds (B), the following may be mentioned. That is, for example, unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid Acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloyloxyethyl succinate, monobasic phthalate Mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends such as [2- (meth) acryloyloxyethyl] and ω-carboxypolycaprolactone mono (meth) acrylate; hydroxyethyl (meth) acrylate malate , Hydroxypropyl (meta) Unsaturated monobasic acids such as rate malate, dicyclopentadiene malate and polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups; triethylene glycol di (meth) acrylate Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanate Unsaturated monobasic acids and esters of polyvalent alcohols or polyhydric phenols such as nurate and polyester (meth) acrylate oligomers; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; Maleic anhydride, B Taconic acid anhydride, citraconic acid anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1 , Acid anhydrides of unsaturated polybasic acids such as 2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride and methylhydric anhydride; (meth) acrylamide, methylene bis- Amides of unsaturated monobasic acids and polyvalent amines such as (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) acrylamide, α-chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide; such as acrolein Unsaturated Unsaturated nitriles such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene Unsaturated aromatic compounds such as styrene, divinyl benzene, vinyl toluene, vinyl benzoic acid, vinyl phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether and vinyl benzyl glycidyl ether; Unsaturation such as methyl vinyl ketone Ketones; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl methyl ether, vinyl ether Vinyl ethers such as ether, n-butyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenyl maleimide and N-cyclohexyl maleimide; indenes such as indene and 1-methyl indene; 1,3- Aliphatic conjugated dienes such as butadiene, isoprene and chloroprene; having mono (meth) acryloyl groups at the end of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane Macromonomers; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole Vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers, vinyl urethane compound polyisocyanate compounds, vinyl epoxy compounds of the hydroxyl group-containing vinyl monomers and polyepoxy compounds.

  A commercial item can also be used as said radically polymerizable compound (B), For example, Kayalad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (made by Nippon Kayaku Co., Ltd.), aronix M-140, M-215, M-350 (manufactured by Toagosei Co., Ltd.), NK ester A-DPH, A-TMPT, A-DCP, A-HD-N, A-9300, TMPT, DCP, NPG and HD- N (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

In the curable composition, the content of the radically polymerizable compound (B) is not particularly limited, but the cationically polymerizable compound (A), the radically polymerizable compound (B), the photopolymerization initiator (C) And preferably 0.5 to 40 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the total mass of the thermal polymerization initiator (D). If the content of the radically polymerizable compound (B) is smaller than 0.5 parts by mass, the cured product after the first curing may not have a sufficient elastic modulus, and if larger than 40 parts by mass, the second Curling or cracking may occur in the cured product after curing.
For example, in the case of forming a cured product having a film thickness of 1 to 100 μm, the content of the radically polymerizable compound (B) is the cationically polymerizable compound (A), the radically polymerizable compound (B), the photopolymerization initiator (C) And preferably 0.5 to 40 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the total mass of the thermal polymerization initiator (D). When the content of the radically polymerizable compound (B) is smaller than 0.5 parts by mass, the cured product after the first curing may not have a sufficient elastic modulus, and when it is larger than 40 parts by mass, the second cure Curing or cracking may occur in the cured product later.

<Photoinitiator (C)>
Although the said photoinitiator (C) is not specifically limited, A radical photopolymerization initiator and a cationic photopolymerization initiator are preferable.

  The photo radical polymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and conventionally known compounds can be used. For example, benzophenone compounds, acetophenone compounds, thioxanthone compounds And ketone compounds such as benzyl compounds, benzoin compounds and oxime ester compounds, oxime ester compounds, α-hydroxy ketone compounds, α-aminoalkylphenone compounds and phosphine oxide compounds titanocene compounds and the like are preferable. It can be illustrated as

  Examples of benzophenone compounds include benzophenone, methyl O-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone and fluorenone.

  Examples of acetophenone compounds include 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl Ketone, 2-hydroxy-2-methyl 1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-1-one Examples include {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -phenyl} -2-methylpropan-1-one and methyl phenylglyoxylate.

  A commercial item can also be used as said acetophenone type compound, For example, IRGACURE 127, IRGACURE 184, IRGACURE 651, IRGACURE 907, DAROCUR 1173 (made by BASF Corporation), LUNA100, LUNA200 (made by DKSH Japan company) etc. are mentioned.

  As a thioxanthone type-compound, thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2-chloro thioxanthone, diethyl thioxanthone etc. are mentioned, for example.

  Examples of the benzyl compounds include benzyl, benzyldimethyl ketal and benzyl-β-methoxyethyl acetal.

  Examples of benzoin compounds include benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like.

  A commercial item can also be used as said benzoyl type-compound, For example, DAROCURE1173 (made by BASF Corporation) etc. are mentioned.

  Examples of oxime compounds include 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1 -Phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime) Ethanone) and 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- - (O-acetyl oxime), and the like.

  A commercial item can also be used as said oxime type compound, For example, IRGACURE OXE01 and IRGACURE OXE02 (made by BASF Corporation) etc. are mentioned.

  As the α-hydroxy ketone compound, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl- Examples include 1-propan-1-one and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane and the like.

  Examples of α-aminoalkylphenone compounds include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2-dimethylamino-2- (4-methylbenzyl) -1 And-(4-morpholin-4-yl-phenyl) butan-1-one and the like.

  A commercial item can also be used as said (alpha)-amino alkyl phenone type-compound, For example, IRGACURE 369 and IRGACURE 379 (made by BASF Corporation) etc. are mentioned.

  Examples of phosphine oxide compounds include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and , 4, 6-trimethyl benzoyl diphenyl phosphine oxide and the like.

  A commercial item can also be used as said phosphine oxide type compound, For example, DAROCURE TPO and IRGACURE 819 (made by BASF Corporation) etc. are mentioned.

  Examples of the titanocene compounds include bis (ビ ス 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and the like. .

  A commercial item can also be used as said titanocene type compound, For example, IRGACURE 784 (made by BASF Corporation) etc. are mentioned.

The photocationic polymerization initiator may be any compound as long as it is a compound capable of generating an acid upon irradiation with energy rays, but preferably it is an onium salt which releases a Lewis acid upon irradiation of energy rays. It is a double salt or a derivative thereof. Representative examples of such compounds include the following general formula:
[A] ^{r +} [B] ^r-
And salts of cations and anions represented by

Here, the cation [A] ^{r +} is preferably onium, and its structure is, for example,
[(R ¹ ) _a Q] ^{r +}
Can be represented by

Furthermore, here, R ¹ is an organic group which has ¹ to 60 carbon atoms and may contain any number of atoms other than carbon atoms. a is an integer of 1 to 5; The a pieces of R 1 may be each independently, the same or different. In addition, at least one is preferably an organic group as described above having an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F and N = N. Further, when the valence of Q in the cation [A] ^{r +} is q, it is necessary that the relationship r = a−q holds (however, N = N is treated as having a valence of 0).

The anion [B] ^r- is preferably a halide complex, and its structure is, for example, a compound represented by the following formula:
[Lx _b ] ^r-
Can be represented by

Furthermore, here, L is a metal or metalloid (Metalloid) which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn and Co. X is a halogen atom. b is an integer of 3 to 7; Also, when the valence of L in the anion [B] ^r − is p, it is necessary that the relationship r = b−p holds.

From the viewpoint of sensitivity and availability for the anion [LX _b ] ^{r −} of the above general formula, the following anion can be preferably used. For example, tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF ₄ ) ⁻ , hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆₎ ^-, hexafluoroarsenate (AsF ₆₎ ^-, and hexachloroantimonate (SbCl ₆₎ ^-, and the like.

Further, the anion [B] ^r- has the following general formula,
[LX _b-1 (OH)] ^r-
The thing of the structure represented by these can be mentioned. L, X and b are as described above. Other anions that can be used include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , toluene sulfonate anion And trinitrobenzene sulfonic acid anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraaryl borate and tetrakis (pentafluorophenyl) borate.

  In the present invention, among such onium salts, it is particularly effective to use the following aromatic onium salts (i) to (iii) from the viewpoint of sensitivity and availability. Among these, one of them may be used alone, or two or more of them may be mixed and used.

(I) aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate and 4-methylphenyl diazonium hexafluorophosphate.

(Ii) Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate and tolycamyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt

(C) Sulfonium salts represented by Group I or Group II below and sulfonium salts such as hexafluoroantimony ion and tetrakis (pentafluorophenyl) borate ion

  (Η5-2,4-Cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron-hexafluorophosphate as another onium salt Mixtures of iron-arene complexes such as: aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum and tris (salicylaldehyde) aluminum; and silanols such as triphenylsilanol; Can also be mentioned.

A commercial item can also be used for the said photocationic polymerization initiator.
Examples of the cationic photopolymerization initiator of aromatic iodonium salt include IRUGACURE 261 (manufactured by BASF), BBI-103 and MPI-103 (manufactured by Midori Kagaku).
As a photocationic polymerization initiator of aromatic sulfonium salt, for example, Adeka optomer SP-150, SP-151, SP-152, SP-170, SP-171, SP-172 (made by Adeka company), Uvacure 1590 (Daicel) UCB), CYRACURE UVI-6990 (manufactured by Union Carbide), TPS-103, MDS-103, DTS-103 and NDS-103 (manufactured by Midori Chemical Co., Ltd.), and the like.

  These photopolymerization initiators (C) may be used alone or in combination of two or more.

In the above curable composition, the content of the photopolymerization initiator (C) is not particularly limited, but the cationically polymerizable compound (A), the radically polymerizable compound (B), the photopolymerization initiator (C) And 0.1 to 5.0 parts by mass, more preferably 0.2 to 3.0 parts by mass with respect to 100 parts by mass of the total mass of the thermal polymerization initiator (D). When the content of the photopolymerization initiator (C) is smaller than 0.1 part by mass, it is conceivable that the polymerization reaction by light does not proceed sufficiently, and when it is larger than 5.0 parts by mass, the photopolymerization initiator (C) May precipitate out.
For example, in the case of forming a cured product having a film thickness of 1 to 100 μm, the content of the photopolymerization initiator (C) is a cationically polymerizable compound (A), a radically polymerizable compound (B), a photopolymerization initiator (C) And 0.1 to 5.0 parts by mass, more preferably 0.2 to 3.0 parts by mass with respect to 100 parts by mass of the total mass of the thermal polymerization initiator (D). When the content of the photopolymerization initiator (C) is smaller than 0.1 parts by mass, the polymerization reaction by light may not proceed sufficiently, and when it is larger than 5.0 parts by mass, the photopolymerization initiator (C) is May precipitate out.

<Thermal polymerization initiator (D)>
The thermal polymerization initiator (D) is not particularly limited, but a thermal radical polymerization initiator and a thermal cationic polymerization initiator are preferable.

  The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and conventionally known compounds can be used, and examples thereof include azo compounds and peroxides.

As an azo compound, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-) Dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), (1-phenylethyl) azodiphenylmethane, dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2-phenylazo -2,4-Dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (N, N'-dimethylene isobutyl amidine), 2,2'-azobis (2-amidinops Pan) dihydrochloride, 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (isobutyramide), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) Propionamide], 2,2′-azobis [2-methyl-N- (1,1-bis (hydroxymethyl) ethyl) propionamide] and 2,2′-azobis [2-methyl-N- (1,1 And -bis (hydroxymethyl) -2-hydroxyethyl) propionamide] and the like.
As the peroxide, for example, diisopropyl peroxy dicarbonate, 2,4-dichlorobenzoyl peroxide, t-butyl peroxy pivalate, octanoyl peroxide, stearoyl peroxide, lauroyl peroxide, acetyl peroxide, t-butyl Peroxyisobutyrate, benzoyl peroxide, cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, di-t-butyl diperoxy phthalate, t-butylperoxy acetate, 2,5-dimethyl-2,5-di (Benzoylperoxy) hexane, t-butylperoxylaurate, t-butylperoxybenzoate, dicumylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylhigh Roperoxide, methyl ethyl ketone peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, pinane hydroperoxide, Examples thereof include cumene hydroperoxide and 2,5-dimethylhexane-2,5-dihydroperoxide.

  The thermal cationic polymerization initiator is not particularly limited as long as it is a compound that generates a cationic species or a Lewis acid upon heating, and a conventionally known compound can be used, and for example, an onium salt initiator can be used .

  Examples of the onium salt initiators include aryldialkylsulfonium hexafluoroantimonate, aryldialkylsulfonium hexafluorophosphate, diarylalkylsulfonium hexafluoroantimonate, aryldialkylsulfonium tetraperfluorophenyl borate and the like. Examples include sulfonium salts, iodonium salts such as diaryliodonium hexafluoroantimonate, diaryliodonium hexafluorophosphate and diaryliodonium tetraperfluorophenyl borate. These are readily available in the market.

  A commercial item can also be used for the said thermal cationic polymerization initiator. For example, Adekaopton CP-77, Adeka Opton CP-66 (made by ADEKA), CI-2639, CI-2624 (Nippon Soda), San Aid SI-60L, San Aid SI-80 L, San Aid SI-100 L (manufactured by Sanshin Chemical Industries) etc. Can be mentioned.

  The said thermal-polymerization initiator (D) may use only 1 type, and may use 2 or more types together.

In the above curable composition, the content of the thermal polymerization initiator (D) is not particularly limited, but the cationically polymerizable compound (A), the radically polymerizable compound (B), the photopolymerization initiator (C) And 0.1 to 5.0 parts by mass, more preferably 0.5 to 3.0 parts by mass, per 100 parts by mass of the sum of the mass of the thermal polymerization initiator (D). When the content of the thermal polymerization initiator (D) is smaller than 0.1 parts by mass, the polymerization reaction by heat may not proceed sufficiently, and when the content is larger than 5.0 parts by mass, the thermal polymerization initiator (D) May precipitate out.
For example, in the case of forming a cured product having a film thickness of 1 to 100 μm, the content of the thermal polymerization initiator (C) is a cationically polymerizable compound (A), a radically polymerizable compound (B), a photopolymerization initiator (C) And 0.1 to 5.0 parts by mass, more preferably 0.5 to 3.0 parts by mass, per 100 parts by mass of the sum of the mass of the thermal polymerization initiator (D). When the content of the thermal polymerization initiator (D) is smaller than 0.1 part by mass, it is conceivable that the polymerization reaction by light does not proceed sufficiently, and when it is larger than 5.0 parts by mass, the thermal polymerization initiator (D) May precipitate out.

<Cation Curing Retarder (E)>
The cationic curing retarder (E) is not particularly limited, and a compound having an effect of delaying the cationic curing can be preferably used.
An appropriate amount of the cationic curing retarder (E) may be further added to the curable composition for the purpose described below. The purpose of adding the cationic curing retarder is to control the cationic curing, to maintain the tackiness after the first curing for a long time, and to raise the glass transition temperature of the cured product after the second curing. .

Examples of the cation curing retarder (E) include onium salts such as sulfonium salts, polyols, aliphatic compounds having a hydroxyl group, ether compounds, amine compounds and alkyl sulfide compounds, etc., but the second curing From the viewpoint of being capable of delaying the cationic curing without significantly reducing the reaction rate at the time of performing the reaction, it is preferable to exhibit a delayed curing property by salt exchange, and specifically, a sulfonium salt is more preferable. There is no restriction | limiting in particular in a cation site | part as a sulfonium salt which can be used as a cation hardening retarder (E), It is necessary to select a suitable counter anion. Suitable counter anions, for _{example, BF 4, NC-N-} CN, CH 3 -Ph-SO 3 and C _{(CN) 3} and the like

  A commercial item can also be used for the said cation curing retarder (E). As a cationic curing retarder (E) marketed, for example, Cyracure UVI-6990 (manufactured by Union Carbite Co., Ltd.) and Sanaid SI-S (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like can be mentioned.

In the above curable composition, the content of the cationic curing retarder (E) is not particularly limited, but the cationically polymerizable compound (A), the radically polymerizable compound (B), the photopolymerization initiator (C) And 0 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, per 100 parts by mass of the sum of the mass of the thermal polymerization initiator (D). When the content of the cation curing retarder (E) is more than 10 parts by mass, the cationic polymerization reaction may not proceed.
For example, in the case of forming a cured product having a film thickness of 1 to 100 μm, the content of the cationic curing retarder (E) is as large as the cationic polymerizable compound (A), the radical polymerizable compound (B), and the photopolymerization initiator (C). And 0 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, per 100 parts by mass of the sum of the mass of the thermal polymerization initiator (D). When the content of the cation curing retarder (E) is more than 10 parts by mass, the cationic polymerization reaction may not proceed.

  If necessary, a solvent capable of dissolving or dispersing the components (A) to (E) can be added to the curable composition. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, methanol , Ethanol and isopropanol can be added.

  In the above curable composition, other monomers (especially alcohol monomers), other energy ray sensitive polymerization initiators, inorganic fillers, organic fillers, pigments, silanes, if necessary, as long as the effects of the present invention are not impaired. Coupling agents, coloring agents such as dyes, photosensitizers, antifoaming agents, thickeners, thixo agents, surfactants, leveling agents, flame retardants, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, Various resin additives such as an antioxidant, an antistatic agent, a flow control agent and an adhesion promoter can be added.

  The alcohol monomer is not particularly limited as long as it is a compound having a hydroxyl group, and a conventionally known compound can be used.

  As the alcohol monomer, it is preferable to use a polyhydric alcohol because of its good curability. Examples of polyhydric alcohols include ethylene glycol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, polyethylene glycol, 2-methyl-2-ethyl-1,3-propanediol Aliphatic diols such as 2, 2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, alicyclic diols such as 1,2-cyclohexanediol, sorbitol, 1 , 2,3,6-Hexanetetrarole, 1,4-sorbitan, pentae Slititol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol And trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and polycaprolactone triol having three hydroxyl groups at the end.

  A commercial item can be used as said polycaprolactone triol which has three hydroxyl groups at the terminal. Plaxel 300, 305, 306, 308, 312 and 320 (manufactured by Daicel Chemical Industries, Ltd.) and the like.

  In the above curable composition, other than the radically polymerizable compound (A), the cationically polymerizable compound (B), the photopolymerization initiator (C), the thermal polymerization initiator agent (D), the cationic curing retarder (E) and the solvent The content of the optional component is suitably selected according to the purpose of use and is not particularly limited, but preferably, it is 20 parts by mass or less in total with respect to 100 parts by mass of the solid content of the curable composition. If the content of the optional component exceeds 20 parts by mass, the effects of the present invention may not be sufficiently exhibited.

  About the manufacturing method of the hardened | cured material of this invention, the preferable coating method, hardening method, and hardening conditions are shown below.

The curable composition can be applied by any known means such as die coater, roll coater, curtain coater, various printing, immersion, etc. Diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, Cellulose esters such as lyl cellulose, acetyl propionyl cellulose and nitrocellulose; polyamide; polycarbonate; polyethylene terephthalate; polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane- Polyesters such as 4,4'-dicarboxylate and polybutylene terephthalate; Polystyrene; Polyolefins such as polyethylene, polypropylene and polymethylpentene; Poly Acrylic resins such as methyl methacrylate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; polyether imide; plastics such as polyoxyethylene and norbornene resin; glass such as soda glass and quartz glass; semiconductor substrate; metal; Etc. on a supporting substrate. Moreover, it can also apply | coat to a peeling film etc. once and it can also transfer on another support base after 1st hardening, and there is no restriction | limiting in the application method.
Although there is no restriction | limiting in particular about the film thickness of a curable composition, In order to obtain the hardened | cured material excellent in flexibility, low moisture permeability, and a high elasticity modulus, 1-10 micrometers is preferable.

The curing method of the curable composition includes photopolymerization and thermal polymerization. The curing conditions are appropriately selected according to the purpose of use as long as the modulus of elasticity of the cured product after the first curing and the modulus of elasticity of the cured product after the second curing each fall within the above ranges, and is not particularly limited. Is as described below.
Photopolymerization is cured by irradiation with active energy rays. As an active energy ray, an ultraviolet ray, an electron beam, an X ray, radiation, a high frequency etc. can be mentioned, An ultraviolet ray is economically most preferable. Examples of the ultraviolet light source include ultraviolet lasers, mercury lamps, xenon lasers, metal halide lamps, and sunlight. When thermal polymerization is performed after photopolymerization, it is desirable that the curable composition is not excessively heated when light irradiation is performed. As a method of not heating excessively, for example, introduction of a heat ray cut filter, limitation of irradiation amount (preferably 100 mJ / cm ^{2 to} 1000 mJ / cm ² ), cooling of an adherend, etc. may be mentioned.
Thermal polymerization is preferably carried out at a temperature of 200 ° C. or less for 1 hour or less, in consideration of the thermal stability of the polymerizable compound which is cured by photopolymerization, in the case of photopolymerization after thermal polymerization.

  In the method for producing a cured product of the present invention, there is no particular limitation on the combination of the polymerization reaction for performing the first curing and the polymerization reaction for performing the second curing, but when the polymerization reaction for the first curing is a radical reaction, Since there is no dark reaction observed, the polymerization reaction does not proceed when stored after the first curing. Therefore, the developed adhesiveness is maintained for a long time, and the pot life is useful for a long time. Moreover, when the polymerization reaction which performs 2nd hardening is cationic polymerization, since the hardened | cured material after 2nd hardening becomes high adhesive strength and low moisture permeability, it is preferable.

  In the method for producing a cured product of the present invention, the combination of the polymerization reaction for the first curing and the polymerization reaction for the second curing is not particularly limited, but the polymerization reaction for the first curing is a photopolymerization reaction to perform the second curing. When the polymerization reaction is a thermal polymerization reaction, it is preferable because it easily adapts to an opaque adherend.

Hereinafter, although the specific example is given about the manufacturing method of hardened | cured material, this invention is not limited to the following manufacturing method.
For example, after the curable composition is applied to a readily adhesive-treated polyethylene terephthalate film by a die coater to a film thickness of 5 μm, ultraviolet light is irradiated with 500 mJ / cm ² (first curing) by a high pressure mercury lamp to bond to glass; A laminate is obtained by heating (second curing) for 1 hour.
After the curable composition was applied to a peeling film with a die coater to a film thickness of 5 μm, ultraviolet light was irradiated with 500 mJ / cm ² (first curing) by a high pressure mercury lamp to bond to glass, and the peeling film was peeled Thereafter, glass is further bonded to the peeled surface, and heating (second curing) is performed at 120 ° C. for 1 hour to obtain a laminate.

  Specific applications of the cured product obtained by the method for producing a cured product according to the present invention are glasses, optical materials represented by imaging lenses, printing plates, insulating varnishes, insulating sheets, laminates, printed substrates, glass fibers Impregnation agents, passivation films (for semiconductors and solar cells, etc.), interlayer insulating films, protective films, prism lens sheets used for backlights of liquid crystal display devices, Fresnel lens sheets used for screens of projection televisions and the like, and lenticular The lens portion of a lens sheet such as a lens sheet or a backlight using such a sheet can be used for various applications such as an optical lens such as a micro lens, an optical element, an optical connector and an optical waveguide There is no particular limitation on the application.

  Specific applications of the curable resin composition include glasses, optical materials represented by imaging lenses, paints, coatings, lining agents, inks, resists, liquid resists, adhesives, printing plates, insulating varnishes, Insulating sheets, laminates, printed circuit boards, sealants (for semiconductor devices, for LED packages, for liquid crystal injection ports, for organic EL, for optical devices, for electrical insulation, for electronic parts, for separation films, etc.), molding materials , Putty, glass fiber impregnating agent, filler, passivation film (for semiconductor and solar cell etc.), interlayer insulating film, protective film, prism lens sheet used for back light of liquid crystal display, projection television etc. Lens portion of lens sheet such as Fresnel lens sheet and lenticular lens sheet used for screen, or for such sheet Backlights were, an optical lens such as a micro lens, the optical element, the optical connector can be used for various purposes casting agent for optical waveguides and optical shaping is not particularly limited in its application.

  The curable composition can be suitably used as an adhesive. Specific applications of adhesives include optical materials represented by glasses and imaging lenses; electronic materials applications represented by laminates and printed substrates; automotive devices represented by head-up displays and car navigation; It can be used in various applications such as display panels represented by organic EL and liquid crystal, and the application thereof is not particularly limited. The adhesive of the present invention is particularly useful as an adhesive for display panels for which optical properties are required.

  EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[Examples 1 to 12 and Comparative Examples 1 to 5] Preparation of Curable Composition
Each component was mixed according to the mixing | blending of [Table 1]-[Table 3], and the curable composition (Examples 1-12 and Comparative Examples 1-5) was obtained. The numbers in the table represent parts by mass. Moreover, the code | symbol of each component in a table | surface represents the following components.
A-1 Adeka Resin EP-4100 E (diglycidyl ether compound; manufactured by ADEKA)
A-2 Celoxide 2021 P (alicyclic epoxy compound; manufactured by Daicel Chemical Industries, Ltd.)
A-3 Adeka Glycyrol ED-505 (Multifunctional Epoxy Compound; Made by Adeka)
A-4 Aron oxetane OXT-221 (oxetane compound; manufactured by Toagosei Co., Ltd.)
A-5 Adeka Resin EP-4080 (diglycidyl ether compound; manufactured by Adeka)
A-6 Adeka Resin EP-4088 (diglycidyl ether compound; manufactured by Adeka)
A-7 Adekasizer BF-1000 (polybutadiene epoxy compound; manufactured by ADEKA)
A-8 3,3 '-(propane-2,2-diyl) bis (7-oxabicyclo [4.1.0] heptane)
A-9 Aron Oxetane OXT-101 (Oxetane Compound; manufactured by Toagosei Co., Ltd.)
A-10 1,4-butanediol divinyl ether B-1 NK ester A-DCP (acrylic compound having a saturated aliphatic ring in the structure; manufactured by Shin-Nakamura Chemical Co., Ltd.)
B-2 NK Ester BPE-500 (Epoxy Methacrylic Compound; Shin-Nakamura Chemical Co., Ltd.)
B-3 ARONIX M-140 (monofunctional acrylic compound; manufactured by Toagosei Co., Ltd.)
B-4 NK Ester A-9300 (Multifunctional Acrylic Compound; Shin-Nakamura Chemical Co., Ltd.)
B-5 NK Ester A-TMPT (Multifunctional Acrylic Compound; Shin-Nakamura Chemical Co., Ltd.)
C-1 LUNA 100 (photo radical initiator; manufactured by Nihon Shiver Hegner)
C-2 IRGACURE-651 (photo radical initiator; manufactured by BASF)
C-3 Adeka Optomer SP-170 (photocation initiator; manufactured by ADEKA)
D-1 San Aid SI-B3 (Thermal cationic initiator; manufactured by Sanshin Chemical Industry Co., Ltd.)
D-2 Adekaopton CP-66 (Thermal cationic initiator; manufactured by ADEKA)
D-3 San Aid SI-100 L (Thermal cationic initiator; manufactured by Sanshin Chemical Industry Co., Ltd.)
E-1 SANAID SI-S (cationic curing retarder; manufactured by Sanshin Chemical Industries, Ltd.)
F-1 Plaxel 300 (polyhydric alcohol; manufactured by Daicel Chemical Industries, Ltd.)
F-2 acrylic polymer (copolymer of butyl acrylate, hydroxyethyl acrylate and acrylic acid MW 600000)
F-3 Coronate L 45 (polyisocyanate; manufactured by Nippon Polyurethane Industry Co., Ltd.)
F-4 Ethyl acetate

Evaluation Examples 1 to 12 and Comparative Evaluation Examples 1 to 5
The polymerization reaction was performed under curing conditions I to IV shown below to obtain a cured product.
The obtained cured product was evaluated for elastic modulus, total light transmittance, moisture permeability, adhesive strength and flexibility by the methods described below. The results are shown in [Table 1] to [Table 3].
Curing conditions I:
[First cure] photopolymerization reaction, high pressure mercury lamp 500 mJ / cm ² (80 mW / cm ² )
[Second Curing] Thermal polymerization reaction, heating at 120 ° C. for 1 hour Curing conditions II:
[First cure] photopolymerization reaction, high pressure mercury lamp 100 mJ / cm ² (80 mW / cm ² )
[Second Curing] Thermal polymerization reaction, heating at 120 ° C. for 1 hour Curing conditions III:
[First cure] photopolymerization reaction, high pressure mercury lamp 1000 mJ / cm ² (80 mW / cm ² )
[Second Curing] Thermal polymerization reaction, heating at 120 ° C. for 1 hour Curing conditions IV:
[First curing] solvent drying, 80 ° C. × 3 minutes [Second curing] thermal polymerization reaction, heating at 40 ° C. × 24 hours

(Elastic modulus)
A curable composition prepared to have a film thickness of 50 μm by using Anton Paar's Rheometer. After the first curing, the modulus of elasticity after further 3 hours at 25 ° C. after the first curing and after the second curing The results are shown in the stability of elastic modulus after first curing and the elastic modulus after second curing in [Table 1] to [Table 3], respectively. In Comparative Example 1 (curing condition IV), the modulus of elasticity is measured immediately after drying, after 3 hours at 25 ° C. after drying, and after thermal polymerization reaction, respectively, after the first curing in [Table 3]. It is described in the stability of the elastic modulus and the elastic modulus after the second curing.

(Total light transmittance)
The curable composition described in [Table 1] to [Table 3] is formed into a glass plate so as to have a film thickness of 50 μm, and cured under the curing conditions described in [Table 1] to [Table 3] Then, the total light transmittance of 400 to 800 nm was measured. The measurement was performed using a haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.

(Moisture permeability)
Place a spacer on a transparent release support plate to a film thickness of 50 μm, and after flowing the curable composition described in [Table 1] to [Table 3], another transparent release form After sandwiching by the support plate, the curable composition was cured under the curing conditions described in [Table 1] to [Table 3]. Thereafter, the cured product was peeled off from the transparent release support plate to obtain a single film. The moisture permeability of the prepared single film was measured by the MOCON method (humidity 90 RH% temperature 40 ° C.).

(Adhesive strength)
The curable composition described in [Table 1] to [Table 3] is coated on a PET film so as to have a film thickness of 50 μm, and after being made the first curing (comparative example 1 is drying), it is pasted to glass The second curing was performed. The adhesive strength of the obtained cured product was measured using an AIKOH load tester FTN 1-13A. Adhesive strength exceeding 10 N / 25 mm was ◎, that of 5 to 10 N / 25 mm was ○, and that of 1 to 5 N / 25 mm was Δ: less than 1 N / 25 mm was x.

(Flexibility)
The curable composition was applied onto easy-to-adhere PET film (A-4300 / film thickness 100 μm) to a film thickness of about 10 μm, and the coated curable composition is shown in [Table 1] to [Table 3]. The film was cured under the conditions described to obtain a film having a film formed on the surface. The obtained film was wound around a metallic cylinder of 2 mm in diameter so that the surface on which the film was formed was directed outward, and it was visually confirmed whether or not there was an abnormality such as a crack in the film on the film surface. The thing in which abnormality was not observed was made into O, and the thing in which abnormality was observed was made into x.

From the above results, in the curable composition, the elastic modulus does not greatly change depending on the curing conditions after the first curing, and the stability of the elastic modulus is good, and the high transparency and low after the second curing It is clear that simultaneously the moisture permeability, the strong adhesion and the flexibility are satisfied. Accordingly, the curable composition is also applicable to opaque adherends, and can be suitably used as an adhesive that requires high transparency, low moisture permeability, strong adhesion and flexibility. In particular, it is useful as an adhesive for display panels.

Claims (4)

In a method of producing a cured product using a curable composition,
It is essential to carry out two or more kinds of polymerization reactions,
In the process of converting the curable composition into a cured product, it is essential to go through the first curing with an elastic modulus of 10 ³ to 10 ⁶ Pa,
The elastic modulus of the second cured product is 10 ⁷ Pa or more,
The method of first curing the curable composition is a radical polymerization reaction by irradiation of active energy rays, and the method of second curing is a cationic polymerization reaction,
The dose of the active energy ray ^{is 100mJ / cm 2 ~500mJ / cm 2} ,
The curable composition contains a cationically polymerizable compound (A), a radically polymerizable compound (B), a photopolymerization initiator (C) , a thermal polymerization initiator (D) and a cationic curing retarder (E) ,
The cationically polymerizable compound (A) is at least one selected from the group consisting of diglycidyl ether compounds, polyfunctional epoxy compounds and alicyclic epoxy compounds,
The radically polymerizable compound (B) is selected from the group consisting of monofunctional (meth) acrylic compounds, (meth) acrylic compounds having a saturated aliphatic ring in the structure, polyfunctional (meth) acrylic compounds and epoxy (meth) acrylic compounds At least one or more,
Content of a cationically polymerizable compound (A) is a total of 100 mass parts of mass of a cationically polymerizable compound (A), a radically polymerizable compound (B), a photoinitiator (C), and a thermal-polymerization initiator (D) The manufacturing method of hardened | cured material which is a curable composition which is 50-95 mass parts with respect to. In the method for producing the cured product,
The method for producing a cured product according to claim 1, wherein the second curing method is a thermal polymerization reaction. It is a curable composition used by the manufacturing method of the hardened | cured material of Claim 1 or 2 , Comprising:
The curable composition contains a cationically polymerizable compound (A), the radical polymerizable compound (B), the photopolymerization initiator (C), a thermal polymerization initiator (D) and cationic retarder (E),
The cationically polymerizable compound (A) is at least one selected from the group consisting of diglycidyl ether compounds, polyfunctional epoxy compounds and alicyclic epoxy compounds,
The radically polymerizable compound (B) is selected from the group consisting of monofunctional (meth) acrylic compounds, (meth) acrylic compounds having a saturated aliphatic ring in the structure, polyfunctional (meth) acrylic compounds and epoxy (meth) acrylic compounds At least one or more,
Content of a cationically polymerizable compound (A) is a total of 100 mass parts of mass of a cationically polymerizable compound (A), a radically polymerizable compound (B), a photoinitiator (C), and a thermal-polymerization initiator (D) The curable composition which will be 50-95 mass parts with respect to. An adhesive comprising the curable composition according to claim 3 .