JP2006063148A - Photo setting adhesive resin composition and cured article of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photo setting resin composition with low refractive index and excellent in transparency and imparting a cured article excellent in transparency, adhesion and resistance to solvents, usable for adhesives of optical elements, optical communication goods. <P>SOLUTION: The invention relates to the photo setting resin composition comprising (A) a copolymer of fluorine containing monofunctional (meth)acrylate and glycidyl(meth)acrylate, (B) a cationically polymerizable diluent and (C) an optical cation polymerization initiator. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is characterized by containing a copolymer of a fluorine atom-containing monofunctional (meth) acrylate and glycidyl (meth) acrylate, a cationic polymerizable diluent and a photocationic polymerization initiator, and if necessary, a photosensitizer. A photocurable low refractive index resin composition that can be quickly cured and adhered by irradiating active energy rays such as ultraviolet rays, and an optical article having a layer obtained by curing it, for optical communication It relates to goods.

  In recent years, the advancement of polymer materials to optical articles and optical communication articles has been remarkable, and liquid crystal display panels, color filters, spectacle lenses, Fresnel lenses, lenticular lenses, TFT (Thin Film Transistor) prism sheets, and aspherical surfaces. Studies on lenses, optical disk coating agents and adhesives, optical fiber core materials and clad materials, optical fiber connection adhesives, optical waveguide core materials and clad materials, and the like have been actively conducted. In the light-related member composed of these optical articles, the adhesive plays a particularly important role.

  In general, as described in Patent Document 1, an organic solvent-based or water-based adhesive has been mainly developed and used as an adhesive. However, in the case of conventional organic solvent-based adhesives, since a large amount of organic solvent is used, the cost is required for the recovery, the working environment is deteriorated, and the solvent resistance of the resulting product is related. The problem is that the ink that can be used is limited. On the other hand, in the case of water-based adhesives, it takes a long time to dry, and when the adherend is weak to heat, the adherend deteriorates due to the heat at the time of drying, causing a problem of dimensional change and curling. . Both organic solvent-based and water-based adhesives require a longer drying time if the adherend is made of an organic solvent or water-impervious material. In the worst case, the organic solvent is contained in the adhesive. Or it may not adhere | attach with water contained. In order to solve such a problem, a resin composition for an adhesive (for example, (meth) acrylic acid and a carboxyl group is curable by irradiating an active energy ray such as ultraviolet rays, which can be cured without a solvent). An adhesive resin composition comprising at least one selected from the group consisting of (meth) acrylate compounds and polyurethane poly (meth) acrylate) has been proposed (see, for example, Patent Document 2). Patent Document 3 includes, for example, fluorine obtained by reacting 2- (meth) acryloyloxyethyl isocyanate with a (meth) acrylate compound having a specific structure having a fluorine atom and a hydroxyl group in the molecule without using an organic solvent. There is a description about a resin composition for low refractive index adhesives containing urethane (meth) acrylate having atoms. As its use, an optical fiber is cited. In addition, in the case where the material of the adherend is an inorganic material such as glass, it is often not bonded even when a normal resin composition is cured. In such a case, as described in Patent Document 4, bonding to an inorganic material is performed. In order to improve property, the method of using a silane coupling agent is mentioned.

Japanese Patent Publication No.47-1188 JP-A-6-184498 JP 2000-44650 A JP 2004-168840 A

  In recent years, resin compositions for adhesives are often used in optical articles and optical communication articles, and as light-related members become more sophisticated, resin compositions for adhesives from the viewpoint of light transmission. The cured product is required to have a refractive index within a certain range. Particularly, the refractive index is low, and there is an increasing demand for development of a resin composition suitable for an adhesive.

  As a result of intensive studies to solve the above problems, the present inventor has found that a copolymer of a fluorine atom-containing monofunctional (meth) acrylate and glycidyl (meth) acrylate, a cationic polymerizable diluent, and a photocationic polymerization. By blending an initiator and, if necessary, a photosensitizer, coating is easy without blending a volatile organic solvent that does not have cationic polymerizability, and a low refractive index and transparency. It can be cured by irradiating active energy rays such as ultraviolet rays, and the cured product is excellent in transparency, adhesion to glass and solvent resistance, optical articles, optical communication It has been found that a photocurable resin composition useful as an adhesive for articles can be obtained, and the present invention has been completed.

That is, the present invention
[1] A copolymer containing a fluorine atom-containing monofunctional (meth) acrylate and glycidyl (meth) acrylate (A), a cationic polymerizable diluent (B), and a photocationic polymerization initiator (C). A photocurable resin composition,
[2] The photocurable resin composition according to [1], wherein the refractive index of the copolymer (A) is 1.50 or less,
[3] The weight ratio of the copolymer (A) and the cationic polymerizable diluent (B) is copolymer (A): cationic polymerizable diluent (B) = 10-80: 90-20 [1] Or the photocurable resin composition according to [2],
[4] The weight ratio of the total weight of the copolymer (A) and the cationic polymerizable diluent (B) to the cationic photopolymerization initiator (C) is (copolymer (A) + cationic polymerizable diluent (B )): Photo-cationic polymerization initiator (C) = 100: The photocurable resin composition according to any one of [1] to [3], which is 0.1 to 10,
[5] The photocurable resin composition according to any one of [1] to [4], wherein the cationic photopolymerization initiator (C) is an iodonium salt compound,
[6] The photocurable resin composition according to any one of [1] to [5], which contains a photosensitizer (D),
[7] The photocurable resin composition according to any one of [1] to [6], which does not contain a compound other than the cationic polymerizable diluent (B) as a diluent.
[8] The photocurable resin composition according to any one of [1] to [7], wherein the use is an adhesive for optical articles,
[9] The photocurable resin composition according to any one of [1] to [7], wherein the use is an adhesive for optical communication articles,
[10] An optical article having a cured product layer of the photocurable resin composition according to [8],
[11] An article for optical communication having a cured product layer of the photocurable resin composition according to [9],
It is about.

  The photocurable resin composition containing the copolymer (A) of the fluorine atom-containing monofunctional (meth) acrylate and glycidyl (meth) acrylate of the present invention contains a volatile organic solvent having no cationic polymerizability. Coating is easy, low refractive index and excellent transparency, it can be cured by irradiating active energy rays such as ultraviolet rays, and the cured product becomes transparent As an adhesive for optical articles and optical communication articles because of excellent adhesion to glass, no generation of voids (bubbles) because it does not contain the organic solvent, and excellent solvent resistance. Useful.

  The copolymer (A) used in the photocurable resin composition of the present invention can be obtained by copolymerizing a fluorine atom-containing monofunctional (meth) acrylate and glycidyl (meth) acrylate. Here, the fluorine atom-containing monofunctional (meth) acrylate used for synthesizing the copolymer (A) is a fluorine atom-containing compound having one (meth) acryloyl group in the structure. And (meth) acrylate. Here, the alkyl is a straight or branched chain having 1 to 20 carbon atoms, and the number of fluorine atoms contained is not particularly limited. Specific examples of the fluorine atom-containing alkyl (meth) acrylate include, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 1H, 1H-perfluoro-n-butyl (meth) acrylate, 1H, 1H-perfluoro-n-pentyl (meth) acrylate, 1H, 1H-perfluoro-n-hexyl (meth) acrylate, 1H, 1H-perfluoro-n-octyl ( (Meth) acrylate, 1H, 1H-perfluoro-n-decyl (meth) acrylate, 1H, 1H-perfluoro-n-dodecyl (meth) acrylate, 1H, 1H-perfluoroisobutyl (meth) acrylate, 1H, 1H-perfluoroisooctyl (Meth) acrylate, 1H, 1H- Rufluoroisododecyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-perfluoropentyl (meth) acrylate, 1H, 1H, 7H-perfluoroheptyl (meth) acrylate 1H, 1H, 9H-perfluorononyl (meth) acrylate, 1H, 1H, 11H-perfluoroundecyl (meth) acrylate, 3,3,3-trifluoropropyl (meth) acrylate, 3,3,4,4 4-pentafluorobutyl (meth) acrylate, 2- (perfluoro-n-propyl) ethyl (meth) acrylate, 2- (perfluoro-n-butyl) ethyl (meth) acrylate, 2- (perfluoro-n-hexyl) ethyl (Meth) acrylate, 2- (perfluoro n-octyl) ethyl (meth) acrylate, 2- (perfluoro-n-decyl) ethyl (meth) acrylate, 2- (perfluoroisobutyl) ethyl (meth) acrylate, 2- (perfluoroisooctyl) ethyl (meth) acrylate, 3,3,4,4-tetrafluorobutyl (meth) acrylate, 1H, 1H, 6H-perfluorohexyl (meth) acrylate, 1H, 1H, 8H-perfluorooctyl (meth) acrylate, 1H, 1H, 10H-perfluorodecyl (Meth) acrylate, 1H, 1H, 12H-perfluorododecyl (meth) acrylate and the like can be mentioned. These can be easily obtained from the market. Specific examples thereof include fluorester (2,2,2-trifluoroethyl methacrylate manufactured by Tosoh F-Tech Co., Ltd.), biscort 8F (Osaka Organic Chemical Industry). 1H, 1H, 5H-pentafluoropentyl acrylate), Biscote 8FM (1H, 1H, 5H-pentafluoropentyl methacrylate), Biscote 17F (Osaka Organic Chemical Co., Ltd.) 2- (perfluoro-n-octyl) ethyl acrylate), Biscoat 17FM (2- (perfluoro-n-octyl) ethyl methacrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like. Here, only one type of fluorine atom-containing monofunctional (meth) acrylate used for synthesizing the copolymer (A) may be used. Two or more kinds of fluorine atom-containing monofunctional (meth) acrylates may be mixed and used in an arbitrary ratio.

  Moreover, the glycidyl (meth) acrylate used in order to synthesize | combine the copolymer (A) used in the photocurable resin composition of this invention can usually purchase and use a commercial item. Examples of commercially available products of glycidyl acrylate include SR-378 (manufactured by Sartomer), and examples of commercially available products of glycidyl methacrylate include light ester G (manufactured by Kyoeisha Chemical Co., Ltd.) and Blemmer G (Japan). And the like, SR-379 (manufactured by Sartomer), and the like. Here, the use ratio of glycidyl (meth) acrylate is fluorine atom-containing monofunctional (meth) acrylate: glycidyl (meth) acrylate = 60 to 99:40 to 1, more preferably fluorine atom-containing monofunctional (meth) acrylate: glycidyl. It is good to make it copolymerize by the molar ratio of (meth) acrylate = 70-95: 30-5.

  When synthesizing the copolymer (A) used in the photocurable resin composition of the present invention, a polymerization initiator is used. Here, as the polymerization initiator, an azo compound or an organic peroxide is mainly used. Examples of azo compounds that can be used include azonitriles, azoalkyls, 2-cyano-2-propylazoformamide, dimethyl-2,2′-azobis- (2-methylpropionate), 2,2′-azobis ( 2-hydroxymethylpropionitrile) and the like. Specifically, examples of the azonitriles include 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyrate. Ronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile) and the like, and examples of azoalkyls include 2 , 2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis (2-methylpropane) and the like. Examples of organic peroxides include ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, alkyl peresters, and carbonates. . Specifically, as ketone peroxides, for example, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, etc., as hydroperoxides, for example, 1,1,3,3- Tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide and the like, and diacyl peroxides include, for example, isobutyryl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, lauroyl Peroxides, benzoyl peroxides and the like as dialkyl peroxides include, for example, dicumyl peroxide, 2,5-dimethyl-2,5-di- (tert-butyl peroxide). Xoxy) hexane, 1,3-bis- (tert-butylperoxyisopropyl) benzene, tert-butylcumyl peroxide, di-tert-butyl peroxide, tris- (tert-butylperoxy) triazine and the like. Examples of ketals include 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, 2,2-di- (tert- (Butylperoxy) butane and the like as alkyl peresters include, for example, tert-butylperoxyneoheptanoate, tert-hexylperoxypivalate, tert-amylperoxy-2-ethylhexanoate, Examples of percarbonates include di-3- Butoxy butyl peroxydicarbonate, diisopropyl peroxydicarbonate, tert- butyl peroxy-2-ethylhexyl carbonate may be mentioned, respectively. Among these polymerization initiators, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), benzoyl par Oxides can be mentioned. The usage-amount of a polymerization initiator is 0.01 to 5 weight% with respect to the total weight of a fluorine atom containing monofunctional (meth) acrylate and glycidyl (meth) acrylate.

  When synthesizing the copolymer (A), a cationic polymerizable diluent (B) described later can be selected as a reaction solvent, and can be synthesized by solution polymerization in the reaction solvent. However, a vinyl ether compound having radical polymerizability cannot be used as a reaction solvent. When the cationic polymerizable compound (B) is used as a reaction solvent, the amount used is when the total weight of the fluorine atom-containing monofunctional (meth) acrylate, glycidyl (meth) acrylate and the cationic polymerizable diluent (B) is 100 The total weight of the fluorine atom-containing monofunctional (meth) acrylate and glycidyl (meth) acrylate is preferably 10 to 60, more preferably 20 to 50. The reaction temperature is usually 50 to 120 ° C., preferably 70 to 90 ° C., and the reaction time is usually 1 to 60 hours, preferably 3 to 15 hours. The molecular weight of the copolymer (A) is preferably 1,000 to 1,000,000, more preferably 5,000 to 100,000, in terms of number average molecular weight. The refractive index of the copolymer (A) can be adjusted by appropriately changing the component ratio of the copolymer (A), and the value measured with an Abbe refractometer is 1.50 or less at 25 ° C. It is preferable that there is, more preferably 1.45 or less.

  When synthesizing copolymer (A), it is involved in radical polymerization reaction of fluorine atom-containing monofunctional (meth) acrylate and glycidyl (meth) acrylate, which will be described later, instead of cationic polymerizable diluent (B) as a reaction solvent. Volatile organic solvents that are not used can be selected and used. Specific examples of the organic solvent not involved in the radical polymerization reaction include, for example, a linear, branched or cyclic aliphatic compound having 5 to 15 carbon atoms, an aromatic compound optionally having a substituent, and alcohols. , Ethers, ketones, esters and the like can be used. Specific examples of the linear, branched or cyclic aliphatic compound having 5 to 20 carbon atoms include, for example, n-hexane, 2-methylpentane, n-heptane, n-octane, 2,2,3- Examples include trimethylpentane, isooctane, n-nonane, 2,2,5-trimethylhexane, n-decane, n-dodecane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, p-menthane, and decalin. Specific examples of the aromatic compound which may have a substituent include, for example, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, cumene, mesitylene, tetralin, n-butylbenzene, p-cymene. O-diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-pentylbenzene, p-dipentylbenzene and the like. Specific examples of alcohols include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, n-hexanol, n-heptanol, n- Octanol, 2-ethyl-1-hexanol, benzyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2-isopropoxyethanol, 2 -Butoxyethanol, 2-isopentyloxyethanol, 2-hexyloxyethanol, 2-benzyloxyethanol, tetrahydrofurfuryl alcohol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, Tylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether, dipropylene glycol monobutyl ether, triethylene glycol, tripropylene glycol, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetraethylene glycol, 1,3-butanediol, 1,4-butanediol, , 5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, and the like. Specific examples of ethers include, for example, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-n-hexyl ether, anisole, ethyl phenyl ether, n-butyl phenyl ether, n-pentyl phenyl ether. , O-methoxytoluene, m-methoxytoluene, p-methoxytoluene, benzyl ethyl ether, tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-di-n-butoxyethane , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n Butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol di -n- butyl ether. Specific examples of ketones include, for example, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetonyl acetone, dichlorohexanone, methylcyclohexanone, and the like. Can be mentioned. Specific examples of esters include, for example, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2 -Ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, n-butyl propionate, isopentyl propionate, methyl butyrate, ethyl butyrate, n-butyl butyrate, isopentyl butyrate, isobutyl isobutyrate, ethyl isovalerate , Methyl benzoate, ethyl benzoate, n-butyl benzoate, bis (2-ethylhexyl) adipate, diethyl oxalate, diethyl malonate, ethylene glycol diacetate, glycerin triacetate, 2-methoxyethyl acetate 2-ethoxyethyl acetate, 2-n-butoxyethyl acetate, 2-phenoxyethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono Examples include butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate. In addition, although only 1 type may be used for these organic solvents, 2 or more types can also be used as needed. The amount of the organic solvent used, the reaction temperature, the reaction time, etc. are the same as when the cationic polymerizable diluent (B) is used as the reaction solvent. When the copolymer (A) is synthesized in an organic solvent that does not participate in the radical polymerization reaction, the organic solvent is removed by a method such as aeration after completion of the reaction, and then a predetermined amount of the cationic polymerizable diluent (B ), Or after synthesizing the copolymer (A) in the organic solvent, it is diluted by adding a predetermined amount of the cationic polymerizable diluent (B), and then a method such as aeration. The organic solvent may be removed. When the organic solvent is removed by a method such as aeration, the fluorine atom-containing monofunctional (when the total weight of the fluorine atom-containing monofunctional (meth) acrylate, glycidyl (meth) acrylate and organic solvent is 100) The total amount of the meth) acrylate and glycidyl (meth) acrylate can be adjusted to 60 or more by weight ratio to reduce the amount of the organic solvent used. Further, when the copolymer (A) is synthesized in an organic solvent that does not participate in radical polymerization reaction, it is also possible to dilute after the reaction by adding a vinyl ether compound (e) as a cationic polymerizable diluent (B).

  The photocurable resin composition of the present invention is prepared by blending the copolymer (A) with the cationic polymerizable diluent (B). In addition, the cationically polymerizable diluent (B) used here can be used as a reaction solvent when synthesizing the copolymer (A) other than the vinyl ether compound described later. Specific examples of the cationic polymerizable diluent (B) used herein include, for example, an epoxy group-containing compound (a), an oxetane ring-containing compound (b), a lactone (c), and a cyclic carbonate (d). Can be mentioned. In addition, when these cationic polymerizable diluents (B) are mixed and used when synthesizing the copolymer (A), they do not have a radically polymerizable vinyl group, acryloyl group, methacryloyl group or the like in the structure. is required. Therefore, when the cationic polymerizable diluent (B) is mixed and used when synthesizing the copolymer (A), a vinyl ether compound cannot be used as the cationic polymerizable diluent (B). Further, since the copolymer (A) used in the present invention is a low refractive index resin having a fluorine atom, the cationic polymerizable diluent (B) does not have an aromatic ring from the viewpoint of refractive index and compatibility. It is preferred that a compound is used.

  Specific examples of the compound (a) having an epoxy group used as the cationic polymerizable diluent (B) in the photocurable resin composition of the present invention include, for example, 3,4-epoxycyclohexylmethyl-3,4-epoxy. Cyclohexanecarboxylate, bis- (3,4-epoxycyclohexyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis- (2,3 -Epoxycyclopentyl) ether, 2-ethylhexyl diglycol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol Diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, etc. it can. Similarly, as the compound (b) having an oxetane ring, for example, 3,3-dimethyloxetane, 2-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-oxetanemethanol, 3-methyl- 3-methoxymethyl oxetane and the like can be mentioned. Furthermore, specific examples of lactones (c) include β-propiolactone, γ-butyrolactone, ε-caprolactone, σ-valerolactone, and the like. Furthermore, specific examples of the cyclic carbonates (d) include ethylene carbonate, propylene carbonate, butylene carbonate and the like.

  The cationic polymerizable diluent (B) described above may be used alone, or a plurality of compounds may be mixed and used. These cationic polymerizable diluents (B) are copolymer (A): cationic polymerizable diluent (B) = 10-80: 90-20 (however, (A) + (B) = 100 in weight ratio). It is preferable that the weight ratio of copolymer (A): cationically polymerizable diluent (B) = 20-60: 80-40 is more preferable. It is good to be. The viscosity of the cationic polymerizable diluent (B) varies depending on the required viscosity of the photocurable resin composition of the present invention, but is generally preferably 1000 mPa · s or less at 25 ° C., and particularly used. When the weight ratio of the copolymer (A) to the cationic polymerizable diluent (B) is in the range of copolymer (A): cation polymerizable diluent (B) = 40-80: 60-20, 25 It is preferably 100 mPa · s or less at ° C.

  The copolymer (A) is synthesized in an organic solvent that does not participate in the radical polymerization reaction, and after completion of the reaction, the organic solvent is removed by a method such as aeration, and then a predetermined amount of the cationic polymerizable diluent (B) is added. When diluting, a vinyl ether compound (e) can be used as the cationic polymerizable diluent (B). Specific examples thereof include, for example, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 1,4-butanediol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, propylene Examples include glycol divinyl ether, neopentyl glycol divinyl ether, glycerol trivinyl ether, trimethylolpropane trivinyl ether, and cyclohexanedimethanol divinyl ether. In addition, although only 1 type may use these vinyl ether compounds, 2 or more types of vinyl ether compounds can also be used as needed.

  In the photocurable resin composition of the present invention, a photocationic polymerization initiator (C) is blended as a curing catalyst. The photocationic polymerization initiator (C) used in the photocurable resin composition of the present invention can be used without particular limitation as long as it generates an acid upon irradiation with active energy rays. Specific examples of the cationic photopolymerization initiator (C) that can be used in the photocurable resin composition of the present invention include iodonium salts, sulfonium salts, phosphonium salts, and pyridinium salts. Of these, iodonium salts and sulfonium salts are preferred.

  Examples of the iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-methylphenyl) iodonium hexafluorophosphate, bis ( 4-methylphenyl) iodonium hexafluoroantimonate, bis (4-methylphenyl) iodonium trifluoromethanesulfonate, bis (4-methylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (4-tert-butylphenyl) iodonium hexa Fluorophosphate, bis (4-tert-butylphenyl) iodonium Hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (4-octylphenyl) iodonium hexafluorophosphate, bis (4-octylphenyl) iodonium hexafluoroantimonate, bis (4-octylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (4-dodecylphenyl) iodonium hexafluorophosphate, bis (4-dodecylphenyl) iodonium hexafluoro Antimonate, bis (4-dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, (4-methoxy Phenyl) phenyliodonium hexafluorophosphate, (4-methoxyphenyl) phenyliodonium hexafluoroantimonate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, (tolylcumyl) iodonium hexafluorophosphate, (tolylcumyl) iodonium hexafluoroantimonate, (Tolylcumyl) iodonium tetrakis (pentafluorophenyl) borate, (4-methylphenyl) (4′-isobutylphenyl) iodonium hexafluorophosphate, (4-methylphenyl) (4′-isobutylphenyl) iodonium hexafluoroantimonate, 4-methylphenyl) (4'-isobutylphenyl) iodonium tetrakis (pentafluoro Phenyl) borate and the like.

  Examples of the sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoromethanesulfonate, tris (4-methylphenyl) sulfonium hexafluorophosphate, tris (4 -Methylphenyl) sulfonium hexafluoroantimonate, 4-phenylthiophenyl-diphenylsulfonium hexafluorophosphate, 4-phenylthiophenyl-diphenylsulfonium hexafluoroantimonate, di- (4-methylphenyl) -4-phenylthiophenylsulfonium Hexafluorophosphate, di- (4-methylphenyl) -4-phenylthio Phenylsulfonium hexafluoroantimonate, di- (4-fluorophenyl) -4-phenylthiophenylsulfonium hexafluorophosphate, di- (4-fluorophenyl) -4-phenylthiophenylsulfonium hexafluoroantimonate, 4- (4 -Benzoyl-phenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (4-benzoyl-phenylthio) phenyl-diphenylsulfonium hexafluoroantimonate, 4- (4-benzoyl-phenylthio) phenyl-di (4-methylphenyl) sulfonium Hexafluorophosphate, 4- (4-benzoyl-phenylthio) phenyl-di (4-methylphenyl) sulfonium hexafluoroantimonate, 4- (4- Nzoyl-phenylthio) phenyl-di (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (4-benzoyl-phenylthio) phenyl-di (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (4- (4- Methylbenzoyl) phenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (4- (4-methylbenzoyl) phenylthio) phenyl-diphenylsulfonium hexafluoroantimonate, 4- (4- (4-methylbenzoyl) phenylthio) phenyl- Di (4-methylphenyl) sulfonium hexafluorophosphate, 4- (4- (4-methylbenzoyl) phenylthio) phenyl-di (4-methylphenyl) sulfonium hexafluoroan Timonate, 4- (4- (4-methylbenzoyl) phenylthio) phenyl-di (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (4- (4-methylbenzoyl) phenylthio) phenyl-di (4-fluorophenyl) ) Sulfonium hexafluoroantimonate, 4- (4- (4-tert-butylbenzoyl) phenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (4- (4-tert-butylbenzoyl) phenylthio) phenyl-diphenylsulfonium hexa Fluoroantimonate, 4- (4- (4-tert-butylbenzoyl) phenylthio) phenyl-di (4-methylphenyl) sulfonium hexafluorophosphate, 4- (4- (4-tert-butylbenzoate) Zoyl) phenylthio) phenyl-di (4-methylphenyl) sulfonium hexafluoroantimonate, 4- (4- (4-tert-butylbenzoyl) phenylthio) phenyl-di (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (4- (4-tert-butylbenzoyl) phenylthio) phenyl-di (4-fluorophenyl) sulfonium hexafluoroantimonate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate, 4, 4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis (di (4-fluorophenyl) sulfonio) phenyl sulfide-bis-hexafluorophosphate, 4 4′-bis (di (4-fluorophenyl) sulfonio) phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis (di (4-methylphenyl) sulfonio) phenyl sulfide-bis-hexafluorophosphate, 4 , 4′-bis (di (4-methylphenyl) sulfonio) phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis (di (β-hydroxyethoxy) phenylsulfonio) phenyl sulfide-bis-hexafluoro Mention may be made of phosphate, 4,4′-bis (di (β-hydroxyethoxy) phenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate, and the like.

  Examples of the phosphonium salt include tetraphenylphosphonium hexafluorophosphate, tetrafluorophosphonium hexafluoroantimonate, triphenyl (3,3-dicyano-2-propenyl) phosphonium hexafluorophosphate, triphenyl (3,3-dicyano-2). -Propenyl) phosphonium hexafluoroantimonate, triphenylmethoxyphosphonium hexafluorophosphate, triphenylmethoxyphosphonium hexafluoroantimonate, n-butoxytriphenylphosphonium hexafluorophosphate, n-butoxytriphenylphosphonium hexafluoroantimonate, etc. Can do. Examples of the pyridinium salt include N- (α-phenylbenzyl) -2-cyanopyridinium hexafluorophosphate, N- (α-phenylbenzyl) -2-cyanopyridinium hexafluoroantimonate, N- (α-naphthyl). Methyl) -2-cyanopyridinium hexafluorophosphate, N- (α-naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, N-benzyl-2-cyanopyridinium hexafluorophosphate, N-benzyl-2-cyanopyridinium hexa Fluoroantimonate and the like can be mentioned.

  These cationic photopolymerization initiators (for example, rhodosyl photopolymerization initiator 2074 (tricumyl) iodonium tetrakis (pentafluorophenyl) borate manufactured by Rhodia), Irgacure 250 (4-methylphenyl) manufactured by Ciba Geigy Co., Ltd. (4′-isobutylphenyl) iodonium hexafluorophosphate), BBI-102 (bis (4-tert-butylphenyl) iodonium hexafluorophosphate) manufactured by Midori Kagaku Co., Ltd., and Cyracure UVI-6974 (sulfurium salt type). A mixture of 4-phenylthiophenyl-diphenylsulfonium hexafluoroantimonate and 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate) And Cyracure UVI-6990 (mixture of 4-phenylthiophenyl-diphenylsulfonium hexafluorophosphate and 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate) (both manufactured by Union Carbide), Adekaoptomer SP-170 (4,4′-bis (di (β-hydroxyethoxy) phenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate) and SP-150 (4,4′-bis (di (β -Hydroxyethoxy) phenylsulfonio) phenyl sulfide-bis-hexafluorophosphate) (all manufactured by Asahi Denka Kogyo Co., Ltd.), Kayacure PCI-220 (manufactured by Nippon Kayaku Co., Ltd. 4- (4- (4-tert) -Butylbenzoyl) pheny Thio) phenyl - di (4-methylphenyl) sulfonium hexafluorophosphate) and the like are available from each market.

  In the photocurable resin composition of the present invention, the above-described photocationic polymerization initiator (C) may be used alone, or a plurality may be used as necessary. Moreover, the usage-amount of the photocationic polymerization initiator (C) in this invention is 0.1-10 weight ratio, when the sum total of the weight of a copolymer (A) and a cationically polymerizable diluent (B) is set to 100. It is preferable to use it so that it may become in the range of 0.5-5, More preferably in the range of 0.5-5. When the above cationic photopolymerization initiator (C) is difficult to dissolve in the copolymer (A) and the cationic polymerizable diluent (B), the cationic photopolymerization initiator (C) is made of propylene carbonate or γ-butyrolactone. Such a low molecular weight and highly soluble cationic polymerizable diluent may be pre-diluted and blended. In addition, it is preferable that the usage-amount of a cationic polymerization diluent with high solubility like propylene carbonate and (gamma) -butyrolactone is used so that the density | concentration of a photocationic polymerization initiator (C) may be 25 to 80 weight%. .

  If necessary, the photocurable resin composition of the present invention can further improve the sensitivity to active energy rays by blending a photosensitizer (D), and the photocurability having a faster curing rate. It can be set as a resin composition. Specific examples of the photosensitizer (D) that can be used in the present invention include, for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, chrysene derivatives, perylene derivatives, pentacene derivatives, acridine derivatives, benzothiazole derivatives, Benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, xanthone derivatives, thioxanthene derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, trines Examples include allylmethane derivatives, phthalocyanine derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, and organoruthenium complexes. Among them, preferred are naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, chrysene derivatives, perylene derivatives, acridine derivatives, and among them, an alkyl group having 1 to 4 carbon atoms that may particularly contain an oxygen atom. Is preferably a 9,10-dialkoxyanthracene derivative or a 9,10-di (alkoxyalkoxy) anthracene derivative.

  Here, specific examples of the 9,10-dialkoxyanthracene derivative or the 9,10-di (alkoxyalkoxy) anthracene derivative having an alkyl group having 1 to 4 carbon atoms which may contain an oxygen atom as a substituent include, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-tert-butyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, 9,10-diethoxy Anthracene, 2-ethyl-9,10-diethoxyanthracene, 2-tert-butyl-9,10-diethoxyanthracene, 2,3-dimethyl-9,10-diethoxyanthracene, 9,10-di (n- Propoxy) anthracene, 2-ethyl-9,10-di (n-propoxy) a Tracene, 9,10-diisopropoxyanthracene, 2-ethyl-9,10-diisopropoxyanthracene, 9,10-di (2-methoxyethoxy) anthracene, 2-ethyl-9,10-di (2-methoxy) Ethoxy) anthracene, 2-tert-butyl-9,10-di (2-methoxyethoxy) anthracene, 2,3-dimethyl-9,10-di (2-methoxyethoxy) anthracene, 9,10-di (n- Butoxy) anthracene, 2-ethyl-9,10-di (n-butoxy) anthracene, 2-tert-butyl-9,10-di (n-butoxy) anthracene, 2,3-dimethyl-9,10-di ( n-butoxy) anthracene, 9,10-di (2-ethoxyethoxy) anthracene, 2-ethyl-9,10-di (2-ethoxyethylene) Alkoxy) anthracene, 2-tert-butyl-9,10-di (2-ethoxyethoxy) anthracene, 2,3-dimethyl-9,10-di (2-ethoxyethoxy) can be mentioned anthracene.

  In the photocurable resin composition of the present invention, the above-described photosensitizer (D) may be used alone, or may be used in combination as necessary. Moreover, the usage-amount of the photosensitizer (D) in the photocurable resin composition of this invention shall be 0.001-1 of weight ratio with respect to 1 weight part of usage-amounts of a photocationic polymerization initiator (C). Is more preferable, and 0.05 to 0.5 is more preferable.

  Here, the blending ratio of the copolymer (A), the cationic polymerizable diluent (B) and the cationic photopolymerization initiator (C) used in the photocurable resin composition of the present invention is (A) by weight ratio. Component: (B) component: (C) component = 10-80: 90-20: 0.1-10 (however, (A) component + (B) component = 100, the same shall apply hereinafter) More preferably, (A) component: (B) component: (C) component = 20-60: 80-40: 0.5-5. Moreover, when using a photosensitizer (D) as needed, (A) component: (B) component: (C) component: (D) component = 10-80: 90-20: 0.1 by weight ratio. -10: 0.0001-10, more preferably (A) component: (B) component: (C) component: (D) component = 20-60: 80-40: 0.5-5 : 0.025 to 2.5. The copolymer (A) component is obtained by copolymerizing a fluorine atom-containing monofunctional (meth) acrylate and glycidyl (meth) acrylate, but the fluorine atom-containing monofunctional (meth) acrylate and glycidyl (meth) acrylate. The copolymerization ratio of fluorine atom-containing monofunctional (meth) acrylate: glycidyl (meth) acrylate = 99-60: 1-40 (however, fluorine atom-containing monofunctional (meth) acrylate and glycidyl (meth) acrylate) The total number of moles of these is preferably 100), and more preferably copolymerized at a molar ratio of fluorine atom-containing monofunctional (meth) acrylate: glycidyl (meth) acrylate = 95 to 70: 5 to 30 It is good to let them.

  The photocurable resin composition of the present invention comprises the above-mentioned copolymer (A), cationic polymerizable diluent (B) and photocationic polymerization initiator (C), and, if necessary, a photosensitizer (D ) Is mixed and dissolved. In addition, although it is preferable to implement the photocurable resin composition of this invention at room temperature or less, when it does not become a uniform solution, you may heat and melt | dissolve each component. When the photocurable resin composition of the present invention is prepared by heating, the heating temperature is preferably 40 to 90 ° C.

  The photocurable resin composition of the present invention further includes fillers, color pigments, leveling agents, antifoaming agents, antioxidants, silane coupling agents, epoxy resins (for example, bisphenol type epoxy resins, novolak type epoxy resins, etc. ) Etc. can be mixed.

  The photo-curable resin composition of the present invention can be applied to any substrate such as glass, metal, plastic, etc. without using an organic solvent such as esters that do not have cationic polymerizability. It is possible to use the organic solvent depending on the case. Examples of the esters having no cationic polymerizability include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, and 2-ethyl. Butyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, n-butyl propionate, isopentyl propionate, methyl butyrate, ethyl butyrate, n-butyl butyrate, isopentyl butyrate, isobutyl isobutyrate, Ethyl isovalerate, methyl benzoate, ethyl benzoate, n-butyl benzoate, bis (2-ethylhexyl) adipate, diethyl oxalate, diethyl malonate, ethylene glycol diacetate, glycerol triacetate, 2-methyl Xylethyl acetate, 2-ethoxyethyl acetate, 2-n-butoxyethyl acetate, 2-phenoxyethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Examples thereof include monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate and the like. Examples of the method for applying the photocurable resin composition of the present invention to a substrate include, for example, a method of directly applying by brush coating, a bar coater, an applicator, a roll coater or a roll brush, an air spray or an air spray coating machine, etc. A spray coating method, a flow coating method using a shower coater or a curtain flow coater (flow coating), a dipping method, a casting method, a spin coating method, and the like can be used. Among these, a spin coating method is most suitable. In addition, it is preferable to use properly the coating method mentioned above according to the material, shape, use, etc. of a base material.

The cured product (cured film) of the present invention can be obtained by irradiating the photocurable resin composition of the present invention with active energy rays such as ultraviolet rays after coating. Examples of the light source used for curing the photocurable resin composition of the present invention include, for example, a xenon lamp, a carbon arc, a germicidal lamp, a fluorescent lamp for ultraviolet rays, a medium pressure mercury lamp, a high pressure mercury lamp, and an ultrahigh pressure mercury lamp. An electrodeless lamp, a metal halide lamp, or an electron beam using a scanning type or curtain type electron beam acceleration path can be used. Moreover, when hardening the photocurable resin composition of this invention by ultraviolet irradiation, the ultraviolet irradiation amount required for hardening may be about 300-3000 mJ / cm < ² >. Furthermore, you may heat-process the cured | curing material of this invention obtained by irradiating an active energy ray to 50-250 degreeC in order to complete the hardening by superposition | polymerization. In the case of heat treatment, in consideration of the heat resistance of the substrate to which the photocurable resin composition of the present invention is applied and the resulting coating film, the heat treatment is performed in as short a time as possible when the heat treatment is performed at a high temperature of 100 ° C. or higher. It is preferable to carry out.

  The cured product of the present invention can be used effectively as an adhesive for optical articles such as optical lenses, optical fiber and device connections, and optical communication articles such as optical connectors. It can be used as a protective film for color filters used in displays, etc., and as a resist underlayer film, but as other applications, liquid crystal display panels, etc., other optical articles, paints, clear coatings other than optical articles Etc. can also be used.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited at all by the following examples.

Synthetic example of copolymer (A) Synthetic example 1:
In a 500 ml four-necked flask, 1H, 1H, 5H-pentafluoropentyl methacrylate (trade name: Biscoat 8FM, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 73.3 g, 2,2,2-trifluoroethyl methacrylate (product) Name: Fluorester, manufactured by Tosoh F-Tech Co., Ltd.) 27.4 g, glycidyl methacrylate (trade name: Light Ester G, manufactured by Kyoeisha Chemical Co., Ltd.) 19.3 g, α, α′-azobis (isobutyronitrile) 0.5 g and 18-g of 1,6-hexanediol diglycidyl ether (trade name: Epolite 1600, manufactured by Kyoeisha Chemical Co., Ltd.) were charged, and nitrogen gas was allowed to flow into the flask for 15 minutes while stirring. And stirred at 86-91 ° C. for 5 hours. When the reaction solution was cooled to 20 to 25 ° C. after completion of the reaction, the obtained reaction solution did not become cloudy or separated into two layers, and the reaction solution was a colorless to slightly yellow transparent uniform liquid. The obtained reaction solution was further filtered to obtain a 1,6-hexanediol diglycidyl ether solution of the copolymer (A-1). The viscosity of the obtained copolymer (A-1) solution was 463 mPa · s at 25 ° C., and the refractive index at 25 ° C. was 1.4452. The viscosity was measured with an E-type viscometer (model number: DVR-EII, manufactured by Tokimec Co., Ltd.), and the refractive index was measured with an Abbe refractometer (model number: DR-M2, manufactured by Atago Co., Ltd.) (about the following examples) Similarly, the viscosity of the reaction product was measured with the E-type viscometer and the refractive index was measured with the Abbe refractometer). The copolymer (A-1) component in the copolymer (A-1) solution was 40.1% by weight from the calculated value, and the refractive index of 1,6-hexanediol diglycidyl ether at 25 ° C. Was 1.4600, and the refractive index of the copolymer (A-1) component at 25 ° C. is estimated to be 1.4231.

Synthesis example 2:
In a 500 ml four-necked flask, 2- (perfluoro-n-octyl) ethyl methacrylate (trade name: Biscote 17FM, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 87.9 g, 2,2,2-trifluoroethyl methacrylate 21 .6 g, 10.5 g of glycidyl methacrylate, 0.4 g of α, α′-azobis (isobutyronitrile) and 180.0 g of 1,6-hexanediol diglycidyl ether were charged in a flask with stirring for 15 minutes. Then, the mixture was heated up and stirred at 84 to 89 ° C. for 5 hours. When the reaction solution was cooled to 20 to 25 ° C. after completion of the reaction, the obtained reaction solution did not become cloudy or separated into two layers, and the reaction solution was a colorless to slightly yellow transparent uniform liquid. The obtained reaction liquid was further filtered to obtain a 1,6-hexanediol diglycidyl ether solution of the copolymer (A-2). The viscosity of the obtained copolymer (A-2) solution was 360 mPa · s at 25 ° C., and the refractive index at 25 ° C. was 1.4390. The copolymer (A-2) component in the copolymer (A-2) solution was 40.1% by weight from the calculated value, and the refractive index of 1,6-hexanediol diglycidyl ether at 25 ° C. Was 1.4600, and thus the refractive index of the copolymer (A-2) component at 25 ° C. is estimated to be 1.4076.

Synthesis Example 3:
In a 500 ml four-necked flask, 88.4 g of 2- (perfluoro-n-octyl) ethyl methacrylate, 49.8 g of 1H, 1H, 5H-pentafluoropentyl methacrylate, 11.8 g of glycidyl methacrylate, α, α′-azobis ( (Isobutyronitrile) 0.7 g and diethylene glycol diglycidyl ether (trade name: EPOLIGHT 100E, manufactured by Kyoeisha Chemical Co., Ltd.) 150.0 g were charged, and nitrogen gas was allowed to flow in the flask for 15 minutes with stirring, followed by heating. And stirred at 85 to 92 ° C. for 5 hours. When the reaction solution was cooled to 20 to 25 ° C. after completion of the reaction, the obtained reaction solution did not become cloudy or separated into two layers, and the reaction solution was a colorless to slightly yellow transparent uniform liquid. The obtained reaction solution was further filtered to obtain a diethylene glycol diglycidyl ether solution of copolymer (A-3). The viscosity of the obtained copolymer (A-3) solution was 565 mPa · s at 25 ° C., and the refractive index at 25 ° C. was 1.4288. The copolymer (A-3) component in the copolymer (A-3) solution is 50.1% by weight from the calculated value, and the refractive index of diethylene glycol diglycidyl ether at 25 ° C. is 1.4659. Therefore, the refractive index at 25 ° C. of the copolymer (A-3) component is estimated to be 1.3918.

Synthesis Example 4:
To a 500 ml four-necked flask equipped with a condenser, 2- (perfluoro-n-octyl) ethyl methacrylate (trade name: Biscoat 17FM, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 88.4 g, 1H, 1H, 5H- 49.8 g of pentafluoropentyl methacrylate (trade name: Biscoat 8FM, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 11.8 g of glycidyl methacrylate, 0.7 g of α, α′-azobis (isobutyronitrile) and n-butyl acetate After charging 150.0 g and flowing nitrogen gas into the flask for 15 minutes while stirring, the temperature was raised and the mixture was stirred at 90 to 93 ° C. for 5 hours. After completion of the reaction, the reaction solution was cooled to 20 to 25 ° C., and the resulting reaction solution did not cause turbidity or two-layer separation, and was a colorless to slightly yellow transparent uniform copolymer (A-4). It was an n-butyl acetate solution.

  Next, 200 g of an n-butyl acetate solution of the obtained copolymer (A-4) was charged into a 500 ml eggplant-shaped flask, and 100.0 g of diethylene glycol diglycidyl ether was charged into the flask and attached to a rotary evaporator. Aeration was performed at 0 ° C. to recover n-butyl acetate, and after the distillation of n-butyl acetate was stopped, aeration was further performed for 2 hours to cool. The diethylene glycol diglycidyl ether solution of the obtained copolymer (A-4) is a colorless to slightly yellow transparent uniform liquid, the viscosity is 540 mPa · s at 25 ° C., and the refractive index at 25 ° C. is 1.4286. Met. The copolymer (A-4) component in the copolymer (A-4) solution is 50.0% by weight from the calculated value, and the refractive index of diethylene glycol diglycidyl ether at 25 ° C. is 1.4659. Therefore, the refractive index at 25 ° C. of the copolymer (A-4) component was estimated to be 1.3913, and it was the same compound as the copolymer (A-3) obtained in Synthesis Example 3. It was.

Examples of Photocurable Resin Composition and Cured Product Creation of the Present Invention In the examples, the viscosity is measured with an E-type viscometer (model number: DVR-EII, manufactured by Tokimec Co., Ltd.), and the refractive index is an Abbe refractometer ( Model number: DR-M2, manufactured by Atago Co., Ltd.).

Example 1
In a 200 ml brown transparent eggplant-shaped flask, 100.0 g of the copolymer (A-1) solution obtained in Synthesis Example 1, (Tricumyl) iodonium tetrakis (pentafluorophenyl) borate (trade name: Rhodosyl photopolymerization initiator) 2074, manufactured by Rhodia Co., Ltd.) 2.0 g was charged and dissolved by heating at 50 to 60 ° C. to obtain a colorless to slightly yellow transparent and uniform photocurable resin composition of the present invention. This had a refractive index of 1.4514 at 25 ° C. The obtained photocurable resin composition of the present invention was coated on a release-treated aluminum plate with a bar coater so as to have a thickness of about 50 μm, and further, 1500 mJ / cm with a high-pressure mercury lamp from above. After irradiating with ultraviolet rays at an irradiation amount of ^2, a colorless and transparent cured product (cured film) of the present invention was obtained by heating at 120 ° C. for 15 minutes. When the obtained cured film was visually observed, opaque parts such as whitening and turbidity were not seen at all in the cured film.

  Further, after the photocurable resin composition of the present invention was applied to a fluororesin plate in the same manner and cured, the cured film was peeled off from the fluororesin plate, and the refractive index of the cured film was measured. 4711.

Example 2
A 200 ml brown transparent eggplant-shaped flask was charged with 100.0 g of the copolymer (A-2) solution obtained in Synthesis Example 2 and 1.8 g of (triccumyl) iodonium tetrakis (pentafluorophenyl) borate, and 50-60 A colorless to slightly yellow transparent and uniform photocurable resin composition of the present invention was obtained by heating and dissolving at 0 ° C. This had a refractive index of 1.4447 at 25 ° C. The obtained photocurable resin composition of the present invention was coated on a release-treated aluminum plate with a bar coater so as to have a thickness of about 50 μm, and further, 1500 mJ / cm with a high-pressure mercury lamp from above. After irradiating with ultraviolet rays at an irradiation amount of ^2, a colorless and transparent cured product (cured film) of the present invention was obtained by heating at 120 ° C. for 15 minutes. When the obtained cured film was visually observed, opaque parts such as whitening and turbidity were not seen at all in the cured film.

  Further, after the photocurable resin composition of the present invention was applied to a fluororesin plate in the same manner and cured, the cured film was peeled off from the fluororesin plate, and the refractive index of the cured film was measured. 4646.

Example 3
In a 200 ml brown transparent eggplant-shaped flask, 100.0 g of the copolymer (A-3) solution obtained in Synthesis Example 3, bis (4-tert-butylphenyl) iodonium hexafluorophosphate (trade name: BBI-102) 1.5 g, 2-ethyl-9,10-dimethoxyanthracene (0.5 g), prepared by Midori Chemical Co., Ltd., and dissolved by heating at around 60 ° C. A functional resin composition was obtained. This had a refractive index of 1.4349 at 25 ° C. The obtained photocurable resin composition of the present invention was coated on a release-treated aluminum plate with a bar coater so as to have a thickness of about 50 μm, and further, 1500 mJ / cm with a high-pressure mercury lamp from above. After irradiating with ultraviolet rays at an irradiation amount of ^2, a colorless and transparent cured product (cured film) of the present invention was obtained by heating at 120 ° C. for 15 minutes. When the obtained cured film was visually observed, opaque parts such as whitening and turbidity were not seen at all in the cured film.

  Further, after the photocurable resin composition of the present invention was applied to a fluororesin plate in the same manner and cured, the cured film was peeled off from the fluororesin plate, and the refractive index of the cured film was measured. 4528.

Example of evaluation of cured product (cured film) of the present invention Example 4: Adhesion test to glass The photo-curable resin composition of the present invention prepared in Example 1 was cast on quartz glass, and quartz was formed from the cast. piled glass is irradiated with ultraviolet irradiation amount of 2000 mJ / cm ² from the quartz glass in a high-pressure mercury lamp and heated at 100 ° C. 30 minutes to obtain a sample piece of the cured product of the present invention (hardened film). Inserting a metal spatula between the quartz glass and the quartz glass of the obtained sample piece, and trying to peel off the quartz glass by tapping the spatula pattern part with a mallet, one of the two pieces The quartz glass plate broke down. When the same test was performed on the photocurable resin composition of the present invention prepared in Example 2 and Example 3, the same result as that of the photocurable resin composition of the present invention prepared in Example 1 was obtained. It was.

Example 5: Solvent resistance test The surface of the cured product (cured film) of the present invention produced in Examples 1 to 3 was rubbed 20 times with gauze soaked with methyl ethyl ketone, and the condition of the cured film surface was observed. As a result, no change was observed on the surface of all the cured films.

  From the results of Examples 1 to 3, it was found that the photocurable resin composition of the present invention was colorless and transparent and had a low refractive index, and was cured rapidly upon irradiation with ultraviolet rays. It was also shown that the cured product of the present invention is excellent in transparency and has a low refractive index. Furthermore, from the results of Examples 4 and 5, it was found that the cured product of the present invention has high adhesion to glass and solvent resistance, which are the objects of the present invention.

Claims (11)

Light containing a copolymer (A) of a fluorine atom-containing monofunctional (meth) acrylate and glycidyl (meth) acrylate, a cationic polymerizable diluent (B), and a photocationic polymerization initiator (C) Curable resin composition. The photocurable resin composition of Claim 1 whose refractive index of a copolymer (A) is 1.50 or less. The weight ratio of the copolymer (A) and the cationic polymerizable diluent (B) is copolymer (A): cationic polymerizable diluent (B) = 10-80: 90-20. The photocurable resin composition as described. The weight ratio of the total weight of the copolymer (A) and the cationic polymerizable diluent (B) to the photocationic polymerization initiator (C) is (copolymer (A) + cationic polymerizable diluent (B)): The photocurable resin composition according to any one of claims 1 to 3, wherein the photocationic polymerization initiator (C) is 100: 0.1 to 10. The photocurable resin composition according to any one of claims 1 to 4, wherein the cationic photopolymerization initiator (C) is an iodonium salt compound. The photocurable resin composition according to any one of claims 1 to 5, further comprising a photosensitizer (D). The photocurable resin composition according to any one of claims 1 to 6, wherein a compound other than the cationic polymerizable diluent (B) is not contained as a diluent. The photocurable resin composition according to any one of claims 1 to 7, wherein the use is an adhesive for optical articles. The photocurable resin composition according to any one of claims 1 to 7, wherein the use is an adhesive for optical communication articles. An optical article having a cured product layer of the photocurable resin composition according to claim 8. An article for optical communication having a cured product layer of the photocurable resin composition according to claim 9.