JP2006241241A - Photosensitive material and laminated product given by using the photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive material having a high refractive index by the material itself and further having enough resistance to yellowing. <P>SOLUTION: This photosensitive material contains a compound expressed by general formula (1) (R<SB>1</SB>, R<SB>2</SB>and R<SB>3</SB>are each a monovalent organic residue, provided that at least one of R<SB>1</SB>, R<SB>2</SB>and R<SB>3</SB>has substituted or unsubstituted phenyl, at least one of R<SB>1</SB>, R<SB>2</SB>and R<SB>3</SB>is an organic residue containing an unsaturated double bond, and R<SB>3</SB>may form a ring together with R<SB>1</SB>or with R<SB>2</SB>). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive material. The photosensitive material of the present invention can be used for lenses, waveguides, optical fibers, or optical elements such as interference films, optical filters, and holograms alternately laminated with low refractive index layers.

  In recent years, a transparent photosensitive material having a high refractive index has been demanded for optical articles. Such photosensitive materials are actively studied for lenses, waveguides, optical fibers, or optical elements such as interference films, optical filters, and holograms alternately laminated with low refractive index layers. (See Patent Documents 1-5)

In these applications, in addition to high refractive index properties, there are various required physical properties such as yellowing resistance. However, in the past, in order to increase the refractive index, it was dealt with by increasing the blending ratio of the inorganic material, but as the blending ratio of the inorganic material increases, the advantage of the organic material becomes harder to develop, and crack resistance, etc. It becomes difficult to express. Therefore, it is necessary to increase the refractive index of the photosensitive material itself and reduce the compounding ratio of the inorganic fine particles.
Moreover, since there exists a material which becomes easy to yellow by mixing with an inorganic material depending on the photosensitive material, it is necessary to exclude such a material.
JP-A-7-13472 JP-A-8-217825 Japanese Patent Laid-Open No. 9-208529 JP-A-11-240864 Japanese Patent Laid-Open No. 10-73718

  An object of the present invention is to provide a photosensitive material which has a high refractive index by itself and has sufficient yellowing resistance.

  That is, the present invention relates to a photosensitive material comprising a compound (A) having a phenylphosphoryl residue and having a polymerizable unsaturated bond.

The present invention also includes a compound (A) having a phenylphosphoryl residue and having a polymerizable unsaturated bond, and a photopolymerization initiator (B),
The present invention relates to a photosensitive material comprising

  Moreover, this invention relates to the said photosensitive material whose compound (A) which has a phenylphosphoryl residue and has a polymerizable unsaturated bond is following General formula (1).

General formula (1)

(In the formula, R1, R2, and R3 each independently represent a monovalent organic residue, but at least one has a substituted or unsubstituted phenyl group, and at least one contains an unsaturated double bond. Represents an organic residue, R1 and R3, and R2 and R3 may form a ring together.)
The present invention also relates to the above photosensitive material having a refractive index after exposure of 1.58 or more.
Moreover, this invention relates to the laminated body formed by laminating | stacking the said photosensitive material on a base material.
The present invention also includes a step of laminating the photosensitive material on a substrate,
And a step of irradiating the photosensitive material with light.

  According to the present invention, a photosensitive material having a refractive index of 1.58 or more alone and having good yellowing resistance can be provided.

<Compound (A) having a phenylphosphoryl residue and having a polymerizable unsaturated bond>
The compound (A) having a phenylphosphoryl residue and having a polymerizable unsaturated bond is represented by the following general formula (1).

General formula (1)

(In the formula, R1, R2, and R3 each independently represent a monovalent organic residue, but at least one has a substituted or unsubstituted phenyl group, and at least one contains an unsaturated double bond. Represents an organic residue, R1 and R3, and R2 and R3 may form a ring together.)

  Here, the monovalent organic residue is an atomic group formed by combining an aliphatic, aromatic, or heteroatom-containing atomic group alone, or specifically, an alkyl group, a cycloalkyl group, or an alkyloxy group. And aliphatic organic residues such as aryl groups and the like, and these may further have a substituent.

  Unless otherwise specified, the substituent in the present invention includes a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an amino group, a cyano group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and the like. Say.

  At least one of R1, R2, and R3 is an organic residue containing a substituted or unsubstituted phenyl group, preferably a substituted or unsubstituted phenyl group, so that the refractive index after exposure is 1.58. It is. Preferably, all of R1, R2, and R3 are organic residues containing a substituted or unsubstituted phenyl group, and preferably a substituted or unsubstituted phenyl group. Specifically, the organic residue containing a substituted or unsubstituted phenyl group includes a phenyl group, a substituted phenyl group, a benzyl group, a substituted benzyl group, a phenacyl group, a substituted phenacyl, a phenyloxy group, a substituted And the like phenyloxy group.

Examples of the substituted phenyl group include fluorine, chlorine, bromine, cyano group, nitro group, trifluoromethyl group, hydroxyl group, mercapto group, methylsulfinyl group, methylsulfonyl group, acetyl group, benzoyl group, and C _{1 to} C ₁₈ . linear, branched, cyclic alkyl group, C ₁ -C ₁₈ linear, branched, cyclic alkoxyl group, C ₂ -C ₁₈ linear, branched, selected from the cyclic alkoxycarbonyl group a phenyl group substituted by a group mentioned that, further, the benzene ring in the phenyl group, the unsaturated hydrocarbon group, condensed polycyclic aromatic rings formed even though a good structure of C ₁₀ -C ₂₂ can give.

Examples of the substituted benzyl group include fluorine, chlorine, bromine, cyano group, nitro group, trifluoromethyl group, hydroxyl group, mercapto group, methylsulfinyl group, methylsulfonyl group, acetyl group, benzoyl group, and C _{1 to} C ₁₈ . linear, branched, cyclic alkyl group, C ₁ -C ₁₈ linear, branched, cyclic alkoxyl group, C ₂ -C ₁₈ linear, branched, selected from the cyclic alkoxycarbonyl group a benzyl group substituted by a group mentioned that, further, the benzene ring in the benzyl group, the unsaturated hydrocarbon group, condensed polycyclic aromatic rings formed even though a good structure of C ₁₀ -C ₂₂ can give.

Examples of the substituted phenacyl group include fluorine, chlorine, bromine, cyano group, nitro group, trifluoromethyl group, hydroxyl group, mercapto group, methylsulfinyl group, methylsulfonyl group, acetyl group, benzoyl group, and C _{1 to} C ₁₈ . linear, branched, cyclic alkyl group, C ₁ -C ₁₈ linear, branched, cyclic alkoxyl group, C ₂ -C ₁₈ linear, branched, selected from the cyclic alkoxycarbonyl group is phenacyl group which is substituted with a group mentioned that, further, the benzene ring in the phenacyl group, the unsaturated hydrocarbon group, condensed polycyclic aromatic rings formed even though a good structure of C ₁₀ -C ₂₂ can give.

  Moreover, at least one of R1, R2, and R3 is an organic residue containing an unsaturated double bond. When the organic residue containing a substituted or unsubstituted phenyl group contains an unsaturated double bond, the organic residue is also an organic residue containing an unsaturated double bond. Specifically, organic residues containing unsaturated double bonds include (meth) acryloyl group, vinyl group, vinyloxy group, allyl group, (meth) acryloylphenyl group, vinylphenyl group, vinyloxyphenyl group, allylphenyl. Groups and the like.

The compound (A) having a phenylphosphoryl residue and having a polymerizable unsaturated bond includes a compound (a) having a phenylphosphory residue and having a reactive substituent, and a compound (a) It can also synthesize | combine by reaction with the compound (b) which has a functional group and unsaturated double bond which react with this reactive substituent.
As the compound (a), any compound having a phenylphosphoryl residue and a reactive substituent may be used.

Examples of the reactive substituent mentioned here include a hydroxyl group, a carboxyl group, a glycidyl group, an amino group, an isocyanato group, and the like.
Specific examples of the compound (a) include Phosphoric Acid Divenzyl Ester, Phosphoric Acid Diphenyl Ester, Phosphoric Acid 4-Methylumbiferyl Estel, 2- (Diphenylphosphinyl) Kogyo HQ Etc.).

<Compound (b) having a functional group that reacts with the reactive substituent of compound (a) and an unsaturated double bond>

  Examples of the reactive substituent include a hydroxyl group, a carboxyl group, a glycidyl group, an amino group, and an isocyanato group.

  Examples of the functional group capable of reacting with a hydroxyl group include an epoxy group, an isocyanato group, an acid halide, an acid anhydride group, and a carboxyl group.

  Examples of the functional group capable of reacting with a carboxyl group include an epoxy group, an oxazoline group, an amino group, a carbodiimide group, an isocyanato group, and an isothiocyanate group. An epoxy group is particularly useful as a functional group capable of reacting with a carboxyl group.

  Examples of the functional group capable of reacting with the glycidyl group include a hydroxyl group, an amino group, a mercapto group, a carboxyl group, and an N-methylol group.

  Examples of the functional group capable of reacting with an amino group include an epoxy group, an isocyanate group, an N-methylol group, a carboxyl group, an alkyl halide group, an acid anhydride group, an acid chloride group, and a formyl group.

  Examples of the functional group capable of reacting with the isocyanato group include a hydroxyl group, a mercapto group, an amino group, a carboxyl group, and an N-methylol group.

  The reaction between the reactive substituent and the functional group capable of reacting with the reactive substituent may be performed without a solvent, or may be performed in a solvent inert to the reaction. Examples of the solvent include hydrocarbon solvents such as n-hexane, benzene and toluene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, diethyl ether, tetrahydrofuran or Ether solvents such as dioxane, halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, or parkrene, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazo Examples include polar solvents such as lysinone. Two or more of these solvents may be used in combination.

  A well-known thing can be used as a compound which has an epoxy group and a polymerizable double bond. For example, glycidyl (meth) acrylate, 4 hydroxybutyl (meth) acrylate glycidyl ether, glycidyl allyl ether, 2,3-epoxy-2-methylpropyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate 4-vinyl-1-cyclohexene 1,2 epoxide, glycidyl cinnamate, 1,3-butadiene monoepoxide, Celoxide 2000 (manufactured by Daicel Chemical Industries, Ltd.), and the like.

  Examples of the compound having an isocyanato group and a polymerizable double bond include methacryloyloxyethyl isocyanate (MOI), vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate (MAI), isopropenyl-α, α-dimethylbenzyl isocyanate (TMI). ) Etc. 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanic acid Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Nisocyanate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, diisocyanate ester compounds such as dimer acid diisocyanate and hydroxyl group, carboxyl group, and amide group-containing vinyl monomers are reacted in equimolar amounts. It can be used as an ester compound.

  Alternatively, acid halides of (meth) acrylic acid, halopropionic acids, or acid halides thereof can be used. When halopropionic acids or acid halides thereof are used, the resulting halopropionic acid ester compound is dehalogenated to produce a (meth) acrylic acid ester compound. Later hardness can be increased.

  In addition, when a reaction with an acid halide of (meth) acrylic acid is performed, hydrogen halide (for example, hydrogen chloride) is by-produced. For example, triethylamine, pyridine, picoline, dimethylaniline, diethylaniline, Organic bases such as 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), or sodium bicarbonate, sodium carbonate Inorganic bases such as potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium oxide may be used as the dehydrochlorinating agent.

  In addition, in the reaction between the compound (a) and the compound (b), a compound (c) that does not have a functional group that reacts with the reactive substituent of the compound (a) and an unsaturated double bond may be used. it can.

  Known compounds can be used as the compound having an epoxy group and no polymerizable double bond. Examples thereof include styrene oxide and phenyl glycidyl ether.

A well-known thing can be used as a compound which has a functional group which can react with a hydroxyl group, and does not have a polymerizable double bond. For example, monoisocyanate can be mentioned. Examples of the monoisocyanate include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate, and phenyl isocyanate.
1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanic acid Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Nate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, diisocyanate ester compounds such as dimer acid diisocyanate, and equimolar amounts of hydroxyl group, carboxyl group and amide group-containing compounds without unsaturated double bonds The compound reacted with can also be used as an isocyanate compound.

<Catalyst>
When the reaction of the functional group that reacts with the epoxy group and the epoxy group proceeds, a catalyst such as amines may be added as necessary. As the catalyst used, a known catalyst can be used. Examples of the catalyst include the following compounds. Although the preferable specific example of a catalyst is shown below, this invention is not limited to these at all.

(1) Tertiary amines and / or salts thereof Triethylamine, tributylamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N-methylpiperazine, etc. (2) Imidazoles and / or salts thereof 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl- (1 )]-Ethyl-S-triazine, etc.

(3) Diazabicyclo compounds
1,5-diazabicyclo [5.4.0] -7-undecane, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,4-diabicyclo [2.2.2] octane, etc. (4) Phosphines tributylphosphine, Triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, tris (cyanoethyl) phosphine, etc. (5) Phosphonium salts tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate, methyltricyanoethylphosphonium tetraphenylborate etc

  The compounding ratio of the compound having an epoxy group and the catalyst used in the present invention is 0.01 to 10 parts by weight with respect to 100 parts by weight of the compound having an epoxy group. If the catalyst is less than 0.01 parts by weight, the reaction is slow, and if it exceeds 10 parts by weight, the water resistance of the cured product is lowered, which is not preferable.

  When the reaction of the epoxy group with the functional group that reacts with the epoxy group is allowed to proceed, the compound having the epoxy group to be used can be carried out without a solvent if the softening temperature is lower than the reaction temperature range. Moreover, it can also carry out using a suitable solvent irrespective of the softening temperature of the compound which has an epoxy group to be used. The solvent used at this time is not particularly limited as long as it does not react with an epoxy group, a hydroxyl group, or an organic acid. For example, known solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, acetone, and benzene can be used.

<Photoinitiator (B)>
The photopolymerization initiator is added when the photosensitive composition is cured by ultraviolet rays. In addition, an initiator is not particularly necessary when curing with an electron beam.
The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation. For example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acylphosphine oxide compound, an aminocarbonyl A compound etc. can be used.

Specific monocarbonyl compounds include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl-enetanone 3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, 3,3'4,4'-tetra ( t-Butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-trimethylbenzenemethammonium chloride, 2-hydroxy-3- (4-benzoyl-phenoxy) -N, N, N-trimethyl-1-propanamine Hydrochloride, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxyethyl) methammonium bromide, 2- / 4-iso-propylthioxanthone, 2,4-diethyl Thioxanthone, 2,4-dichlorothioxanthone 1-chloro-4-propoxythioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9Hthioxanthone-2-yloxy) -N, N, N-trimethyl-1-propanamine hydrochloride, benzoyl And methylene-3-methylnaphtho (1,2-d) thiazoline.
Examples of the dicarbonyl compound include 1,7,7-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, methyl-α-oxobenzeneacetate, 4-phenylbenzyl and the like can be mentioned.

  Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- ( 4-Isopropylphenyl) 2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymerization , Diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino-phenyl) butan-1-one, 1-phenyl-1,2- Propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholino-propanonyl) -9- Chill carbazole, and the like.

Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.
Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide.

  Examples of aminocarbonyl compounds include methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-nbutoxyethyl-4- (dimethylamino) benzoate, isoamyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, 2,5'-bis- (4-diethylaminobenzal) cyclopenta Non etc. are mentioned.

  These are not limited to the above compounds, and any compounds can be used as long as they have the ability to initiate polymerization by ultraviolet rays. These can be used alone or in combination, and the amount used is not limited, but it is preferably added in the range of 1 to 20 parts by weight relative to 100 parts by weight of the total dry weight of the cured product. Moreover, a well-known organic amine can also be added as a sensitizer.

  If necessary, a binder resin, an unsaturated compound, a photopolymerization initiator, and the like can be added to the photosensitive composition of the present invention. Examples of the binder resin include polyurethane resin, polyurea resin, polyurethane urea resin, polyester resin, polyether resin, polycarbonate resin, epoxy resin, amino resin, styrene resin, acrylic resin, melamine resin, polyamide resin, phenol resin, vinyl resin. Etc. In these resins, a polymerizable unsaturated double bond may be introduced. Any method for introducing a polymerizable unsaturated double bond may be used. These resins may be added alone, or a plurality of resins including other resins may be mixed and added.

  Examples of unsaturated compounds include alkyl (meth) acrylates and alkylene glycol (meth) acrylates as (meth) acrylate compounds.

  More specifically, as the alkyl-based (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) Acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadeci There are alkyl (meth) acrylates having 1 to 22 carbon atoms such as (meth) acrylate, icosyl (meth) acrylate, henecosyl (meth) acrylate, docosyl (meth) acrylate, etc. Examples thereof include an alkyl group-containing acrylate having a C 2-10 alkyl group, more preferably a C 2-8 alkyl group, or a corresponding methacrylate. For the purpose of adjusting leveling properties, it is preferable that the number of carbon atoms is 6 or more.

  Examples of the alkylene glycol (meth) acrylate include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, and polyethylene glycol. Mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth), etc. A monoacrylate having a polyoxyalkylene chain or a corresponding monomethacrylate,

Methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate , N-butoxytetraethylene glycol (meth) acrylate, n-pentoxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxy Tetrapropylene glycol (meth) acrylate, ethoxytetrapropyleneglycol (Meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetra Methylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, monoacrylate having an alkoxy group at the terminal and having a polyoxyalkylene chain, or a corresponding monomethacrylate, such as phenoxydiethylene glycol ( (Meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (me ) Acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxytetrapropylene glycol (meth) acrylate, etc. Polyoxyalkylene having a phenoxy or aryloxy group at the terminal There are system acrylates or corresponding methacrylates.

  Carboxylic group-containing unsaturated compounds include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth) Examples include acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and the like. I can do it.

  Examples of hydroxyl-containing unsaturated compounds other than those described above include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and 4-hydroxyvinylbenzene. And so on.

Examples of the nitrogen-containing unsaturated compound include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, and N-propoxymethyl- (meth) acrylamide. , N-butoxymethyl- (meth) acrylamide, monoalkylol (meth) acrylamide such as N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl ( (Meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, Acrylamide-type unsaturated compounds such as N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide, dialalkylol (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( (Meth) acrylate methylethylaminoethyl (meth) acrylate, unsaturated compounds having a dialkylamino group such as dimethylaminostyrene and diethylaminostyrene, and halogen ions such as Cl ⁻ , Br ⁻ and I ⁻ as counter ions. Examples thereof include quaternary ammonium salts of dialkylamino group-containing unsaturated compounds having ON or QSO ₃ ⁻ (Q: an alkyl group having 1 to 12 carbon atoms).

Further, other unsaturated compounds include perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2 -Perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) ) Acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate, etc. Perfluoroalkylalkyl (meth) acrylates having a kill group; perfluoroalkyl group-containing vinyl monomers such as perfluoroalkyls such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene, and alkylenes , Vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane and other alkoxysilyl group-containing vinyl compounds and derivatives thereof, glycidyl acrylate, 3,4-epoxycyclohexyl Examples thereof include glycidyl group-containing acrylates such as acrylate, and a plurality of them can be used from these groups.

Examples of the fatty acid vinyl compound include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, and vinyl stearate.
Examples of the alkyl vinyl ether compound include butyl vinyl ether and ethyl vinyl ether.

Examples of the α-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like.
Examples of vinyl compounds include allyl compounds such as allyl acetate, allyl alcohol, allylbenzene, and allyl cyanide, vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, styrene, α-methylstyrene, 2-methylstyrene, and chlorostyrene. Can be mentioned.
Examples of the ethynyl compound include acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol and the like. These can be used alone or in combination of two or more.

  Specific examples of the polyfunctional compound having at least one polymerizable double bond include the following.

  First, among the compounds having a polymerizable ethylenically unsaturated group, non-halogen aliphatic compounds are exemplified. Specifically, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Bis (acryloxy neopentyl glycol) adipate, bis (methacryloxy neopentyl glycol) adipate, epichlorohydrin modified 1,6-hexanediol di (meth) acrylate: Nippon Kayaku Kayrad R-167, hydroxypivalate neopentyl glycol di (Meth) acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate: Nippon Kayaku Kayrad HX series alkyl type (meth) acrylate, ethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -811, epichlorohydrin modified diethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -851, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified proleng Cold di (meth) acrylate: alkylene glycol type (meth) acrylate such as Nagase Sangyo Denacol DA (M) -911, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, neopentyl glycol modified trimethylolpropane Di (meth) acrylate: Nippon Kayaku Kayrad R-604, ethylene oxide modified trimethylolpropane tri (meth) acrylate: Sartomer SR-454, propylene oxide modified trimethylolpropane tri (meth) acrylate: Nippon Kayaku TPA- 310, epichlorohydrin-modified trimethylolpropane tri (meth) acrylate: trimethylolpropane type (meth) acrylate such as Nagase Sangyo DA (M) -321, pentae Rithritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate: Toagosei Aronix M-233, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta ( (Meth) acrylates, alkyl-modified dipentaerythritol poly (meth) acrylates: Kaprorad-modified dipentaerythritol poly (meth) acrylates such as Nippon Kayaku Kayrad D-310, 320, 330, etc .: Nippon Kayaku Kayrad DPCA-20 , 30, 60, 120, etc. Pentaerythritol type (meth) acrylate, glycerol di (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate Nagase Sangyo Denacol DA (M) -314, glycerol type (meth) acrylate such as triglycerol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclopentanyl di (meth) acrylate, cyclohexyl Di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate: cycloaliphatic (meth) acrylate such as Sanyo Kokusaku Pulp CAM-200, tris (acryloxyethyl) isocyanurate: Toa Gosei Aronix M-315, Tris (methacrylic) Isocyanurate type (meth) acrylates such as (Roxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (methacryloxyethyl) isocyanurate, etc. It is.

  Moreover, the compound which further contains a sulfur atom in a molecule | numerator among the compounds which have a polymerizable ethylenically unsaturated group comprised only from an aliphatic group is illustrated. 1,3-propanediol dithio (meth) acrylate, 1,4-butanediol dithio (meth) acrylate, 1,6-hexanediol dithio (meth) acrylate, neopentyl glycol dithio (meth) acrylate, bis (thioacryloxy) Neopentyl glycol) adipate, bis (thiomethacryloxy neopentyl glycol) adipate, epichlorohydrin modified 1,6-hexanediol dithio (meth) acrylate, hydroxypivalate neopentyl glycol dithio (meth) acrylate, caprolactone modified hydroxypivalate neopentyl Alkyl thio (meth) acrylate such as glycol dithio (meth) acrylate, ethylene glycol dithio (meth) acrylate, diethylene glycol dithio (Meth) acrylate, triethylene glycol dithio (meth) acrylate, tetraethylene glycol dithio (meth) acrylate, polyethylene glycol dithio (meth) acrylate, epichlorohydrin modified ethylene glycol dithio (meth) acrylate, epichlorohydrin modified diethylene glycol dithio (meth) acrylate, propylene Glycol dithio (meth) acrylate, dipropylene glycol dithio (meth) acrylate, tripropylene glycol dithio (meth) acrylate, tetrapropylene glycol dithio (meth) acrylate, polypropylene glycol dithio (meth) acrylate, epichlorohydrin modified prolene glycol dithio (meth) ) Alkylene glycol type thio such as acrylate (Meth) acrylate, trimethylolpropane trithio (meth) acrylate, ditrimethylolpropane trithio (meth) acrylate, neopentyl glycol modified trimethylolpropane dithio (meth) acrylate, ethylene oxide modified trimethylolpropane trithio (meth) acrylate, Trimethylolpropane type thio (meth) acrylate such as propylene oxide modified trimethylolpropane trithio (meth) acrylate, epichlorohydrin modified trimethylolpropane trithio (meth) acrylate, pentaerythritol trithio (meth) acrylate, pentaerythritol tetrathio ( (Meth) acrylate, stearic acid-modified pentaerythritol dithio (meth) acrylate, dipentaerythritol Pentaerythritol-type thio (meth) such as hexahexa (meth) acrylate, dipentaerythritol monohydroxypentathio (meth) acrylate, alkyl-modified dipentaerythritol polythio (meth) acrylate, caprolactone-modified dipentaerythritol polythio (meth) acrylates Glycerol-type thio (meth) acrylate such as acrylate, glycerol dithio (meth) acrylate, epichlorohydrin modified glycerol trithio (meth) acrylate, triglycerol dithio (meth) acrylate, dicyclopentanyl dithio (meth) acrylate, tricyclopentanyl Dithio (meth) acrylate, cyclohexyldithio (meth) acrylate, methoxylated cyclohexyldithio (meth) acrylate Any cycloaliphatic thio (meth) acrylate, tris (thioacryloxyethyl) isocyanurate, tris (thiomethacryloxyethyl) isocyanurate, caprolactone-modified tris (thioacryloxyethyl) isocyanurate, caprolactone-modified tris (thiomethacryloxyethyl) ) Isocyanurate type thio (meth) acrylate such as isocyanurate. These may be used alone or in combination.

  Aromatic polyhydroxy compounds such as diquinone or poly (meth) acrylate compounds such as hydroquinone, resorcin, catechol, pyrogallol, bisphenol A di (meth) acrylate, ethyl (propi) lene oxide modified bisphenol A di (meth) acrylate, bisphenol F Di (meth) acrylate, Ethi (propi) ylene oxide modified bisphenol F Di (meth) acrylate, Bisphenol S di (meth) acrylate, Ethi (propi) lene oxide modified bisphenol S di (meth) acrylate, Epichlorohydrin modified phthalic acid di (Meth) acrylate compounds having aromatic groups such as (meth) acrylate, tetrachlorobisphenol S ethyl (propi) ylene oxide modified di (meth) acrylate, tetrabromobi Phenol S ethyl (prop) Ren'okishido modified di (meth) acrylate styrenes and (meth) acrylate compound having an aromatic group substituted by a halogen atom with chlorine or atomic weight, such as and the like.

  Urethane acrylate, for example, phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer: Kyoeisha Chemical AH-600, phenylglycidyl ether acrylate tolylene diisocyanate urethane prepolymer: Kyoeisha Chemical AT-600, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer: Kyoeisha Chemical UA-306H, phenylglycidyl ether acrylate isophorone diisocyanate urethane prepolymer: Kyoeisha Chemical AI-600, glycerol dimethacrylate tolylene diisocyanate urethane prepolymer: Kyoeisha Chemical UA-101T, glycerin dimethacrylate isophorone diisocyanate urethane prepolymer: Kyoeisha Chemical UA -1 1I, pentaerythritol triacrylate tolylene diisocyanate urethane prepolymer Kyoeisha Chemical UA-306T, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer and the like Kyoeisha Chemical UA-306I and the like.

<Organic solvent>
The curable composition of the present invention can be used as a curable composition containing no organic solvent or as a curable composition containing an organic solvent.
In the case of containing an organic solvent, it may be applied to various substrates, and after the organic solvent is volatilized, active energy rays such as ultraviolet rays and electron beams necessary for curing may be irradiated.
Known organic solvents can be used as the organic solvent used in the coating agent of the present invention. Specific examples include cyclohexanone, methyl ethyl ketone, toluene, methyl propylene glycol acetate and the like.

<Others>
In addition to the above, the photosensitive composition of the present invention includes optional components as long as the purpose is not impaired, and further includes solvents, dyes, antioxidants, polymerization inhibitors, leveling agents, humectants, viscosity modifiers, antiseptics, antibacterial agents. An antistatic agent, an antiblocking agent, an ultraviolet absorber, an infrared absorber, an electromagnetic wave shielding agent, a spherical filler, and the like can be added.

The photosensitive composition of the present invention can be cured by a known radiation curing method to obtain a cured product, and as an active energy ray, an electron beam, an ultraviolet ray, or visible light of 400 to 500 nm can be used.
A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source to be irradiated. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) of ultraviolet light and visible light of 400 to 500 nm. Specifically, an ultra-high pressure mercury lamp or a xenon mercury lamp is often used because of the point light source and the stability of luminance. The active energy dose to be irradiated can be set in a timely manner within a range of 5 to 2000 mJ, but is preferably within a range of 50 to 1000 mJ that can be easily managed in the process.
Further, these ultraviolet rays or electron beams can be used in combination with heat by infrared rays, far infrared rays, hot air, high frequency heating or the like.

  The photosensitive oligomer composition of the present invention may be subjected to radiation curing after natural or forced drying after coating on a substrate, or may be naturally or forcedly dried after radiation curing subsequent to coating. However, it is preferable that the radiation curing is performed after natural or forced drying. In the case of curing with an electron beam, it is preferable to perform radiation curing after natural or forced drying in order to prevent curing inhibition due to water or reduction in strength of the coating film due to residual organic solvent. The timing of radiation curing may be simultaneous with coating or after coating.

Hereinafter, the present invention will be described in detail with reference to production examples and examples, but the present invention is not limited thereto. In addition, a weight average molecular weight shows the standard polystyrene conversion molecular weight measured by GPC.
Unless otherwise specified, the numbers are based on weight.

Synthesis example 1
A 4-neck flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 30.0 g of 2- (diphenylphosphinyl) hydroquinone (made by Hokuko Chemical Co., Ltd.), glycidyl methacrylate (Dow Chemical Japan Co., Ltd.) 27.5 g (manufactured by company), 0.03 g hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.) and 38.3 g cyclohexanone were charged and heated to 85 ° C. Next, 0.46 g of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst, stirred at 90 ° C. for 10 hours, and cooled to room temperature to complete the reaction. This reaction solution was brown and had a solid content of 60%, a number average molecular weight MN260, and a weight average molecular weight MW280.

Synthesis example 2
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 30.0 g of 2- (diphenylphosphinyl) hydroquinone (made by Hokuko Chemical Co., Ltd.), Karenz MOI (made by Showa Denko KK) ) 30.0 g, hydroquinone 0.03 g (manufactured by Wako Pure Chemical Industries, Ltd.) and cyclohexanone 40.0 g were charged and heated to 90 ° C. Next, 0.30 g of dibutyltin dilaurate was added as a catalyst, stirred at 90 ° C. for 10 hours, and cooled to room temperature to complete the reaction. This reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight MN240, and a weight average molecular weight MW260.

Synthesis example 3
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 30.0 g of 2- (diphenylphosphinyl) hydroquinone (made by Hokuko Chemical Co., Ltd.), Karenz MOI (made by Showa Denko KK) ) 15.0 g, hydroquinone 0.02 g (manufactured by Wako Pure Chemical Industries, Ltd.) and cyclohexanone 30.0 g were charged and heated to 90 ° C. Next, 0.23 g of dibutyltin dilaurate was added as a catalyst, stirred at 90 ° C. for 10 hours, and cooled to room temperature to complete the reaction. This reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight MN200, and a weight average molecular weight MW220.

Synthesis example 4
In a 4-neck flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 30.0 g of 2- (diphenylphosphinyl) hydroquinone (made by Hokuko Chemical Co., Ltd.), 21.5 g of triethylamine, and 100 g of toluene To the added mixed solution, 20.2 g of methacrylic acid chloride was added dropwise under ice water cooling (10 ° C.). After completion of the dropwise addition, the reaction was carried out by further stirring for 5 hours at 90 ° C., and then the amine hydrochloride formed as a by-product was removed by filtration. The toluene solution of the filtrate was further washed with 100 g of dilute hydrochloric acid, and then washed with water until the drainage layer became neutral, followed by liquid separation to take out the organic layer. Toluene was distilled off at 60 ° C. under reduced pressure to obtain a pale yellow transparent liquid crude product. This product had a solid content of 40%, a number average molecular weight MN180, and a weight average molecular weight MW200.

Synthesis example 5
In a 4-neck flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 30.0 g of 2- (diphenylphosphinyl) hydroquinone (made by Hokuko Chemical Co., Ltd.), 21.5 g of triethylamine, and 100 g of toluene 17.5 g of acrylic acid chloride was added dropwise to the added mixed solution under ice water cooling (10 ° C.). After completion of the dropwise addition, the reaction was carried out by further stirring for 5 hours at 90 ° C., and then the amine hydrochloride formed as a by-product was removed by filtration. The toluene solution of the filtrate was further washed with 100 g of dilute hydrochloric acid, and then washed with water until the drainage layer became neutral, followed by liquid separation to take out the organic layer. Toluene was distilled off at 60 ° C. under reduced pressure to obtain a pale yellow transparent liquid crude product. This product had a solid content of 40%, a number average molecular weight MN180, and a weight average molecular weight MW190.

Synthesis Example 6
A four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 30.0 g of HCA-HQ (manufactured by Sanko), 28.7 g of Karenz MOI (manufactured by Showa Denko), 03 g (manufactured by Wako Pure Chemical Industries, Ltd.) and 39.1 g of cyclohexanone were charged and heated to 90 ° C. Next, 0.29 g of dibutyltin dilaurate was added as a catalyst, stirred at 90 ° C. for 10 hours, and cooled to room temperature to complete the reaction. This reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight MN260, and a weight average molecular weight MW280.

Comparative Synthesis Example 1
As a photosensitive material for comparison, p-styryl diphenylphosphine (manufactured by Hokuko Chemical Co., Ltd.) was used.

Examples 1 to 6, Comparative Example 1
<High refractive index coating evaluation>
<Coating method>
Methyl isobutyl ketone was added to the photosensitive material solution obtained in each synthesis example to adjust the viscosity to 10 to 100 mPa · S. 5 parts by weight of photopolymerization initiator Ircagua 184 is added to 100 parts by weight of this photosensitive material solution, and applied to a PET film with a bar coder so that the dry coating film becomes 5 μm, and dried at 100 ° C. for 2 minutes, A 400 mJ ultraviolet ray was irradiated with a metal halide lamp to prepare a coated product. What passed 1 week at room temperature was used for the following measurements.

<Refractive index>
The refractive index of the coated product was measured using an Abbe refractometer (Atago Co., Ltd.). The refractive index was as shown in Table 1.
○ with a refractive index of 1.58 or more
X less than 1.58
As evaluated.

<Anti-yellowing resistance by mixing with inorganic substances>
<Coating method>
Methyl isobutyl ketone was added to the photosensitive material solution obtained in each synthesis example to adjust the viscosity to 10 to 100 mPa · S. To 100 parts by weight of this photosensitive material solution, 5 parts by weight of photopolymerization initiator Irukagua 184 and 50 g of MZ-505S (manufactured by Teika Co., Ltd.) are added, and the dry coating film is 5 μm with a bar coder on PET film. It was coated, dried at 100 ° C. for 2 minutes, and irradiated with 500 mJ ultraviolet rays with a metal halide lamp to prepare a coated product. What passed 1 week at room temperature was used for the following measurements.
The coated material was exposed to a carbon arc for 30 hours, and a change in b value (Δb) was obtained using a colorimeter before and after that, and the degree of yellowing was evaluated according to the following criteria.
Δb is less than 4:
Δb is 4 or more: ×

Claims (6)

A photosensitive material comprising a compound (A) having a phenylphosphoryl residue and having a polymerizable unsaturated bond. A compound (A) having a phenylphosphoryl residue and having a polymerizable unsaturated bond, and a photopolymerization initiator (B),
A photosensitive material comprising: The photosensitive material according to claim 1 or 2, wherein the compound (A) having a phenylphosphoryl residue and having a polymerizable unsaturated bond is represented by the following general formula (1).
General formula (1)

(In the formula, R1, R2, and R3 each independently represent a monovalent organic residue, but at least one has a substituted or unsubstituted phenyl group, and at least one contains an unsaturated double bond. Represents an organic residue, R1 and R3, and R2 and R3 may form a ring together.) The photosensitive material according to claim 1, wherein the refractive index after exposure is 1.58 or more. The laminated body formed by laminating | stacking the photosensitive material in any one of Claims 1-4 on a base material. A step of laminating the photosensitive material according to any one of claims 1 to 4 on a substrate;
And a step of irradiating the photosensitive material with light.