JP2017179166A - Curable composition, and method for producing cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that has excellent storage stability and a high curing rate as an adhesive.SOLUTION: A curable composition comprises a glycidyl group compound, at least one selected from an alicyclic epoxy compound and an oxetane compound, a compound represented by formula (1) and a compound represented by diphenyl,4-(phenylsulfide) sulfonium hexafluoro phosphate.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition and a method for producing the cured product, and more particularly to a curable composition having excellent adhesion and storage stability and a high curing rate, and a method for producing the cured product.

  Curable compositions are widely used as adhesives, and adhesives are used in a wide range of fields including automobiles, aircraft, and electrical / electronic devices. In particular, in recent years, the application of adhesive technology in electrical and electronic equipment has become increasingly diverse and sophisticated. In addition, materials used in electrical and electronic equipment have been newly developed and have become diverse and diverse, and conventional adhesives cannot satisfy sufficient requirements. In particular, conventional adhesives are unable to satisfy sufficient requirements for producing fine optical components typified by polarizing plates used in liquid crystal display devices.

  As conventional adhesives, for example, in Patent Document 1, a photocationically curable adhesive and an aliphatic epoxy containing an aliphatic epoxy compound, an alicyclic epoxy compound and / or an oxetane compound, and a photopolymerization initiator. A thermal cation curable adhesive containing a compound, an alicyclic epoxy compound and / or an oxetane compound, and a thermal polymerization initiator has been proposed. Patent Document 2 proposes an adhesive mainly composed of an epoxy resin that does not contain an aromatic ring. As a polymerization initiator, Patent Document 3 proposes an energy ray-sensitive cationic polymerization initiator having an excellent function.

Japanese Patent No. 5037074 JP 2004-245925 A JP 2004-359605 A

  However, the conventionally proposed adhesives have problems that adhesion is insufficient, the curing rate is slow, and the viscosity changes when stored for a long period of time. Furthermore, the energy ray-sensitive cationic polymerization initiator proposed in Patent Document 3 has a problem that the curing rate may be slow depending on the combination with the resin component, and further improvement is desired. is the current situation.

  Then, the objective of this invention is providing the curable composition which is excellent in adhesiveness and storage stability, and has a quick hardening rate, and the manufacturing method of the hardened | cured material.

  As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by a curable composition having a specific composition, and has completed the present invention.

で表される化合物と、下記一般式（２）、

（式（１）、（２）中、Ｒ^１〜Ｒ^４７は、各々独立して水素原子、ハロゲン原子、炭素原子数１〜１２のアルキル基、炭素原子数１〜１２のヒドロキシアルキル基、炭素原子数１〜１２のアルコキシ基、炭素原子数１〜１２のヒドロキシアルコキシ基、置換基を有していてもよいフェニル基、置換基を有していてもよいフェノキシ基およびニトロ基のいずれかから選択される基であり、Ｘは１価のアニオンになりうる原子団である。）で表される化合物と、を含む硬化性組成物において、
前記グリシジル基を有する化合物１００質量部当たり、前記脂環式エポキシ化合物０〜５０質量部、前記オキセタン化合物０〜５０質量部、上記一般式（１）で表される化合物０．１〜１０質量部、上記一般式（２）で表される化合物０．１〜１０質量部、を含むことを特徴とするものである。 That is, the curable composition of the present invention includes a compound having a glycidyl group, at least one selected from the group consisting of an alicyclic epoxy compound and an oxetane compound, the following general formula (1),

A compound represented by the following general formula (2),

(In the formulas (1) and (2), R ^{1 to} R ⁴⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 1 to 12 carbon atoms, or carbon. From any one of an alkoxy group having 1 to 12 atoms, a hydroxyalkoxy group having 1 to 12 carbon atoms, an optionally substituted phenyl group, an optionally substituted phenoxy group and a nitro group A selected group, and X is an atomic group that can be a monovalent anion).
0-100 parts by mass of the alicyclic epoxy compound, 0-50 parts by mass of the oxetane compound, 0.1-10 parts by mass of the compound represented by the general formula (1) per 100 parts by mass of the compound having the glycidyl group. And 0.1 to 10 parts by mass of the compound represented by the general formula (2).

In the curable composition of the present invention, in the general formula (1) and the general formula (2), the anion moiety represented by X ⁻ is SbF ₆ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , BF ₄ ^−. , SbCl ₆ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , FSO ₃ ⁻ , F ₂ PO ₂ ⁻ , p-toluene sulfonate, camphor sulfonate, nonafluorobutane sulfonate, It is preferably at least one selected from the group consisting of hexadecafluorooctane sulfonate and tetraarylborate.

The method for producing a cured product according to the present invention includes a substrate preparation step for preparing a substrate, a coating step for applying the curable composition to the substrate, and an irradiation step for irradiating energy rays.
The curable composition is the curable composition of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in adhesiveness and storage stability, and can provide the curable composition with a quick hardening rate, and the manufacturing method of the hardened | cured material.

  The curable composition of the present invention can be suitably used as an adhesive because of its effects, and more specifically, is suitably used for applications of a photocationic curable adhesive and a thermal cation curable adhesive. Among them, it is particularly suitable as a photocationic curable adhesive. In addition, the curable composition of the present invention is suitable as an adhesive used when producing a fine optical component represented by a polarizing plate because of its high curing speed and high adhesion. As an adhesive used for the polarizing plate, for example, a triacetyl cellulose (hereinafter sometimes abbreviated as TAC) film is bonded to both surfaces of a polyvinyl alcohol (hereinafter sometimes abbreviated as PVA) polarizer film. Adhesive used at the time, polyester resin, polycarbonate resin, acrylic resin, amorphous polyolefin resin or cycloolefin resin as a protective film or optical compensation film on one side, and TAC film on the other side Adhesives used for combining can be mentioned as suitable applications.

  Hereinafter, the curable composition of the present invention and the method for producing the cured product will be described in detail.

  The curable composition of the present invention is represented by the following general formula (1), at least one selected from the group consisting of a compound having a glycidyl group, a compound having a glycidyl group, an alicyclic epoxy compound and an oxetane compound. And a compound represented by the following general formula (2). In the hardened | cured material composition of this invention, 0-100 mass parts of alicyclic epoxy compounds, 0-50 mass parts of oxetane compounds, and the compound represented by following General formula (1) per 100 mass parts of compounds which have a glycidyl group. 0.1-10 mass parts and 0.1-10 mass parts of compounds represented by following General formula (2) are included.

ここで、式（１）、（２）中、Ｒ^１〜Ｒ^４７は、各々独立して水素原子、ハロゲン原子、炭素原子数１〜１２のアルキル基、炭素原子数１〜１２のヒドロキシアルキル基、炭素原子数１〜１２のアルコキシ基、炭素原子数１〜１２のヒドロキシアルコキシ基、置換基を有していてもよいフェニル基、置換基を有していてもよいフェノキシ基およびニトロ基のいずれかから選択される基であり、Ｘは１価のアニオンになりうる原子団である。

Here, in formulas (1) and (2), R ^{1 to} R ⁴⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or a hydroxyalkyl group having 1 to 12 carbon atoms. Any of an alkoxy group having 1 to 12 carbon atoms, a hydroxyalkoxy group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, and a nitro group X is an atomic group that can be a monovalent anion.

  The compound having a glycidyl group used in the curable composition of the present invention is not particularly limited as long as it is a compound having a glycidyl group, and an aliphatic epoxy compound can be preferably used. Or the polyglycidyl ether of the alkylene oxide adduct can be used preferably.

  For example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol di Glycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane diglycidyl ether, polyethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol bonolac type epoxy resin, etc. Can be mentioned. From the viewpoint of low viscosity, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether are preferable.

  Examples of commercially available compounds having a glycidyl group include ADEKA glycylol ED-523 (neopentyl glycol diglycidyl ether) and ADEKA glycilol ED-503 (1,6-hexanediol diglycidyl ether) manufactured by ADEKA Corporation. Adeka Resin EP-4085 (cyclohexanedimethanol diglycidyl ether), Adeka Resin EP-4080 (hydrogenated bisphenol A diglycidyl ether), Adeka Resin EP-4100L, Adeka Resin EP-4901, Epolite 100MF (Trimethylol) manufactured by Kyoeisha Chemical Co., Ltd. Propane triglycidyl ether) and Nagase ChemteX Corporation EX-321L (trimethylolpropane diglycidyl ether). Among these, when the weight average molecular weight is 500 or less, it is preferable because the effect of making the coated surface uniform when coating the curable composition of the present invention is high and the adhesive strength is high. Further, it is preferable to use a compound having a glycidyl group having a chemical purity of 98% or more. The chemical purity of 98% or more means a case where the amount of impure organic substances other than the compound having a glycidyl group present in the compound having a glycidyl group is less than 2%.

  Examples of the alicyclic epoxy compound used in the curable composition of the present invention include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9 diepoxy limonene, 3,4- And epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate. These are commercially available from Daicel Chemical Industries, Ltd. under the trade names CEL2000, CEL3000, and CEL2021P. The alicyclic epoxy compound used in the curable composition of the present invention preferably has two or more epoxy groups in its structure.

  The oxetane compound is a compound having a 4-membered ring ether, that is, an oxetane ring in the molecule. Examples of oxetane compounds used in the curable composition of the present invention include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] benzene, 3-ethyl. -3- (phenoxymethyl) oxetane, bis (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane), 3-ethyl-[{(3-triethoxy Silylpropoxy) methyl) oxetane, oxetanylsilsesquioxane, phenol novolac oxetane and the like. Here, the oxetanyl silsesquioxane is obtained by hydrolytic condensation of a silane compound having an oxetanyl group, for example, the aforementioned 3-ethyl-3-[{(3-triethoxysilyl) propoxy} methyl] oxetane. A network-like polysiloxane compound having a plurality of oxetanyl groups. Among these oxetane compounds, 3-ethyl-3-hydroxymethyloxetane, bis (3-ethyl-3-oxetanylmethyl) ether, and 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane are preferable.

  Commercially available products of oxetane compounds include, for example, trade names OXT-101 (3-ethyl-3-hydroxymethyloxetane) and OXT-211 (3-ethyl-3- (phenoxy) commercially available from Toagosei Co., Ltd. Methyl) oxetane), OXT-221 (3-ethyl-3-{[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane), OXT-212 (2-ethylhexyloxetane), Thus, those having two or more oxetane rings in the structure are preferred.

  Next, the compounds represented by the general formula (1) and the general formula (2) used in the curable composition of the present invention will be described.

R ^{1 to} R ⁴⁷ in the general formula (1) and the general formula (2) are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or a hydroxyalkyl having 1 to 12 carbon atoms. Group, an alkoxy group having 1 to 12 carbon atoms, a hydroxyalkoxy group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a nitro group It is a group selected from either.

  Among these groups, preferred are hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, propyl group, isopropyl group, hydroxymethyl group, hydroxyethyl group, methoxy group, ethoxy group, methoxyethoxy group, Examples thereof include a hydroxyethyloxy group, a 2-hydroxyethyloxy group, a 1,2-dihydroxypropyloxy group, a phenyl group, a tolyl group, a phenoxy group, and a nitro group.

Further, it may be all of these hydrogen atoms, but all that is curable other than hydrogen atom, the solubility and undesirable from the viewpoint of industrialization suitability preferably identical among R ¹ to R ⁴⁷ At least one of those bonded to the benzene ring is preferably a hydrogen atom. More preferably, all of R ^{1 to} R ⁴⁷ are hydrogen atoms, or, in general formula (1), R ^{11 to} R ¹⁸ are hydrogen atoms, and one of R ^{1 to} R ⁵ is the above hydrogen atom. Other than the atoms, the remainder is a hydrogen atom, one of R ^{6 to} R ¹⁰ is other than the hydrogen atom and the remainder is a hydrogen atom, and one of R ^{19 to} R ²³ is other than the hydrogen atom and the remainder is a hydrogen atom It is preferable that one of R ^{24 to} R ^{28 is} an atom other than the hydrogen atom and the remainder is a hydrogen atom, and in general formula (2), R ^{39 to} R ⁴⁷ are hydrogen atoms, It is preferable that one of R ^{29 to} R ³³ is other than the hydrogen atom and the remaining is a hydrogen atom, and one of R ^{34 to} R ³⁸ is other than the hydrogen atom and the remaining is a hydrogen atom.

X ^{− as} the anion moiety may be a monovalent anion, but preferably SbF ₆ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , SbCl ₆ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ^−. , CH ₃ SO ₃ ⁻ , FSO ₃ ⁻ , F ₂ PO ₂ ⁻ , p-toluene sulfonate, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate It is preferable from the point of sclerosis | hardenability and industrialization suitability that it is at least 1 sort chosen from these.

  In the curable composition of the present invention, the mass ratio of the compound represented by the general formula (1) and the compound represented by the general formula (2) is not particularly limited, but increases the curing rate. And the effect of increasing storage stability are improved, the compound of the general formula (1): the compound of the general formula (2) = 99: 1 to 1:99 (molar ratio) is preferable, and 95: 5 to 5 : 95 is more preferred, 90:10 to 10:90 is more preferred, and 90:10 to 50:50 is most preferred.

  As a method for producing the compound represented by the general formula (1) and the compound represented by the general formula (2) according to the curable composition of the present invention, a known method can be adopted, for example, diaryl sulfide and It can be obtained by a known method such as a method of reacting chlorine, a method of reacting diaryl disulfide with chlorine and benzene, or a method of reacting diaryl sulfide and diaryl sulfoxide.

  Combining five components of a compound having a glycidyl group, an alicyclic epoxy compound, an oxetane compound, a compound represented by the general formula (1), and a compound represented by the general formula (2), In the case of cationic curing, a compound having a glycidyl group alone, a compound having a glycidyl group, an alicyclic epoxy compound or an oxetane compound, a compound represented by the general formula (1), and a general formula (2) This is preferable because it exhibits a stronger adhesive force as compared with the case where the four components are combined with the photocationic curing.

  The mixing ratio of the compound having a glycidyl group, at least one selected from the group consisting of an alicyclic epoxy compound and an oxetane compound, and the compound represented by the general formula (1) is 100 masses of the compound having a glycidyl group. 0 to 50 parts by mass, preferably 5 to 35 parts by mass, 0 to 50 parts by mass, preferably 5 to 35 parts by mass of the oxetane compound, and 5 to 35 parts by mass of the compound represented by the general formula (1). 1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, and 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass of the compound represented by the general formula (2). To do. However, the alicyclic epoxy compound and the oxetane compound should not be 0 parts by mass at the same time.

  In the curable composition of the present invention, other additives such as a polymerization initiator, a photosensitizer, an antioxidant and a silane coupling agent can be blended unless the effects of the present invention are impaired.

  As the polymerization initiator, a known general polymerization initiator can be used, and examples thereof include a photopolymerization initiator and a thermal polymerization initiator.

  When using polyester resin, polycarbonate resin, acrylic resin, amorphous polyolefin resin, cycloolefin resin, etc. as an adhesive for bonding to other resins, such as PVA resin, use a photopolymerization initiator. Photocationic curing is convenient and advantageous.

  For example, acrylic resins and cycloolefin resins that have been specially processed in recent years as protective films or optical compensation films on polarizing plates are problematic in that they can be peeled off immediately even when attached to polarizing plates with conventional adhesives. It was. However, the compound having the glycidyl group of the present invention, at least one selected from the group consisting of an alicyclic epoxy compound and an oxetane compound, a compound represented by the general formula (1), and a general formula (2) 4 or 5 of the above-mentioned compound and an acrylic resin or cycloolefin subjected to special processing by photocationic curing with a photopolymerization initiator or thermal cationic curing with a thermal polymerization initiator Even in the case of a resin, a sufficient adhesive force is exerted on the polarizing plate and does not peel off.

  The photopolymerization initiator generates a cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and starts polymerization of an epoxy group.

  The photopolymerization initiator that can be used in the curable composition of the present invention is not particularly limited, and a well-known general photopolymerization initiator can be used. Examples of the photopolymerization initiator suitably used in the present invention include sulfonium salts and iodonium salts.

  Examples of sulfonium compounds include, for example, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide bishexafluoro 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexa Fluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate, 7- [di (p-toluyl) sulfonio] 2-Isopropylthioxanthone tetrakis (pentafluorophenyl) borate, 4-phenylcarbonyl-4′-diphenylsulfonio-diphenylsulfide hexafluorophosphate, 4- (p-tert-butylphenylcarbonyl) -4′-diphenylsulfonio- Examples include diphenyl sulfide hexafluoroantimonate, 4- (p-tert-butylphenylcarbonyl) -4′-di (p-toluyl) sulfonio-diphenyl sulfide tetrakis (pentafluorophenyl) borate.

  Examples of iodonium salt-based compounds include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like.

  These photopolymerization initiators may be used alone or in combination of two or more. Commercial products of these photopolymerization initiators include, for example, trade name PI-2074 commercially available from Rhodia Corporation.

  The thermal polymerization initiator that can be used in the curable composition of the present invention is not particularly limited, and a known general thermal polymerization initiator can be used. Examples thereof include benzylsulfonium salt, thiophenium salt, thioranium salt, benzylammonium, pyridinium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, and amine imide.

  Commercially available products of these initiators can be obtained. For example, trade names Adeka Opton CP77 (above, manufactured by ADEKA Corporation), CI-2639, CI-2624 (above, manufactured by Nippon Soda Co., Ltd.) , Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. The thermal polymerization initiator is preferably blended in the range of 0.5 to 10 parts by mass per 100 parts by mass of the compound having a glycidyl group.

  Furthermore, a photosensitizer can be used in combination with the curable composition of the present invention as necessary. By using a photosensitizer, the reactivity is improved, and the mechanical strength and adhesive strength of the cured product can be improved. Examples of the photosensitizer include anthracene compounds, naphthalene compounds, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreductive dyes.

  Examples of the anthracene compound include those represented by the following formula (3).

ここで、式（３）中、Ｒ^５０およびＲ^５１は、各々独立に水素原子、炭素原子数１〜６のアルキル基または炭素原子数２〜１２のアルコキシアルキル基を表し、Ｒ^５２は水素原子または炭素原子数１〜６のアルキル基を表す。

Here, in Formula (3), R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 12 carbon atoms, and R ⁵² represents a hydrogen atom. Alternatively, it represents an alkyl group having 1 to 6 carbon atoms.

  Specific examples of the anthracene compound represented by the above formula (3) include the following compounds.

  9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentyloxyanthracene, 9, 10-dihexyloxyanthracene, 9,10-bis (2-methoxyethoxy) anthracene, 9,10-bis (2-ethoxyethoxy) anthracene, 9,10-bis (2-butoxyethoxy) anthracene, 9,10-bis (3-butoxypropoxy) anthracene, 2-methyl- or 2-ethyl-9,10-dimethoxyanthracene, 2-methyl- or 2-ethyl-9,10-diethoxyanthracene, 2-methyl- or 2-ethyl- 9,10-dipropoxyanthracene, 2- Til- or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene and the like.

  As a naphthalene-type compound, what is represented by following formula (4) is mentioned, for example.

ここで、式（４）中、Ｒ^５３およびＲ^５４は各々独立に炭素原子数１〜６のアルキル基を表す。

Here, in formula (4), R ⁵³ and R ⁵⁴ each independently represents an alkyl group having 1 to 6 carbon atoms.

  Specific examples of the naphthalene compound represented by the above formula (4) include the following compounds.

  4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene, 1- Ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1,4-dibutoxynaphthalene and the like.

  Examples of other photosensitizers include, for example, benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, o-benzoylbenzoate Benzophenone derivatives such as methyl acid, 4,4′-bis (diethylamino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N -Acridone derivatives such as methylacridone and N-butylacridone; others, α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds, halogen compounds, photoreduction Examples thereof include, but are not limited to, intrinsic dyes. Moreover, these may be used independently or may use 2 or more types together. Examples of commercially available photosensitizers include Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.). The photosensitizer is preferably blended in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the compound having a glycidyl group.

  In the curable composition of this invention, unless the effect of this invention is impaired, another additive, for example, antioxidant, a silane coupling agent, can be mix | blended.

  As the antioxidant, a known general antioxidant can be used. Examples of commercially available antioxidants include AO-20, AO-30, AO-50 and AO-80 (above, manufactured by ADEKA Corporation), dibutylhydroxytoluene (BHT), Irganox 1010, Irganox. 1035FF, Irganox 565, and the like. The usage-amount of antioxidant is 0-10 mass parts per 100 mass parts of compounds which have a glycidyl group, Preferably it is 0.5-5 mass parts.

  As the silane coupling agent, a known general silane coupling agent can be used. Commercially available silane coupling agents include, for example, epoxy (eg KBM403, KBM303), vinyl (KBM1003), acrylic silane coupling agent (KBM503), 3-ethyl (triethoxysilylpropoxymethyl) oxetane (TESOX). (Toagosei Co., Ltd.)). The usage-amount of a silane coupling agent is 0-10 mass parts per 100 mass parts of compounds which have a glycidyl group, Preferably it is 0.5-5 mass parts.

  The curable composition of the present invention preferably has a viscosity of 200 mPa · s or less (25 ° C.), preferably 120 mPa · s or less (25 ° C.). The lower the viscosity, the easier it is to apply the adhesive, and the thinner the adhesive layer can be applied. For example, the adhesive can be suitably used for attaching a protective film or an optical compensation film to the polarizing plate.

  The curable composition of the present invention can be obtained by stirring the above-described components in a container and stirring until a uniform liquid is obtained.

  A method for producing a cured product from the curable composition of the present invention includes a substrate preparation step for preparing a substrate, a coating step for applying the curable composition of the present invention to the substrate, an irradiation step of irradiating energy rays, including.

  Examples of the material of the base used in the base preparation step include silicon; ceramics such as silicon nitride, titanium nitride, tantalum nitride, titanium oxide, ruthenium oxide, zirconium oxide, hafnium oxide, and lanthanum oxide; glass such as soda glass and quartz glass. Metal such as ruthenium metal; cellulose ester such as diacetylcellulose, triacetylcellulose, propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose; polyamide; polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1 , 4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate Polyester such as rate; Polyvinyl alcohol; Polystyrene; Polyolefin such as polyethylene, polypropylene and polymethylpentene; Acrylic resin such as polymethyl methacrylate; Cycloolefin resin; Polysulfone; Polyethersulfone; Polyetherketone; Polyetherimide; Oxyethylene, norbornene resin, etc. can be mentioned, but at least one side of the substrate is a resin film that transmits visible light. Among these, when using PVA, TAC, polyester resin, polycarbonate resin, acrylic resin, amorphous polyolefin resin, and chloroolefin resin, the adhesive strength between the cured product and the substrate is good. To preferred. The amorphous polyolefin-based resin usually has a polymerization unit of a cyclic polyolefin such as norbornene or a polycyclic norbornene-based monomer, and may be a copolymer of a cyclic olefin and a chain cyclic olefin.

  Examples of commercially available non-crystalline polyolefin-based resins include Arton from JSR Corporation, ZEONEX and ZEONOR from Nippon Zeon Co., Ltd., and APO and Appel from Mitsui Chemicals. In order to form the amorphous polyolefin-based resin into a film, a known method such as a solvent casting method or a melt extrusion method is appropriately used. Prior to bonding to the substrate, the bonding surface of the resin film may be subjected to corona treatment, plasma treatment, excimer treatment, and UV treatment. By performing such treatment, adhesion becomes easier. Examples of the shape of the substrate include a plate shape, a spherical shape, a fiber shape, and a scale shape, and the surface of the substrate may be a flat surface or a three-dimensional structure such as a trench structure. The substrate used in the method for forming a cured product of the present invention preferably has a plate shape, and the surface thereof is preferably a flat surface.

  The coating method used in the coating process is not particularly limited. For example, a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, and dipping may be used. it can. Since each coating method has an optimum viscosity range, the viscosity may be adjusted using a solvent. As the solvent for this purpose, a solvent that dissolves the photocationically curable adhesive satisfactorily without degrading the optical performance of the polarizer is used, but the type is not particularly limited. For example, organic solvents such as hydrocarbons typified by toluene and esters typified by ethyl acetate can be used.

  The energy beam used in the irradiation process for irradiating the energy beam is not particularly limited. For example, an ultra high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, a xenon arc. Lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, light emitting diode, electromagnetic wave energy having a wavelength of 2000 angstrom to 7000 angstrom obtained from CRT light source, electron beam, X-ray, radiation, etc. High energy rays can be used. Preferably, an ultrahigh pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, and the like that emit light having a wavelength of 300 to 450 nm are used.

  Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser. Further, lasers that emit light in the visible to infrared region such as various semiconductor lasers and YAG lasers are also used. When these lasers are used, a sensitizing dye that absorbs the visible to infrared region is added. Moreover, it can also be used using a halftone mask. After the step of irradiating with energy rays, it is preferable to cure by heating at room temperature overnight or at 40 to 100 ° C. for 1 to 10 minutes.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited by these Examples.

[Examples 1 to 15 and Comparative Examples 1 to 5]
Using the compounds shown in Table 1, curable compositions of Examples 1 to 15 and Comparative Examples 1 to 5 were produced with the formulations shown in Tables 2 to 5. In addition, the unit of the compounding quantity in a table | surface is a mass part.

※１：一般式（１）で表される化合物
※２：一般式（２）で表される化合物

* 1: Compound represented by general formula (1) * 2: Compound represented by general formula (2)

[Storage stability evaluation]
The viscosities (25 ° C., initial viscosity) of the curable compositions of Examples 1 to 15 and Comparative Examples 1 to 5 were measured and stored at 30 ° C. for 30 days. , Viscosity after storage) was measured, and the viscosity increase rate was calculated as [(viscosity after storage / initial viscosity) × 100] (%). The case where the viscosity increase rate was less than 5% was evaluated as ++, and the case where the viscosity increase rate was 5% or more was evaluated as-. A low viscosity increase rate means a curable composition having high storage stability. The obtained results are also shown in Tables 2-5.

[Curing rate evaluation]
COP (cycloolefin polymer) which applied corona discharge treatment using a laminator after apply | coating the curable composition of Examples 1-15 and Comparative Examples 1-5 to one TAC film which carried out the corona discharge treatment respectively. The test pieces of Examples 1 to 15 and Comparative Examples 1 to 5 were obtained by bonding with a film and irradiating and adhering energy of 100 mJ / cm ² using an electrodeless ultraviolet lamp. All confirmed that it had sufficient adhesiveness.

  In the curable compositions of Examples 1 to 15 and Comparative Examples 1 to 5, the irradiation time necessary to obtain test pieces of the curable compositions of Examples 1 to 15 and Comparative Examples 1 to 5 is measured. The curing speed was evaluated. The case where the curing time was less than 10 seconds was evaluated as ++, and the case where the curing time was 10 seconds or more was evaluated as −. The obtained results are also shown in Tables 2-5. A shorter curing time means a faster curing rate.

  From the results of Tables 2 to 5, it can be seen that the curable compositions of Examples 1 to 15 have a high curing rate and are excellent in storage stability. On the other hand, Comparative Examples 1, 2 and 4 have a slow curing rate, and Comparative Examples 3 and 5 have poor storage stability.

From the results of Tables 2 to 5, it can be seen that the curable composition of the present invention is a curable composition capable of achieving both high storage stability and a high curing rate.

Claims (3)

A compound having a glycidyl group, at least one selected from the group consisting of an alicyclic epoxy compound and an oxetane compound, the following general formula (1),

A compound represented by the following general formula (2),

(In the formulas (1) and (2), R ^{1 to} R ⁴⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 1 to 12 carbon atoms, or carbon. From any one of an alkoxy group having 1 to 12 atoms, a hydroxyalkoxy group having 1 to 12 carbon atoms, an optionally substituted phenyl group, an optionally substituted phenoxy group and a nitro group A selected group, and X is an atomic group that can be a monovalent anion).
0-100 parts by mass of the alicyclic epoxy compound, 0-50 parts by mass of the oxetane compound, 0.1-10 parts by mass of the compound represented by the general formula (1) per 100 parts by mass of the compound having the glycidyl group. The curable composition characterized by including 0.1-10 mass parts of compounds represented by the said General formula (2). In the general formula (1) and the general formula (2), the anion portion represented by X ⁻ is SbF ₆ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , SbCl ₆ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , FSO ₃ ⁻ , F ₂ PO ₂ ⁻ , p-toluene sulfonate, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraaryl The curable composition according to claim 1, which is at least one selected from the group consisting of borates. In a method for producing a cured product comprising a substrate preparation step for preparing a substrate, a coating step for applying a curable composition to the substrate, and an irradiation step for irradiating energy rays.
The said curable composition is the curable composition of Claim 1 or 2, The manufacturing method of the hardened | cured material characterized by the above-mentioned.