JP2006137903A - Curable high refractive index material and laminated body from the curable high refractive index material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive material that has high refractive index even with only oligomer units and shows a sufficient pencil hardness. <P>SOLUTION: A compound (A) bearing an acid anhydride group represented by general formula (1) (wherein R1 and R2 are each independently H or a monovalent organic group, R3 is a divalent organic residual group, R4 and R5 are each independently H or a monovalent organic group or a monovalent organic group, or R1 and R2 may be integrated to form a ring, R3, R4 and R5 may be integrated to form a ring) is allowed to react with (B) a compound bearing a functional group reactive with an acid anhydride and three or more or unsaturated double bonds to prepare (C) a compound bearing functional group, further, the resultant compound (C) is allowed to react with (G) compound bearing functional group reactive with the functional groups in the compound (C) thereby being prepared a photosensitive composition giving a refractive index of more than 1.53 after exposure to light. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a transparent curable material having photocurability, high pencil hardness, good yellowing resistance, and high refractive index. The curable oligomer of the present invention can be used in 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, transparent oligomers having a high refractive index have been demanded for optical articles. Such curable oligomers 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 hard coat properties. 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 the higher the blending ratio of the inorganic material, the harder it is to express the advantages of the organic material, and the hard coat property is manifested. It becomes difficult to let you. Therefore, it is necessary to increase the refractive index of the oligomer itself and reduce the compounding ratio of the inorganic fine particles.
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 having a high refractive index by an oligomer alone and a sufficient pencil hardness.

（式中、Ｒ１およびＲ２は、それぞれ独立に、水素原子もしくは１価の有機残基を表し、Ｒ３は、２価の有機残基を表し、Ｒ４およびＲ５は、それぞれ独立に水素原子もしくは１価の有機残基を表す。Ｒ１，Ｒ２は、それぞれが一体となって環を形成しても良い。Ｒ３，Ｒ４，Ｒ５は、一体となって環を形成してもよい。） That is, the present invention provides a compound (A) having an acid anhydride group represented by the following general formula (1) or general formula (2):
A compound (B) having a functional group capable of reacting with an acid anhydride group and three or more unsaturated double bonds;
To the compound (C) having a functional group obtained by reacting
A photosensitive composition comprising a compound (D) obtained by reacting with a compound (G) having a functional group capable of reacting with the functional group of the compound (C);
The present invention relates to a photosensitive composition having a refractive index after exposure of 1.53 or more.

(Wherein R1 and R2 each independently represent a hydrogen atom or a monovalent organic residue, R3 represents a divalent organic residue, and R4 and R5 each independently represent a hydrogen atom or a monovalent residue. R1 and R2 may be combined to form a ring, and R3, R4, and R5 may be combined to form a ring.)

  The present invention further relates to the above photosensitive composition, wherein the compound (G) is a compound (E) having a functional group capable of reacting with the functional group of the compound (C) and an unsaturated double bond.

Moreover, this invention relates to the said photosensitive composition containing a photopolymerizable initiator further.

  Moreover, this invention relates to the said photosensitive composition whose functional group which can react to an acid anhydride group is a hydroxyl group.

（式中、Ｒ１およびＲ２は、それぞれ独立に、水素原子もしくは１価の有機残基を表し、Ｒ３は、２価の有機残基を表し、Ｒ４およびＲ５は、それぞれ独立に水素原子もしくは１価の有機残基を表す。Ｒ１，Ｒ２は、それぞれが一体となって環を形成しても良い。Ｒ３，Ｒ４，Ｒ５は、一体となって環を形成してもよい。） The present invention also includes a compound (A) having an acid anhydride group represented by the following general formula (1) or general formula (2):
A compound (B) having a functional group capable of reacting with an acid anhydride group and three or more unsaturated double bonds;
To the compound (C) having a functional group obtained by reacting
The present invention relates to a method for producing a photosensitive composition, characterized by reacting with a compound (G) having a functional group capable of reacting with a functional group of the compound (C).

(Wherein R1 and R2 each independently represent a hydrogen atom or a monovalent organic residue, R3 represents a divalent organic residue, and R4 and R5 each independently represent a hydrogen atom or a monovalent residue. R1 and R2 may be combined to form a ring, and R3, R4, and R5 may be combined to form a ring.)

  Moreover, this invention relates to the manufacturing method of the said photosensitive composition whose compound (G) is a compound (E) which has a functional group which can react with the functional group which the said compound (C) has, and an unsaturated double bond. .

  Moreover, this invention relates to the laminated body formed by laminating | stacking the said photosensitive composition on a base material.

The present invention also includes a step of laminating the photosensitive composition on a substrate,
And a step of irradiating the photosensitive composition with light.

  According to the present invention, it was possible to provide a photosensitive material having a refractive index of 1.53 or more by itself and having sufficient pencil hardness and good yellowing resistance.

<Compound (A) having an acid anhydride group represented by general formula (1) or general formula (2); a functional group capable of reacting with an acid anhydride group; and three or more unsaturated double bonds Compound (C) having a functional group obtained by reacting a compound (B) having a compound>
Compound (C) is obtained by reacting the acid anhydride group of compound (A) with a functional group capable of reacting with the acid anhydride group of compound (B). Although the compound (C) has a carboxyl group, the compound (C) may further have a hydroxyl group depending on the type of the compound (B). The compound (D) that reacts with the compound (C) can react with either or both of a carboxyl group and a hydroxyl group. Therefore, in this invention, it calls the compound (C) which has a functional group.

<Compound (A) having acid anhydride group represented by general formula (1) or general formula (2)>
The compound (A) has an acid anhydride group as shown below. These may be a mixture of two or more.

（式中、Ｒ１およびＲ２は、それぞれ独立に、水素原子もしくは１価の有機残基を表し、Ｒ３は、２価の有機残基を表し、Ｒ４およびＲ５は、それぞれ独立に水素原子もしくは１価の有機残基を表す。Ｒ１，Ｒ２は、それぞれが一体となって環を形成しても良い。Ｒ３，Ｒ４，Ｒ５は、一体となって環を形成してもよい。）

(Wherein R1 and R2 each independently represent a hydrogen atom or a monovalent organic residue, R3 represents a divalent organic residue, and R4 and R5 each independently represent a hydrogen atom or a monovalent residue. R1 and R2 may be combined to form a ring, and R3, R4, and R5 may be combined to form a ring.)

    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 referred to in the present invention refers to 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 alkylthio group, and the like.

    The divalent organic residue is an atomic group composed of an aliphatic, aromatic, or heteroatom-containing atomic group alone or in combination. Specifically, an aliphatic group such as an alkylene group, a cycloalkylene group, or an alkyleneoxy group. Aromatic organic residues such as a group and an arylene group may be mentioned, and these may further have a substituent.

Strictly speaking, the general formula (2) is included in the general formula (1), but is specifically described as a particularly preferable form.
Specifically, as the compound of the general formula (2),

    Any compound having two or more carboxylic anhydride groups in one molecule may be used, for example, tetracarboxylic dianhydride, hexacarboxylic dianhydride, hexacarboxylic dianhydride, maleic anhydride copolymer. Examples thereof include polyvalent carboxylic acid anhydrides such as resins. In the present invention, these compounds can be used alone or in combination. In addition, polycarboxylic acid, polycarboxylic acid ester, polycarboxylic acid half ester, and the like that can be converted into an anhydride via a dehydration reaction during the reaction are compounds having two or more carboxylic acid anhydride groups referred to in the present invention. included.

    More specifically, as tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, Diphenyl sulfide tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, "Ricacid TMTA-C", "Ricacid MTA- 10 ”,“ Licacid MTA-15 ”,“ Licacid TMEG series ”,“ Licacid TDA ”and so on.

Maleic anhydride copolymer resins include SMA resin series from Sartomer, GSM series from Gifu Shellac Co., Ltd., styrene-maleic anhydride copolymer resins, p-phenylstyrene-maleic anhydride copolymer resins, polyethylene- Α-olefin-maleic anhydride copolymer resin such as maleic anhydride, “VEMA” (copolymer of methyl vinyl ether and maleic anhydride) manufactured by Daicel Chemical Industries, Ltd., and acrylic anhydride-modified polyolefin (“Aurolen series”) ": Nippon Paper Chemical Co., Ltd.), maleic anhydride copolymer acrylic resin, and the like.
Among them, biphenyltetracarboxylic dianhydride having a biphenyl skeleton, p-phenylstyrene-maleic anhydride copolymer resin, and the like are compounds that can efficiently introduce the biphenyl skeleton into the molecule in the present invention, and are particularly preferable.

    Specifically, as the compound of the general formula (1),

    For example, phthalic anhydride, trimellitic anhydride, methyltetrahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylpentahydrophthalic anhydride, methyltrihydrophthalic anhydride, trialkyltetrahydroanhydride Examples of the acid anhydride include an acid anhydride having an alicyclic structure or an aromatic ring structure such as phthalic acid, methylcyclohexene dicarboxylic acid anhydride, het acid anhydride, and tetrabromophthalic anhydride. Other acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecyl succinic anhydride, butyl maleic anhydride, pentyl malein Acid anhydride, hexyl maleic anhydride, octyl maleic anhydride, decyl maleic anhydride, dodecyl maleic anhydride, butyl glutamic anhydride, hexyl glutamic anhydride, heptyl glutamic anhydride, octyl glutamic anhydride, decyl glutamic acid Anhydride, dodecylglutamic acid anhydride, etc. are mentioned. Among these, one type or two or more types of acid anhydrides can be used in combination.

<Compound (B) having a functional group capable of reacting with an acid anhydride group and three or more unsaturated double bonds>
Examples of the functional group capable of reacting with the acid anhydride group include a hydroxyl group, a glycidyl group, and an amino group, and a hydroxyl group is particularly preferable because of easy control of the reaction.
A well-known thing can be used as a compound (B) which has a hydroxyl group and three or more unsaturated double bonds.
Examples include pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.
In addition, the compound (B) having a functional group capable of reacting with an acid anhydride group and three or more unsaturated double bonds has a functional group capable of reacting with an acid anhydride group and two or less unsaturated double bonds. It is also possible to mix and use a compound having
Examples of the compound having a functional group capable of reacting with an acid anhydride group and two or less unsaturated double bonds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meta ) Acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, glycerol mono (meth) acrylate, 2-hydroxy-3-acryl Leuoxypropyl methacrylate, dihydroxy acrylate, glycerol (meth) acrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaeryth Ritoruji (meth) acrylate, pentaerythritol diacrylate, and the like isocyanuric acid EO-modified diacrylate.

<Compound (D) obtained by reacting with compound (G) having a functional group capable of reacting with the functional group of compound (C)>
The compound (D) is obtained by reacting the carboxyl group or hydroxyl group of the compound (C) with a functional group capable of reacting with the carboxyl group or hydroxyl group of the compound (G).

<Compound (G) having functional group capable of reacting with functional group of compound (C)>

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.
Examples of functional groups capable of reacting with hydroxyl groups include isocyanato groups, acid halides, acid anhydride groups, and carboxyl groups.
An epoxy group is particularly useful as a functional group capable of reacting with a carboxyl group.
In order to increase the hardness of the photosensitive composition after exposure, a compound having a functional group capable of reacting with the functional group of the compound (C) and a polymerizable double bond is useful.
These reactions 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.
In addition, when performing a reaction with an acid halide of (meth) acrylic acid, hydrogen halide (for example, hydrogen chloride) is by-produced. For example, triethylamine, pyridine, picoline, dimethylaniline, diethylaniline 1,4-diazabicyclo [2.2.2] octane (DABCO), organic bases such as 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), or sodium hydrogen carbonate, carbonic acid Inorganic bases such as sodium, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium oxide may be used as the dehydrochlorinating agent.
Hereinafter, the compound (G) is further reacted with the compound (E) having a functional group capable of reacting with the functional group of the compound (C) and a polymerizable double bond, and the functional group of the compound (C). The description will be divided into the compound (F) having a functional group that can be obtained and having no polymerizable double bond.
<Compound (E)>
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 a functional group capable of reacting with a hydroxyl group and a polymerizable double bond include methacryloyloxyethyl isocyanate (MOI), vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate (MAI), isopropenyl-α, α- Examples include dimethylbenzyl isocyanate (TMI). 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.

<Compound (F)>

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 between the functional group (a) 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 functional group (a) that reacts with the epoxy group and the epoxy group is allowed to proceed, the reaction can be carried out without solvent if the softening temperature of the compound having the epoxy group to be used 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.

  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.

<Refractive index of photosensitive composition after exposure>
The photosensitive composition of the present invention needs to have a refractive index of 1.53 or more after exposure, that is, after light irradiation. Therefore, it is preferable that one of the compound (A) and the compound (G) is preferably an aromatic compound. The index that should be called aromatic density when the molecular weight in the calculation of compound (D) is used as the denominator and the number of benzene rings included in the calculation in compound (D) multiplied by 72 (6 carbon atoms) is used as the molecule. The guideline is 6% or more.

<Photopolymerization initiator>
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.

<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-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 80.0 g of phthalic anhydride (Wako Pure Chemical Industries, Ltd.), pentaerythritol triacrylate (Osaka Organic Chemical Co., Ltd., trade name) : Biscoat # 300) 247.9 and hydroquinone 0.16 g (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and heated to 85 ° C. Then, 1.64 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) is added as a catalyst, and the mixture is stirred at 85 ° C. for 8 hours. Glycidyl methacrylate (Dow Chemical Japan Co., Ltd.) 76.7 g and cyclohexanone 174.2 g were added, and then 2.64 g of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. did. This reaction solution was light yellow and transparent and had a solid content of 70%, a number average molecular weight MN640, and a weight average molecular weight MW760.

Synthesis example 2
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, pyromellitic anhydride (manufactured by Nippon Shokubai Co., Ltd.) 50.0 g, pentaerythritol triacrylate (Osaka Organic Chemical Co., Ltd., trade name) : Biscoat # 300) 210.5 and hydroquinone 0.13 g (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and the temperature was raised to 85 ° C. Next, 1.30 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) is added as a catalyst, and the mixture is stirred at 85 ° C. for 8 hours. Glycidyl methacrylate (Dow Chemical Japan Co., Ltd.) Product) 65.2 g and toluene 219.2 g were added, and then 2.10 g of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst. did. This reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight MN1,060, and a weight average molecular weight MW3,070.

Synthesis example 3
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 80.0 g of biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation), pentaerythritol triacrylate (Osaka Organic Chemical Co., Ltd.) , Trade name: Biscoat # 300) 250.0, hydroquinone 0.16 g (manufactured by Wako Pure Chemical Industries, Ltd.) and cyclohexanone 141.2 g were charged and heated to 85 ° C. Next, 1.65 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) is added as a catalyst, and the mixture is stirred at 85 ° C. for 8 hours. Glycidyl methacrylate (Dow Chemical Japan Co., Ltd.) 77.3 g and cyclohexanone 33.9 g were added, and then 2.65 g of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst. did. This reaction solution was light yellow and transparent with a solid content of 70%, a number average molecular weight MN870, and a weight average molecular weight MW2,830.

Synthesis example 4
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 80.0 g of phthalic anhydride (Wako Pure Chemical Industries, Ltd.), pentaerythritol triacrylate (Osaka Organic Chemical Co., Ltd., trade name) : Biscote # 300) 247.9, hydroquinone 0.16 g (manufactured by Wako Pure Chemical Industries, Ltd.) and cyclohexanone 15.1 g were charged and heated to 85 ° C. Next, 1.64 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, stirred at 85 ° C. for 8 hours, and OPP-G (o-phenylphenol glycidyl). (Ether: Sanko Co., Ltd.) 122.2 g and cyclohexanone 178.6 g were added, and then 2.64 g of dimethylbenzylamine (Wako Pure Chemical Industries, Ltd.) was added as a catalyst. The reaction was terminated. This reaction solution was light yellow and transparent and had a solid content of 70%, a number average molecular weight MN660, and a weight average molecular weight MW800.

Synthesis example 5
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 80.0 g of phthalic anhydride (Wako Pure Chemical Industries, Ltd.), pentaerythritol triacrylate (Osaka Organic Chemical Co., Ltd., trade name) : Biscote # 300) 247.9, hydroquinone 0.16 g (manufactured by Wako Pure Chemical Industries, Ltd.) and cyclohexanone 15.1 g were charged and heated to 85 ° C. Then, 1.64 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) is added as a catalyst, and the mixture is stirred at 85 ° C. for 8 hours. Glycidyl methacrylate (Dow Chemical Japan Co., Ltd.) 38.4 g, OPP-G (o-phenylphenol glycidyl ether: Sanko Co., Ltd.) 61.1 g and cyclohexanone 168.8 g were added, and then dimethylbenzylamine (Wako Pure Chemical Industries, Ltd.) 2. 64g was added, it stirred at 85 degreeC for 6 hours, and it cooled to room temperature, and complete | finished reaction. This reaction solution was light yellow and transparent and had a solid content of 70%, a number average molecular weight MN650, and a weight average molecular weight MW770.

Synthesis Example 6
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 80.0 g of biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation), pentaerythritol triacrylate (Osaka Organic Chemical Co., Ltd.) , Trade name: Biscoat # 300) 250.0, hydroquinone 0.16 g (manufactured by Wako Pure Chemical Industries, Ltd.) and cyclohexanone 141.2 g were charged and heated to 85 ° C. Then, 1.65 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, stirred at 85 ° C. for 8 hours, and styrene oxide (manufactured by Daicel Chemical Industries, Ltd., Trade name STO) 65.3 g and cyclohexanone 28.8 g were added, and then 2.65 g of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst, stirred at 85 ° C. for 6 hours, cooled to room temperature and reacted. Ended. This reaction solution was light yellow and transparent and had a solid content of 70%, a number average molecular weight MN750, and a weight average molecular weight MW3,180.

Synthesis Example 7 Comparative Example 1
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 80.0 g of Ricacid HNA-100 (manufactured by Shin Nippon Rika Co., Ltd.), pentaerythritol triacrylate (Osaka Organic Chemical Co., Ltd., product) Name: Biscoat # 300) 203.7 and hydroquinone 0.14 g (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and the temperature was raised to 85 ° C. Next, 1.42 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) is added as a catalyst, and the mixture is stirred at 85 ° C. for 8 hours. Glycidyl methacrylate (Dow Chemical Japan Co., Ltd.) Product) 63.1 g and cyclohexanone 149.3 g were added, and then 2.28 g of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. did. This reaction solution was light yellow and transparent and had a solid content of 70%, a number average molecular weight MN640, and a weight average molecular weight MW780.

Synthesis Example 8 Comparative Example 2
Tetrabromophthalic anhydride (product name: PHT4, 100.0 g), pentaerythritol triacrylate (Osaka Organic Chemical Co., Ltd.) in a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer Industrial Co., Ltd., trade name: Biscote # 300) 128.6 g and hydroquinone 0.11 g (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and heated to 85 ° C. Next, 1.14 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, stirred at 85 ° C. for 10 hours, and glycidyl methacrylate (Dow Chemical Japan Co., Ltd.). Product) 33.4 g and toluene 29.3 g were added, and then 1.84 g of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst, stirred at 85 ° C. for 2 hours, cooled to room temperature, and then 147. 3 g was added to complete the reaction. This reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight MN700, and a weight average molecular weight MW880.

<Evaluation of hard coat use>
<Coating method>
Methyl isobutyl ketone was added to the oligomer 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 oligomer solution, applied to a PET film with a bar coder so that the dry coating film becomes 5 μm, dried at 100 ° C. for 2 minutes, and a metal halide lamp A 400 mJ ultraviolet ray was irradiated 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 1.53 or more
X less than 1.53
As evaluated.

<Pencil hardness>
The pencil hardness was tested according to JIS K 5400 8.4.2.
○ Pencil hardness of H or higher
X lower than H
As evaluated.

<Yellow resistance>
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: ×

<Aromatic ring density>
The aromatic density here means 100 as the numerator of the number of benzene rings included in the calculation of compound (D) multiplied by 72 (6 carbon atoms), with the calculated molecular weight of compound (D) as the denominator. It is a thing.

Table 1

Claims (8)

Compound (A) having an acid anhydride group represented by the following general formula (1) or general formula (2);
A compound (B) having a functional group capable of reacting with an acid anhydride group and three or more unsaturated double bonds;
To the compound (C) having a functional group obtained by reacting
A photosensitive composition comprising a compound (D) obtained by reacting with a compound (G) having a functional group capable of reacting with the functional group of the compound (C);
A photosensitive composition having a refractive index after exposure of 1.53 or more.

(Wherein R1 and R2 each independently represent a hydrogen atom or a monovalent organic residue, R3 represents a divalent organic residue, and R4 and R5 each independently represent a hydrogen atom or a monovalent residue. R1 and R2 may be combined to form a ring, and R3, R4, and R5 may be combined to form a ring.) The photosensitive composition according to claim 1, wherein the compound (G) is a compound (E) having a functional group capable of reacting with a functional group of the compound (C) and an unsaturated double bond. Furthermore, the photosensitive composition of Claim 1 or 2 containing a photopolymerizable initiator.
The photosensitive composition according to claim 1, wherein the functional group capable of reacting with the acid anhydride group is a hydroxyl group. Compound (A) having an acid anhydride group represented by the following general formula (1) or general formula (2);
A compound (B) having a functional group capable of reacting with an acid anhydride group and three or more unsaturated double bonds;
To the compound (C) having a functional group obtained by reacting
A method for producing a photosensitive composition comprising reacting with a compound (G) having a functional group capable of reacting with a functional group of the compound (C).

(Wherein R1 and R2 each independently represent a hydrogen atom or a monovalent organic residue, R3 represents a divalent organic residue, and R4 and R5 each independently represent a hydrogen atom or a monovalent residue. R1 and R2 may be combined to form a ring, and R3, R4, and R5 may be combined to form a ring.) The method for producing a photosensitive composition according to claim 5, wherein the compound (G) is a compound (E) having a functional group capable of reacting with the functional group of the compound (C) and an unsaturated double bond. The laminated body formed by laminating | stacking the photosensitive composition in any one of Claims 1-4 on a base material. A step of laminating the photosensitive composition according to any one of claims 1 to 4 on a substrate;
The manufacturing method of a laminated body including the process of irradiating the said photosensitive composition with light.