JP6509534B2 - Composition, adhesive and optical film - Google Patents

Description

  The present invention relates to a composition, an adhesive and an optical film, and more particularly, it is useful as an adhesive for various functional films for flat panel displays, and in particular, to an adhesive in direct contact with liquid crystals such as a sealing agent for liquid crystal dropping method. The present invention relates to a composition, an adhesive and an optical film which are excellent in transparency, adhesion and resin elution.

  The photocurable composition is a composition that can be polymerized and cured by irradiation with ultraviolet light or electron beam. Nowadays, photocurable compositions are widely used in the fields of inks, paints, various coatings, adhesives, vehicles, construction materials, sealants and the like because they have a high curing rate and are easy to handle.

  For example, Patent Document 1 proposes an energy ray reactive adhesive composition for an optical laminated disc, which comprises a polythiol compound having a primary mercapto group, a polyene compound, and an energy ray sensitive radical polymerization initiator. . Further, Patent Document 2 proposes a liquid crystal sealing agent having low liquid crystal contamination, which contains a radical curable resin having an ethylenic unsaturated bond, a thiol compound, and a radical polymerization initiator. Furthermore, in Patent Document 3, a polyene / polythiol photosensitive resin composition suitable for adhesion of an optical component, which comprises a (meth) acryloyl group-containing silicone compound, a thiol compound, a photopolymerizable monomer and a photoradical polymerization initiator is Proposed.

Japanese Patent Laid-Open No. 9-221651 JP, 2009-0886291, A JP, 2010-168452, A

  In order to use the adhesive composition for an adhesive for functional films, it is required that the transparency, the adhesion and the resin elution be good, but the conventional adhesive composition is not necessarily sufficient. Specifically, when used as an adhesive for direct contact with liquid crystal such as an adhesive for various functional films for flat panel displays, particularly a sealing agent for liquid crystal dropping method, transparency, adhesion and resin elution (liquid crystal contamination Sex) is highly sought after.

  Therefore, the object of the present invention is useful as an adhesive for various functional films for flat panel displays, and particularly suitable for an adhesive in direct contact with liquid crystals such as a sealing agent for liquid crystal dropping method, transparency, adhesion and It is providing a composition, an adhesive agent, and an optical film which are excellent in resin elution.

  As a result of intensive studies to solve the above problems, the present inventor should solve the above problems if it is a pressure-sensitive adhesive composition including an acrylic polymer obtained by polymerizing a monomer having a predetermined structure as an essential component. It has been found that the present invention can be accomplished.

  That is, the composition of the present invention is characterized in that 30 to 70 parts by mass of the epoxidized polyolefin (A) and 30 to 70 parts by mass of the thiol compound (B) are essential components.

（式中、Ｒ^１およびＲ^２は、それぞれ独立して、炭素原子数１〜５のアルキル基、炭素原子数１〜５のアルコキシ基、シクロペンチル基、シクロヘキシル基、炭素原子数６〜３０のアリール基、炭素原子数６〜３０のアルキルアリール基またはハロゲン原子であり、ｎおよびｑは、それぞれ独立して、１〜５の整数であり、ｍおよびｐは、それぞれ独立して、０〜５の整数であり、ｎ＋ｍ＋ｐ＋ｑは２０以下であり、ｒは、１〜５０の整数である。）で表されることが好ましい。また、本発明の粘着剤組成物においては、前記チオール化合物（Ｂ）が、下記一般式（ＩＩ）、

（式中、Ｒ^３は、水素原子または炭素原子数１〜５のアルキル基であり、Ｒ^４は、炭素原子数１〜５のアルキル基であり、Ｒ^５は、直接結合または炭素原子数１〜５のアルキレン基であり、Ｒ^６は、炭素原子数２〜２０の有機基であり、ｓは２〜６の整数である。）で表されることが好ましい。さらに、本発明の組成物においては、さらに、重合開始剤（Ｃ）０．０１〜１．０質量部を含有することが好ましい。 In the composition of the present invention, the epoxidized polyolefin (A) has the following general formula (I),

(Wherein, R ¹ and R ² each independently represent an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aryl of 6 to 30 carbon atoms Group, an alkylaryl group having 6 to 30 carbon atoms or a halogen atom, n and q each independently represent an integer of 1 to 5, and m and p each independently represent 0 to 5 N is preferably an integer, n + m + p + q is 20 or less, and r is an integer of 1 to 50. In the pressure-sensitive adhesive composition of the present invention, the thiol compound (B) is represented by the following general formula (II):

(Wherein, R ³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁴ is an alkyl group having 1 to 5 carbon atoms, and R ⁵ is a direct bond or 1 carbon atom) And R ⁶ is an organic group having 2 to 20 carbon atoms, and s is preferably an integer of 2 to 6). Furthermore, in the composition of this invention, it is preferable to contain 0.01-1.0 mass part of polymerization initiators (C) further.

  The adhesive of the present invention is characterized by containing the composition of the present invention.

  The optical filter of the present invention is characterized by having an adhesive layer comprising the composition of the present invention.

  The adhesive and optical filter of the present invention are suitable for display.

  According to the present invention, transparency, adhesion and resin elution are useful as adhesives for various functional films for flat panel displays, and particularly suitable for adhesives in direct contact with liquid crystals such as sealing agents for liquid crystal dropping methods. It is possible to provide a composition, an adhesive and an optical film which are excellent in properties.

  Hereinafter, the composition, the adhesive and the optical film which are excellent in transparency, adhesion and resin releasability of the present invention will be described in detail. The composition of the present invention comprises 30 to 70 parts by mass of epoxidized polyolefin (A) and 30 to 70 parts by mass of thiol compound (B) (hereinafter referred to as "component (A)" and "component (B) respectively ")).

<(A) component>
The component (A) used in the composition of the present invention is a polyolefin in which an epoxy group is introduced by modifying a polyolefin with an epoxy group-containing monomer. Producing by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and, if necessary, another monomer by any of a copolymerization method and a graft method it can. 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.

  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, Examples thereof include 3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and the like, among which ethylene, propylene, 1,3-butadiene and 1,4-butadiene are preferable. As the epoxidized polyolefin, epoxidized polyethylene, epoxidized polypropylene and epoxidized polybutadiene are preferable.

  Examples of the epoxy group-containing monomer include glycidyl esters of α, β-unsaturated acids, vinyl benzyl glycidyl ether, allyl glycidyl ether and the like. Specific examples of glycidyl esters of α, β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate and the like, 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 Or unsaturated polybasic acid such as polyfunctional (meth) acrylate 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) acid Dimethylaminopropyl methacrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, phenoxyethyl (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, trimethylol Ethane 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 such as cyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloyl ethyl] isocyanurate, polyester (meth) acrylate oligomers and esters of polyhydric alcohols or polyhydric phenols; (meth) acrylic acid Zinc, metal salts of unsaturated polybasic acids such as magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetratetra Hydrophthalic 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, methyl hymic acid anhydride; (meth) acrylamide, methylene bis (meth) acrylamide, diethylene triamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyhydric amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanation Viniride And unsaturated nitriles such as 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; maleimide, N-phenyl maleate Unsaturated imides such as N, N-cyclohexyl maleimide; Indens such as indene, 1-methyl indene; Polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane etc. Macromonomers having a mono (meth) acryloyl group at the terminal of: vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, Vinylcarbazole, vinylpyrrolidone, vinylpyridine, vinyl urethane compound of hydroxyl group-containing vinyl monomer and polyisocyanate compound, vinyl epoxy compound of hydroxyl group-containing vinyl monomer and polyepoxy compound Reaction product of hydroxyl group-containing polyfunctional acrylate such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate with polyfunctional isocyanate such as tolylene diisocyanate and hexamethylene diisocyanate, hydroxyl group-containing polyfunctional such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate A multifunctional acrylate having an acid value which is a reaction product of an acrylate and a dibasic acid anhydride such as succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride and the like can be mentioned.

  In the component (A), the content of the structural unit based on the glycidyl ester of the α, β-unsaturated acid is 1 to 50% by mass, preferably 3 to 40% by mass with respect to 100% by mass of the component (A) is there. The content of structural units based on other monomers is 10% by mass or less, preferably 5% by mass or less, based on 100% by mass of the component (A).

  A commercial item can also be used as said (A) component, For example, epolide PB3600, epolide PB4700 (made by Daicel); BF-1000, FC-3000 (made by ADEKA); Bond first 2C, bond first E, Bond First CG 5001, Bond First CG 5004, Bond First 2 B, Bond First 7 B, Bond First 7 L, Bond First 7 M, Bond First VC 40 (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.); Ricon 657 (manufactured by Arkema) and the like.

  A composition obtained as the component (A) which has an epoxy group in the main chain as represented by the following general formula (I) and at least one or more double bonds has high compatibility. The heat resistance of the hardened | cured material of this becomes high and it is preferable.

Here, in the formula (I), R ¹ and R ² are each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a cyclopentyl group, a cyclohexyl group, the number of carbon atoms 6-30 aryl groups, C6-C30 alkyl aryl groups or halogen atoms are represented, n and q are each independently an integer of 1-5, and m and p are each independently And n is an integer of 0 to 5, n + m + p + q is 20 or less, and r is an integer of 1 to 50.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ¹ and R ² in the general formula (I) include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso -Butyl, pentyl, iso-pentyl, tert-pentyl and the like.

In addition, examples of the alkoxy group having 1 to 5 carbon atoms represented by R ¹ and R ² include methyloxy, ethyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, pentyloxy, Iso-pentyloxy, tert-pentyloxy and the like can be mentioned.

As a C6-C30 aryl group represented by R < ¹ > and R < ² >, a phenyl, a naphthyl, anthracenyl etc. are mentioned.

As a C6-C30 arylalkyl group represented by R < ¹ > and R < ² >, a benzyl, fluorenyl, an indenyl etc. are mentioned.

Examples of the halogen atom represented by R ¹ and R ² include fluorine, chlorine, bromine and iodine.

  The component (A) has a number average molecular weight of 2,000 to 80,000, preferably 10,000 to 50,000, and an epoxy equivalent of 80 to 3,000 g / eq, preferably 100 to 500 g / eq. The vinyl equivalent is 50 to 200 g / eq, preferably 75 to 125 g / eq.

<(B) component>
The component (B) used in the composition of the present invention is not particularly limited, and conventionally known thiol compounds can be appropriately used. For example, 2-butanethiol, cyclohexylmercaptan, cyclopentanethiol, methyl-3- Mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, 1,2- Ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1,9-nonane Dithiol, 1, 10-decanedithiol, 1, 12-do Candithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptomethyl) ether, hexanediol bisthioglycolate, 1,1,1-tris (mercaptomethyl) ethane, 2-ethyl-2-mercapto Methyl-1,3-propanedithiol, 1,2,3-propanetrithiol, tetrakismercaptomethylmethane, pentaerythritol tetrakis (2-mercaptopropionate), pentaerythritol tetrakis mercaptoacetate, pentaerythritol tetrakis (2-mercaptoglyco Rate), dipentaerythritol hexakis (2-mercaptopropionate), dimercaptomethane, trimercaptomethane, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5 Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis ( 3-Mercaptobutyryloxy) butane, trimethylolpropane tris (2-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (2-mercaptoglycolate), ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate) ), D Glycol bis (3-mercapto glycolate), ethylene glycol bis (2-mercapto propionate), tetraethylene glycol bis (3-mercapto propionate), propylene glycol bis (2-mercapto propionate), butanediol Bis (2-mercaptopropionate, octanediol bis (2-mercaptopropionate), trimethylolpropane tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate, ethylene glycol bis (3-mercaptobutyrate) Propylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), ethylene glycol bis (2-mercapto) Tobutylate), propylene glycol bis (2-mercaptobutyrate), butanediol bis (2-mercaptobutyrate), octanediol bis (2-mercaptobutyrate), ethylene glycol bis (4-mercaptovalerate), propylene glycol bis (4-Mercaptoisovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercapto) (Valerate), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-bis (1-mercaptoethyl) benzene, phthalic acid di (1-mercaptoethyl ester), phthalic acid di (2-mercaptopropyl ester), phthalic acid di (3-mercaptobutyl ester), phthalic acid di (3-mercaptobutyl ester) Etc.). The component (B) can be used alone or in combination of two or more.

  Among the above-exemplified compounds, thiol compounds having a secondary mercapto group as represented by HS-CHXY (in the formula, X and Y each represent a functional group other than H), which is not primary, are After mixing with the component A), it is preferable because it is excellent in one-component stability.

  A commercial item can also be used as said (B) component, For example, Kalens MT BD1, Kalens MT PE1, Kalens MT NR1 (made by Showa Denko); QX11, QX40 (made by Mitsubishi Chemical Corporation); Thiokol LP-33 , Thiocol LP-3, Thiocol LP-980, Thiocor LP-23, Thiocol LP-56, Thiocol LP-55, Thiocol LP-12, Thiocol LP-32, Thiocol LP-2, Thiocol LP-31 (manufactured by Toray Industries, Inc.) Adeka Hardener EH-317 (made by Adeka); MPM, EHMP, NOMP, MBMP, STMP, TMMP, TMMP, TMPIC, PEMP, EGMP-4, DPMP (made by Sakai Chemical); HDTG, TMTG, PETG (made by Sakai Chemical) Etc.).

  As the component (B), an esterified product of a polyfunctional alcohol and a mercapto group-containing carboxylic acid represented by the following general formula (II) is easily obtainable, and the curability of the cured product of the composition obtained is It is preferable because it becomes higher.

Here, in the formula (II), R ³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁴ is an alkyl group having 1 to 5 carbon atoms, and R ⁵ is a direct bond Or an alkylene group having 1 to 5 carbon atoms, R ⁶ is an organic group having 2 to 20 carbon atoms, and s is an integer of 2 to 6;

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ³ and R ⁴ in the above general formula (II) include those exemplified for the above general formula (I).

Examples of the alkylene group having 1 to 5 carbon atoms represented by R ⁵ include methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, pentylene, ethane-1,1-diyl, propane-2,2-diyl and the like can be mentioned.

Examples of the organic group having 2 to 20 carbon atoms represented by R ⁶ include linear, branched or cyclic ones, and examples thereof include those exemplified as the alkylene group represented by R ⁵ above, an alkylene group In addition to those in which X is interrupted by an oxygen atom, cyclohexane diyl, cyclopentadiyl, those represented by the following formula and the like can be mentioned.

  The component (B) preferably has a molecular weight of 80 to 10,000, and more preferably 250 to 1,000.

  In the composition of the present invention, the compounding ratio of the component (A) to the component (B) is 30 to 70 parts by mass of the thiol compound (B) with respect to 30 to 70 parts by mass of the component (A) The ratio of SH equivalent of component B) / vinyl equivalent of component (A) is preferably 2: 1 to 1: 2, and more preferably around 1: 1. The component (B) can be added in several times so that the total of the SH equivalents of the component (B) is approximately the same as the vinyl equivalent of the component (A), using a plurality of types of the component (B).

<(C) component>
The composition of this invention can use a polymerization initiator as (C) component as needed. As a polymerization initiator (C), a photoinitiator or a thermal polymerization initiator is mentioned. Any photopolymerization initiator may be used as long as it is a compound capable of initiating radical polymerization upon exposure to light. For example, ketone compounds such as acetophenone compounds, benzyl compounds and thioxanthone compounds are preferable. It can be illustrated as

  Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2 -Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiarybutyl dichloroacetophenone, p-tertiarybutyl trichloroacetophenone, p-azidobenzal Acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1, benzoi , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane- 1-ON etc. are mentioned.

  Examples of the benzyl compounds include benzyl and anisyl.

  Examples of benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and the like. .

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

  Other photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphain oxide, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyr-1-yl)] titanium, etc. Can be mentioned.

  Moreover, as a thermal polymerization initiator, 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethyl valeronitrile, 1, Azo initiators such as 1′-azobis (1-acetoxy-1-phenylethane); benzoyl peroxide, di-t-butyl benzoyl peroxide, t-butyl peroxypivalate, di (4-t-butylcyclohexyl) 2. Peroxide initiators such as peroxydicarbonate, and persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.

  In the composition of the present invention, one or more of these polymerization initiators can be blended and used according to the desired performance.

  The use ratio of the component (C) to the component (A) is not particularly limited, and it may be used generally at a normal ratio within the range that does not inhibit the object of the present invention. On the other hand, the component (C) can be 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass. When the amount is too small, curing tends to be insufficient, and when the amount is too large, various properties such as the water absorption of the cured product and the strength of the cured product may be adversely affected.

  The composition of the present invention may contain a solvent in addition to the components (A) to (C). The solvent is not particularly limited as long as it can dissolve or disperse the components (A) to (C). For example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclopenta Ketones such as nonone, cyclohexanone and isophorone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid ester solvents such as n-propyl, isopropyl acetate, n-butyl acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, cellosolve acetate etc Solb solvents; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol, acetone alcohol etc. ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol methyl acetate etc Ether ester solvents; BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene and pinene; mineral spirits Paraffin solvents such as Swazole # 310 (Cosmo Matsuyama Petroleum Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.), etc .; carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2 Halogenated aliphatic hydrocarbon solvents such as dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Aprotic polar solvents such as N, N-dimethylformamide, N-methyl pyrrolidone, dimethyl sulfoxide; Carbitol solvents And aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, water and the like, and these solvents can be used as one or a mixture of two or more.

  Surfactants can also be used in the composition of the present invention as required. As surfactants, fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates, higher amine halogens Surfactant, cationic surfactant such as quaternary ammonium salt, polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, nonionic surfactant such as fatty acid monoglyceride, amphoteric surfactant, silicone surfactant And the like may be used, and these may be used in combination.

  The composition of the present invention can be coated on a supporting substrate such as glass, metal, paper, plastic and the like by a known means such as roll coater, curtain coater, various printing, immersion and the like. In addition, once applied on a support substrate such as a film, it can be transferred onto another support substrate, and there is no limitation on its application method.

  In addition, as long as the effects of the present invention are not impaired, other monomers, base initiators, inorganic fillers, organic fillers, pigments, colorants such as pigments, dyes, photosensitizers, crosslinking agents, antifoaming agents, and the like may be used. Adhesive, leveling agent, organometallic coupling agent, thixo agent, carbon compound, metal fine particle, metal oxide, flame retardant, plasticizer, light stabilizer, heat stabilizer, anti-aging agent, elastomer particle, polymerization inhibitor, Various resin additives such as an ultraviolet light absorber, an antioxidant, an antistatic agent, a mold release agent, a flow control agent, an adhesion promoter and the like can be added.

  The composition of the present invention cures by light irradiation or heating to cause en-thiol reaction to be cured, and as a light source of active light, one emitting light with a wavelength of 300 to 450 nm can be used, for example, ultra high pressure A mercury, a mercury vapor arc, a carbon arc, a xenon arc or the like can be used.

  Specific applications of the composition of the present invention are glasses, optical materials represented by imaging lenses, paints, coatings, lining agents, inks, resists, liquid resists, adhesives, sealants for liquid crystal dropping methods, Printing plate, insulation varnish, insulation sheet, laminated board, printed circuit board, for semiconductor device, for LED package, for liquid crystal injection port, for organic EL, for optical element, for electrical insulation, for electronic parts, for sealing film Additives, molding materials, putties, glass fiber impregnating agents, fillers, passivation films for semiconductors and solar cells, interlayer insulating films, protective films, prism lens sheets used for backlights of liquid crystal displays, projection Lens portion of a lens sheet such as a Fresnel lens sheet, a lenticular lens sheet or the like used for a screen of a television or the like, or such a sheet Backlights, protective films and spacers for liquid crystal color filters, DNA separation chips, microreactors, nanobio devices, recording materials for hard disks, solid-state imaging devices, solar cell panels, light emitting diodes, organic light emitting devices, luminescent films, fluorescent films , MEMS elements, actuators, holograms, plasmon devices, polarizing plates, polarizing films, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, optical molding casting agents, etc. For example, coating agents As a base material which can be applied, metal, wood, rubber, plastic, glass, ceramic products etc. can be mentioned.

  When the composition of the present invention is used as an adhesive, those obtained by appropriately adding other optional components to the composition of the present invention are uniformly mixed, and they are kneaded by an extruder, a roll, etc. The film is formed into a sheet by a film forming method such as die extrusion or inflation, and the adhesive formed into a sheet is attached to the transparent support, and then heated or irradiated with light such as ultraviolet light from the transparent support under the above conditions. Then, the method of sticking to the other to-be-adhered body is mentioned. Alternatively, light may be emitted after being bonded to the adherend.

  In addition, the above polymer and the above-mentioned additive are uniformly dissolved in a solvent that does not affect the protective film or the liquid crystal cell surface substrate at all, and printing methods such as screen printing, gravure printing, flexo printing, roll coater coating, flow coater After applying uniformly on the surface of a transparent support using coating methods, such as coating and knife coater coating, and temporarily pressing-bonding, it can be irradiated with light and adhesively cured. Further, in the case of relatively narrow surface adhesion, there is a method in which the surface tension of the adhesive is absorbed into the gap between the combined materials.

  Examples of the material of the transparent support include inorganic materials such as glass; cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose and nitrocellulose; polyamide; polycarbonate; polyethylene Polyesters such as terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate; polystyrene; polyethylene , Polyolefins such as polypropylene and polymethylpentene; Acrylic resins such as polymethylmethacrylate; Polycarbonate; Polysulfone ; Polyether sulfone; polyether ketone; polyetherimides; polyoxyethylene, and polymer materials such as norbornene resins. The transmittance of the transparent support is preferably 80% or more, more preferably 86% or more. The haze is preferably 2% or less, and more preferably 1% or less. The refractive index is preferably 1.45 to 1.70.

At the time of light irradiation, irradiation conditions such as wavelength, intensity and irradiation time of the light to be irradiated are appropriately adjusted depending on the activity of the polymerization initiator, the activity of the photopolymerizable resin to be used, etc. Usually, one having a wavelength peak of 350 to 400 nm is preferable in order to allow light to sufficiently enter the interior, and more preferably one having a wavelength peak of 360 to 380 nm. And is preferably 10 to 300 mW / cm ² as light intensity, more preferably 25~100mW / cm ^2, the irradiation time is preferably 1 to 10 minutes, more preferably 3 to 6 minutes.

  In the adhesive of the present invention, a liquid polymerizable acrylic monomer or a liquid polymerizable monovinyl monomer can be used as a reactive diluent in order to reduce the viscosity or to improve the coatability. Liquid polymerizable acrylic monomers are commercially available or can be prepared by known methods. Examples of liquid polymerizable monovinyl monomers include: vinyl esters such as vinyl acetate; monoacrylics such as alkyl acrylate, alkyl methacrylate, hydroxyalkyl methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate and the like Esters: Esters of acrylic acid or methacrylic acid with polyhydric alcohols; and polyhydric alcohols such as glycerol, 1,1,1-trimethylolpropane, trihydroxyethyl isocyanurate, erythritol, pentaerythritol and the like.

  The optical film using the composition of the present invention in the adhesive layer is not particularly limited in terms of the shape, but generally, on a transparent support, if necessary, a subbing layer, an antireflective layer, a hard coat layer, What provided each layer, such as a lubricating layer, a protective layer, a liquid crystal layer, etc. is mentioned. As a method of providing an adhesive layer on an optical film, (1) a method of applying to a transparent support, (2) providing an adhesive layer between any two adjacent selected from a transparent support and optional layers. The method is mentioned.

  Hereinafter, the present invention will be described in more detail by way of examples and the like, but the present invention is not limited to these examples. In Examples and Comparative Examples, parts mean parts by mass.

[Examples 1 to 16 and Comparative Examples 1 to 5]
In the formulations shown in Tables 1 to 3 below, the components (A), (B) and (C) were stirred and mixed to obtain the compositions of Examples and Comparative Examples. The following evaluation was performed about the composition obtained in Examples 1-16 and Comparative Examples 1-5. The results are shown in Tables 1 to 3 below.

(Applicability)
The composition obtained in Examples 1 to 16 and the comparative compositions obtained in Comparative Examples 1 to 5 were coated by selecting a bar coater such that the coating thickness after drying was 10 μm. It was dried in an oven (90 ° C., 600 seconds). The obtained coating film was exposed to light (2,000 mJ / cm ² ) using an extra-high pressure mercury lamp. The state of the surface of the coating film after exposure was observed, and the presence or absence of uniform coating film formation was visually confirmed.
○: uniform coating film was obtained.
X: Peeling or unevenness of the coating film was observed after coating.

(Adhesiveness)
The compositions obtained in Examples 1 to 16 and the comparative compositions obtained in Comparative Examples 1 to 5 are applied to a glass of 25 mm width, and another glass is pasted so as to have an area of 625 mm ^2. It was cured by exposure (2,000 mJ / cm ² ) with a high pressure mercury lamp. The shear adhesive strength (MPa) of the bonded part was measured.

(TNI point)
On the cured film obtained in the above-described coatability test, liquid crystal compound No. 1 shown below was obtained. 1 to No. A liquid crystal composition containing 11 was brought into contact, and after 60 hours at 60 ° C., the liquid crystal composition was taken out to conduct a resin dissolution test. The TNI points (Nematic-Isotropic transition temperature) before and after the resin dissolution test were compared for the liquid crystal composition taken out, and evaluation was made according to the following criteria. In addition, the measurement of the TNI point was performed by reading the temperature of the endothermic peak by differential scanning calorimetry (DSC).
○: Change in TNI point is less than ± 0.5 ° C Δ: Change in TNI point is 0.5-1.0 ° C
×: TNI point change is over 1.0 ° C

(VHR)
The resin dissolution test was conducted, the VHR (voltage holding ratio) before and after the resin dissolution test was compared for the taken out liquid crystal composition, the reduction rate of VHR was determined, and evaluation was performed according to the following criteria. For evaluation, the liquid crystal composition was injected into a TN cell for liquid crystal evaluation (cell thickness 5 μm, electrode area 8 mm × 8 mm alignment film JALS 2096), and VHR was measured using VHR-1A (manufactured by Toyo Corporation). (Measurement conditions: Pulse voltage width 60 μs, frame period 16.7 ms, wave height ± 5 V, measurement temperature 25 ° C.)
:: VHR decrease rate is over 99% Δ: VHR decrease rate is 90 to 99%
X: VHR decrease rate is less than 90%

Compound A-1: BF-1000 (epoxidized polybutadiene; manufactured by ADEKA)
Compound A-2: JP-200 (epoxidized polybutadiene; manufactured by Nippon Soda Co., Ltd.)
Compound A-3: FC-3000 (epoxidized polybutadiene; manufactured by ADEKA)
Compound A-4: Ricon 657 (epoxidized polybutadiene; manufactured by Arkema)
Compound A′-1: polyglycidyl acrylate (molecular weight 4,000)
Compound A′-2: polybutadiene (molecular weight 4,500)
Compound A'-3: polymethyl methacrylate (molecular weight 5,000)
Compound B-1: Karenz MT PE-1; (polyfunctional thiol; manufactured by Showa Denko)
Compound B-2: Karenz MT NR-1; (polyfunctional thiol; manufactured by Showa Denko KK)
Compound B-3: Karenz MT BD-1; (polyfunctional thiol; manufactured by Showa Denko)
Compound B-4: pentaerythritol tetrakis thioglycolate PETG (polyfunctional thiol; manufactured by Sakai Chemical Co., Ltd.)
Compound B-5: pentaerythritol tetrakis (3-mercaptopropionate) PEMP (polyfunctional thiol; manufactured by SC Organic Chemical Company)
Compound B-6: methoxybutyl-3-mercaptopropionate MBMP (thiol; manufactured by SC Organic Chemical Company)
Compound B-7: Tris-[(3-Mercaptopropionyloxy) -ethyl] -isocyanurate (manufactured by TEMPIC SC Organic Chemical Company)
Compound C-1: SP-246 (acyl phosphine type polymerization initiator; manufactured by ADEKA)
Compound C-2: EP-3300 E (a benzophenone type epoxy compound; manufactured by ADEKA)
Compound C-3: Benzophenone Compound C-4: Irg 651 (Alkylphenone-based polymerization initiator; manufactured by BASF)
Compound D-1: triallyl isocyanurate TAIC (manufactured by Nippon Kasei Co., Ltd.)
Compound D-2: Glycerin monoallyl ether neoallyl E-10 (made by Daiso)

From Tables 1 to 3, the composition of the present invention is excellent in coatability, resin elution, adhesion and the like, and can be suitably used for an adhesive.

Claims (6)

30 to 70 parts by mass of an epoxidized polyolefin (A) and 30 to 70 parts by mass of a thiol compound (B) as essential components ,
The epoxidized polyolefin (A) has the following general formula (I),

(Wherein, R ¹ and R ² each independently represent an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aryl of 6 to 30 carbon atoms Group, an alkylaryl group having 6 to 30 carbon atoms or a halogen atom, n and q each independently represent an integer of 1 to 5, and m and p each independently represent 0 to 5 N is an integer, n + m + p + q is 20 or less, and r is an integer of 1 to 50.
The thiol compound (B) has the following general formula (II),

(Wherein, R ³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁴ is an alkyl group having 1 to 5 carbon atoms, and R ⁵ is a direct bond or 1 carbon atom) And R ⁶ is an organic group having 2 to 20 carbon atoms, and the organic group may contain a nitrogen atom and an oxygen atom, and s is an integer of 2 to 6). A composition characterized in that it is represented . Further, (A) component with respect to 100 parts by mass of polymerization initiator component (C) 0.01 to 5.0 parts by weight The composition of claim 1 containing. An adhesive comprising the composition according to claim 1 or 2 . An optical film comprising an adhesive layer comprising the composition according to claim 1 or 2 . The adhesive according to claim 3 , which is for a display. The optical film according to claim 4 , which is for a display.