JP2006045278A - Photosensitive composition and laminate comprising the photosensitive composition - Google Patents

Abstract

The present invention relates to a photosensitive composition having photocurability, and more specifically, it provides excellent adhesion to a polyester film, more specifically, a polyethylene terephthalate film, and has a surface resistance value lower than 10 ¹¹ Ω / □. To do.
SOLUTION: Polycarboxylic acid anhydrides such as tetracarboxylic dianhydride, hexacarboxylic dianhydride, hexacarboxylic dianhydride, maleic anhydride copolymer resin, phthalic anhydride, trimellitic anhydride, Specific having acid anhydride group such as methyltetrahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylpentahydrophthalic anhydride, methyltrihydrophthalic anhydride, trialkyltetrahydrophthalic anhydride A compound (C) obtained by reacting a compound (A) with a compound (B) having a functional group capable of reacting with an acid anhydride group, a polyalkyleneoxy group, and an unsaturated double bond; A photosensitive composition having a surface resistance value lower than 10 ¹¹ Ω / □ when a coating film is photocured.
[Selection figure] None

Description

The present invention relates to a photosensitive composition having photocurability, and relates to a photosensitive composition having a surface resistance value lower than 10 ¹¹ Ω / □ and a laminate using the photosensitive composition. The composition 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.

  Conventionally, the surface of an optical element such as a lens or an interference film or an optical filter laminated alternately with a high refractive index layer and a low refractive index layer is a base film for the purpose of surface protection and functional addition. A surface coating layer is laminated on the substrate.

  These surface coating layers have a problem in that static electricity is generated and surrounding dust is involved.

Accordingly, various measures as described below have been proposed as means for imparting antistatic properties to the surface coating layer.
For example,
(1) imparting antistatic properties to the base film itself constituting the surface coating layer;
(2) In addition to the base film constituting the surface coating layer, a layer having antistatic performance is provided.

The method (1) is a method in which a conductive base material is prepared by kneading an anionic compound such as an organic sulfonate group, a metal powder, or a conductive filler such as carbon black with a thermoplastic resin such as polyester or polyethylene as a raw material for the base film. In this case, the transparency of the base film is lowered or the film is colored.
By the way, a lens or an optical element such as an interference film or an optical filter in which a high-refractive index layer and a low-refractive index layer are alternately laminated is excellent in transparency and has no optical defect. Needed.
Therefore, when a surface coating layer using an antistatic agent-containing base film is used, there is a problem that transparency is deteriorated. There is also a problem that the base film becomes expensive.

The method (2) has various variations as described below (Japanese Patent Laid-Open Nos. 7-26223, 11-256116, 2001-219520, 2002-060707). JP, 2002-275296, A, etc.).
(2-1) depositing a metal compound on at least one surface of the base film;
(2-2) An anionic surfactant such as a quaternary ammonium salt, a long-chain alkyl compound having a sulfonate group, a thiophene derivative, or a nitrogen element ionized in the main chain on at least one surface of the base film And a layer containing various antistatic agents such as sulfonate group-modified polystyrene.
However, since an anionic surfactant such as a long-chain alkyl compound having a sulfonate group has a relatively low molecular weight, a part of the antistatic agent moves through the antistatic coating film to form a base film. There is a problem of accumulating at the interface and transferring to the opposite surface of the base film, and a problem that the antistatic property decreases with time.
In addition, since the polymer having nitrogen element ionized in the main chain, sulfonate group-modified polystyrene, and the like have a relatively high molecular weight, the above-described problems do not occur. However, in order to obtain good antistatic performance, it is necessary to add a large amount of antistatic agent, and it is not economical because it is necessary to increase the thickness of the antistatic layer. Furthermore, when scrap film that has not been turned into a product (for example, film edges cut and removed in the manufacturing process) is collected and used as a recycled material for film production, it is included in the recycled material during melt film formation. There arises a problem that the antistatic agent component is thermally deteriorated, and the film to be regenerated is extremely colored and lacks practicality (recoverability is poor). In addition, there are disadvantages that the films are difficult to peel (block) and the coating film is easily scraped, and the solution is desired.

The use of an antistatic agent that is excellent in transparency and hardly causes coloring problems is disclosed in Japanese Patent No. 2718519.
However, the invention described in Patent Document 2 relates to a conductive pressure-sensitive adhesive, and is a lens or an optical element such as an interference film or an optical filter in which a high refractive index layer and a low refractive index layer are alternately laminated. When coated on the surface, there is a problem that tack remains, and the surface coating layer of an optical element such as a lens or an interference film or an optical filter laminated alternately with a high refractive index layer and a low refractive index layer is present. Was not at all usable.

On the other hand, polyester film represented by polyethylene terephthalate film is inexpensive and can be mass-produced, is easy to mold, lightweight, easy to color, does not rust, has high impact resistance, has electrical insulation, It is widely used due to its properties such as chemical resistance such as water resistance and chemical resistance, and easy transparency, but its surface has a polyester film for the purpose of surface protection and functionality. A surface coating layer is laminated on the substrate. If a thermosetting coating agent is used when the surface coating layer is laminated, the polyethylene terephthalate film may be thermally deformed by heat treatment during curing. Therefore, a resin composition having photosensitivity is applied, and surface protection and functionality are imparted to the surface of the polyethylene terephthalate film by a photocuring reaction.
However, conventionally, the photosensitive resin composition generally has a larger curing strain at the time of curing than the thermosetting resin composition, and the adhesiveness of the cured coating film to the substrate is inferior. In particular, the adhesion to a polyethylene terephthalate substrate is very poor. Therefore, in order to improve the adhesion between the cured coating film and the polyethylene terephthalate film, the polyethylene terephthalate film is preliminarily processed with a polyester resin or acrylic resin, or the polyethylene terephthalate is kneaded with polyester resin or acrylic resin. An easy-adhesive polyethylene terephthalate film obtained by forming a resin composition into a film is often used. However, such an easy-adhesive polyethylene terephthalate film has a drawback of high cost.
Therefore, there is a need for a photosensitive resin composition having good adhesion without subjecting the polyethylene terephthalate film as a base material to the special easy adhesion treatment described above.

  More preferably, a transparent resin having a high refractive index is required for optical articles. A photocurable composition has a characteristic that the time required for curing is very short and the substrate does not heat so much during curing. Such a photosensitive resin is composed of a lens, a waveguide, an optical fiber, Alternatively, studies are actively made on optical elements such as interference films, optical filters, and holograms in which high refractive index layers and low refractive index layers are alternately stacked. (Refer to patent documents 3-7) It uses suitably especially with respect to the base material which is easy to receive the damage by heat.

By the way, an invention relating to a copolymerizable compound having a (meth) acryloyl group, a reactive antistatic agent having a quaternary ammonium base, an ethylene glycol chain, a hydrocarbon group having 4 or more carbon atoms, and a reactive group in the molecule. Is disclosed in Japanese Patent Application Laid-Open No. 6-136354.
However, the cured coating film formed from the resin composition containing the photosensitive resin disclosed in Patent Document 8 has a problem that interference fringes appear when it is laminated on a polyethylene terephthalate film with a low refractive index.
JP-A-1-253482 Japanese Patent No. 2718519 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 JP-A-6-136354

The present invention relates to a photosensitive composition having photocurability, and more specifically, to provide a film having excellent adhesion to a polyester film, specifically, a polyethylene terephthalate film, and having a surface resistance value lower than 10 ¹¹ Ω / □. Objective. Furthermore, if the introduction amount of the phenyl group is increased, it becomes a photosensitive composition capable of forming a cured product having a refractive index higher than 1.50, and can be used for applications requiring high refractive index properties.

That is, the present invention 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, a polyalkyleneoxy group, and an unsaturated double bond;
Comprising a compound (C) obtained by reacting
The present invention relates to a photosensitive composition having a surface resistance value lower than 10 ¹¹ Ω / □ when it is cured as a coating film.

(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 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, a polyalkyleneoxy group, and an unsaturated double bond;
Compound (C) obtained by reacting
Reacting with a compound (D) having a functional group capable of reacting with a carboxyl group,
The present invention relates to a photosensitive composition comprising a compound (E) having a surface resistance value lower than 10 ¹¹ Ω / □ when it is made into a coating film and photocured.

(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 said photosensitive composition further containing a photopolymerization initiator.

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

  Moreover, this invention relates to the said photosensitive composition containing a conductive inorganic substance further.

  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.

By using the photosensitive composition of the present invention having photocurability and conductivity, a coating film having a surface resistance value lower than 10 ¹¹ Ω / □ can be easily obtained.
If the amount of unsaturated double bonds is adjusted, it has excellent adhesion to polyester films and polyethylene terephthalate films, and if the amount of phenyl group introduced is adjusted, the photosensitivity can form a cured product having a refractive index higher than 1.50. A composition could be provided.

  Further, according to the present invention, the photosensitive composition is applied onto a polyester film, and a polyester film laminate formed by forming a cured coating film, a lens, a waveguide, an optical fiber, or a low refractive index layer is alternately laminated. The photosensitive composition which can be used for optical elements, such as an interference film, an optical filter, and a hologram, was able to be provided.

<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; a polyalkyleneoxy group; an unsaturated double bond; Compound (C) obtained by reacting Compound (B) having
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).

<Compound (A) having acid anhydride group represented by general formula (1) or general formula (2)>
The compound (A) includes a phenyl skeleton in the main chain and has an acid anhydride group as shown below. These may be a mixture of two 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.)

  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 functional group capable of reacting with acid anhydride group, polyalkyleneoxy group and unsaturated double bond>
Examples of the functional group capable of reacting with the acid anhydride group include a hydroxyl group, a carboxyl group, an epoxy group, and an amino group.
Examples of the compound (B) having a functional group capable of reacting with an acid anhydride group, a polyalkyleneoxy group, and an unsaturated double bond include (meth) acrylic monomers having an alkyleneoxy group.

  Examples of the acrylic monomer having an alkyleneoxy group include a monomer having an ethylene oxide chain, a monomer having a propyleneoxy group, and a monomer having both.

Examples of the monomer having an ethyleneoxy group include methoxypolyethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate.
Examples of the monomer having a propyleneoxy group include methoxypolypropylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate.

  In the present invention, in view of compatibility with the ionic compound described later, a monomer having an ethylene oxide group is preferable, and methoxypolyethylene glycol (meth) acrylate is particularly preferable.

The purpose of using the (meth) acrylic monomer having an alkyleneoxy group in the present invention is to develop conductivity. Further, this is because a complex is formed between the ionic compound (B) and the alkyleneoxy group to develop conductivity. Therefore, the role of the alkyleneoxy group is very large and not only provides a field for complex formation but also serves as a transfer medium for the ionic compound. In other words, the conductivity in the present invention varies greatly depending on the amount of the ionic compound and the content of the monomer having an alkyleneoxy group. A preferable alkyleneoxy group content is 20 wt% or more and 85 wt% or less of the whole oligomer. If the content of alkyleneoxy groups is less than 20 wt% of the whole oligomer, the surface resistance value becomes larger than 10 ¹¹ Ω / □, and if the content of alkyleneoxy groups is more than 85 wt% of the whole oligomer, it will not be cured sufficiently. End up.

<Compound (E) obtained by further reacting compound (C) with compound (D) having a functional group capable of reacting with a carboxyl group>
Compound (E) is obtained by reacting the carboxyl group of compound (C) with a functional group capable of reacting with the carboxyl group of compound (D).

<Compound (D) having a functional group capable of reacting with 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 isocyanate group, or an isothiocyanate group.
In order to increase the hardness of the compound (C), a compound having a functional group capable of reacting with a carboxyl group and a polymerizable double bond is useful. As a compound having a functional group capable of reacting with a carboxyl group and a polymerizable double bond, a known compound may be used as a compound having both a functional group capable of reacting with a carboxyl group and a polymerizable double bond. it can. 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 and the like.
In order to increase the refractive index of the compound (C), a compound having a functional group capable of reacting with a carboxyl group and a biphenyl skeleton can be used.
Such compounds include:
o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, monostyrenated phenol glycidyl ether, 4-cyano-4-hydroxybiphenyl glycidyl ether, 4,4'-biphenol monoglycidyl ether, 4,4'-biphenol diglycidyl Ether, o-phenylphenol vinyl ether, p-phenylphenol vinyl ether, monostyrenated phenol vinyl ether, 4-cyano-4-hydroxybiphenyl vinyl ether, 4,4′-biphenol monovinyl ether, 4,4′-biphenol divinyl ether, and these Or a brominated product thereof, and also includes a biphenyl skeleton and an oxazoline, an amino group, a carbodiimide group, or an isocyanate group, Others include the compounds having an isothiocyanate group.

<To make a high refractive index compound>
The compound (C) or compound (E) used in the present invention becomes a photosensitive composition capable of forming a cured product having a refractive index higher than 1.50 if the introduction amount of the phenyl group is further increased. It can be used for applications that require the physical properties of Specifically, this can be achieved by the fact that the compound (A), the compound (B), and the compound (D) have a phenyl group. The amount of phenyl group introduced when the refractive index is higher than 1.50 is 5 wt% or more and 50 wt% or less of the whole oligomer. If the phenyl group content is less than 5 wt% of the whole oligomer, the refractive index will not exceed 1.50, and if the phenyl group content is more than 50 wt% of the whole oligomer, adhesion will not be exhibited.

<Catalyst>
When the reaction between the carboxyl group and the epoxy group is allowed to proceed, a catalyst such as amines may be added as necessary. As the catalyst to be 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 epoxy compound and the catalyst used in the present invention is 0.01 to 10 parts by weight of the catalyst with respect to 100 parts by weight of the epoxy compound. 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 between the carboxyl group and the epoxy group is allowed to proceed, it can be carried out without solvent if the softening temperature of the epoxy compound 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 epoxy compound 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.

  A binder resin, an unsaturated compound, a photopolymerization initiator, and the like can be added to the photosensitive material of the present invention as necessary. 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, and vinyl resin. And the like having a polymerizable unsaturated double bond introduced therein. 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.

<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.

<Pigment>
Examples of the pigment used in the photosensitive composition of the present invention include both organic pigments and inorganic pigments. The pigment can be used for the purpose of coloring the cured product. In the present invention, among inorganic pigments, so-called extender pigments that are not intended for coloring are included in the inorganic particles described later.
Examples of pigments include carbon black, iron oxide black, aniline black, titanium oxide, phthalocyanine, monoazo, disazo, nitro, nitroso, perylene, isoindolinone, quinacridone, and other paints and inks. In particular, a pigment is preferable for obtaining a transfer product having good fading properties. Among them, carbon black, fast yellow, cadmium yellow, yellow iron oxide, iron oxide black, chromophthal yellow, anthrapyrimidine yellow, isoindolinone yellow, nickel azo yellow, copper azomethine yellow, benzoimidazolone yellow, quinophthalone yellow, nickel dioxin Yellow, flavanthrone yellow, yellow lead, titanium yellow, disazo yellow, benzimidazolone orange, pyranthrone orange, perinone orange, para red, lake red, naphthol red, pyrazolone red, permanent red, madder lake, thioindigo Bordeaux, Bengala, Red lead, cadmium red, quinacridone magenta, perylene vermilion, perylene red, chromophthale , Anthanthrone Red, Dianthraquinolyl Red, Perylene Maroon, Benzimidazolone Carmine, Perylene Scarlet, Quinacridone Red, Pyranthrone Red, Manganese Violet, Dioxazine Violet, Phthalocyanine Blue, Bituminous, Cobalt Blue, Ultramarine Blue, In Dunslon blue, phthalocyanine green, pigment green, chromium oxide, viridian, benzimidazolone brown, bronze powder, lead white, zinc white, lithopone, titanium oxide and pearl pigment are preferred.

<Inorganic particles>
The photosensitive composition of the present invention can contain various inorganic particles for various purposes.
In general, a photosensitive composition has a larger curing strain than a thermosetting coating agent, and it is difficult to ensure adhesion to a substrate. The coating agent of the present invention is excellent in adhesion to the substrate even if it does not contain inorganic particles, but contains inorganic particles from the viewpoint of increasing the hardness of the cured coating film and preventing scratches on the surface of the cured coating film. It is preferable to do.
Moreover, when used for the use by which electroconductivity is calculated | required, the inorganic particle which has electroconductivity can also be contained from a viewpoint of electroconductivity provision.

Examples of the inorganic particles used in the photosensitive composition of the present invention include silicon oxide, magnesium oxide, a co-oxide of silicon oxide and magnesium oxide, calcium oxide, barium oxide, boron oxide, and aluminum oxide. , Indium oxide, germanium oxide, tin oxide, zinc oxide, titanium oxide, zirconium oxide, cesium oxide, indium tin oxide, calcium carbonate, magnesium carbonate, and aluminum hydroxide.
These inorganic particles can be used alone or in combination as appropriate depending on the use of the coating agent of the present invention.
In addition, when the photosensitive material of the present invention is cured with ultraviolet rays, inorganic particles are not preferable from the viewpoint of curability when the photosensitive composition becomes opaque. Therefore, inorganic particles that are excellent in transparency even when colored are preferable.
<Ionic compounds>

An ionic compound is added as needed to improve conductivity. Examples of ionic compounds used in the present invention include sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate, potassium nitrate, Inorganic salts such as sodium nitrate, sodium carbonate, sodium thiocyanate,
Organic salts such as sodium acetate, sodium alginate, sodium lignin sulfonate, and sodium toluene sulfonate are listed.
These can be used alone or in combination. From the viewpoints of conductivity and safety, sodium chloride, potassium chloride, lithium perchlorate and the like are preferable.

  Moreover, it is preferable that the content is 0.1-50 weight part with respect to 100 weight part of compounds (C). More preferably, it is 1-30 weight part. If the amount is less than 0.1 part by weight, sufficient ionic conductivity cannot be obtained, and even if it contains more than 50 parts by weight of an ionic compound, the effect of improving the conductivity can hardly be expected, and further the compatibility with the oligomer decreases. Since whitening of the coating film easily occurs, it is not preferable.

<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 resin 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 following 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 by water or reduction of the strength of the coating film due to residual organic solvent. The timing of radiation curing may be simultaneous with coating or after coating.
The photosensitive composition of the present invention is preferably applied to a polyethylene terephthalate substrate, but can also be applied to various substrates other than polyethylene terephthalate.

[Polyethylene terephthalate laminate]
The polyethylene terephthalate laminate of the present invention is obtained by coating the above photosensitive composition on polyethylene terephthalate, curing it, and forming a cured coating film on the polyethylene terephthalate.

As the polyethylene terephthalate substrate in the polyethylene terephthalate laminate of the present invention, not only polyethylene terephthalate that is not subjected to any surface treatment but also polyethylene terephthalate obtained by corona-treating the surface can be used. The polyethylene terephthalate as the base material is preferably in the form of a film (also referred to as a sheet). The thickness of the polyethylene terephthalate film varies depending on the application, but is preferably about 12 to 250 μm.
Moreover, although the thickness of a cured coating film also changes with uses, it is preferable that it is about 0.1-10 micrometers.

[Surface resistance value]
The surface resistance referred to in the present invention is the surface resistivity at 23 ° C. and 50% humidity, and can be measured by, for example, R8340A and R12704A manufactured by ADVANTEST. The photosensitive composition of the present invention was measured by installing a coating film having a size of 10 cm × 10 cm or more at a measurement site of R12704A. The surface resistance value is lower than 10 ¹¹ Ω / □.

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
In a 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 27.9 g of biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation), in the above “biphenyltetracarboxylic dianhydride” 72.1 g of polyethylene glycol monoacrylate (Blenmer AE-350, manufactured by Nippon Oil & Fats Co., Ltd.) equivalent to 100 mol% as a hydroxyl group with respect to 100 mol% of carboxylic acid anhydride groups of 0.1 mol (manufactured by Wako Pure Chemical Industries, Ltd.) ), 100.0 g of cyclohexanone was charged and the temperature was raised to 90 ° C. Next, 1.0 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, stirred at 90 ° C. for 6 hours, cooled to room temperature, and the reaction was terminated. . This reaction solution was transparent yellow, had a solid content of 50%, a number average molecular weight MN1,180, and a weight average molecular weight MW1,810.

Synthesis example 2
In a 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 20.9 g of biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation), in the above “biphenyltetracarboxylic dianhydride” Polyethylene glycol monoacrylate (Blenmer AE-400, manufactured by Nippon Oil & Fats Co., Ltd.) 79.1 g and hydroquinone 0.1 g (Wako Pure Chemical Industries, Ltd.) ), 100.0 g of cyclohexanone was charged and the temperature was raised to 90 ° C. Next, 1.0 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, stirred at 90 ° C. for 6 hours, cooled to room temperature, and the reaction was terminated. . This reaction solution was transparent yellow, had a solid content of 50%, a number average molecular weight MN1,650, and a weight average molecular weight MW2,660.

Synthesis example 3
In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introduction tube, and a thermometer, 22.1 g of phthalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), carboxylic anhydride group 100 in the above “phthalic anhydride” Polyethylene glycol monomethacrylate (Blenmer PE-200, manufactured by Nippon Oil & Fats Co., Ltd.) 77.9 g, hydroquinone 0.1 g (manufactured by Wako Pure Chemical Industries, Ltd.) and cyclohexanone 100.0 g corresponding to 100 mol% as a hydroxyl group with respect to mol% The temperature was raised to 90 ° C. Next, 1.0 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, stirred at 90 ° C. for 6 hours, cooled to room temperature, and the reaction was terminated. . This reaction solution was transparent yellow, had a solid content of 50%, a number average molecular weight MN810, and a weight average molecular weight MW1,010.

Synthesis example 4
In a 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 25.2 g of biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation), in the above “biphenyltetracarboxylic dianhydride” Polypropylene glycol monomethacrylate (Blenmer PE-350, manufactured by Nippon Oil & Fats Co., Ltd.) corresponding to 100 mol% as a hydroxyl group with respect to 100 mol% of carboxylic acid anhydride groups of 74.8 g, hydroquinone 0.1 g (manufactured by Wako Pure Chemical Industries, Ltd.) ), 100.0 g of cyclohexanone was charged and the temperature was raised to 90 ° C. Next, 1.0 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, stirred at 90 ° C. for 6 hours, cooled to room temperature, and then glycidyl methacrylate ( Nippon Shokubai Co., Ltd.) 24.3 g, o-phenylphenol glycidyl ether (trade name OPP-G, Sanko Co., Ltd.) 39.0 g, N, N-dimethylbenzylamine (Wako Pure Chemical Industries, Ltd.) 1.31 g Then, 5.0 g of cyclohexanone was added and stirred at 90 ° C. for 6 hours to complete the reaction. This reaction solution was transparent yellow, had a solid content of 60%, a number average molecular weight MN1,600, and a weight average molecular weight MW2,630.

Synthesis example 5
To 100 g of the oligomer synthesized in Synthesis Example 1, 2.0 g of lithium perchlorate (manufactured by Nippon Carlit Co., Ltd.) was added and stirred until completely dissolved to complete mixing.

Comparative Example 1
In a 4-neck flask equipped with a stirrer, a reflux condenser, a dry air inlet tube, and a thermometer, 50.6 g of biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation), in the above “biphenyltetracarboxylic dianhydride” 4-hydroxybutyl acrylate (4HBA, manufactured by Nippon Kasei Co., Ltd.) 49.4 g, hydroquinone 0.05 g (manufactured by Wako Pure Chemical Industries, Ltd.) 100.0 g of cyclohexanone was charged and the temperature was raised to 90 ° C. Next, 1.0 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, stirred at 90 ° C. for 6 hours, cooled to room temperature, and the reaction was terminated. . This reaction solution was transparent yellow, had a solid content of 50%, a number average molecular weight MN570, and a weight average molecular weight MW630.

Comparative Example 2
80.0 g of polyethylene glycol monoacrylate (Blemmer AE-350, manufactured by Nippon Oil & Fats Co., Ltd.) was added to 20.0 g of the oligomer synthesized in Comparative Example 1 and the mixture was stirred until completely dissolved to complete mixing.

  Methyl isobutyl ketone is added to each 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 the solid content of this resin solution, and applied to a polyethylene terephthalate film with a bar coder so that the dry coating film becomes 5 μm, and 80 ° C. for 2 minutes. It dried and irradiated the ultraviolet ray of 400mJ with the metal halide lamp, and produced the laminated body for a test. What passed 1 week at room temperature was used for the following measurements.

<Adhesion to PET>
In the adhesion test, the above-mentioned coated product is subjected to a goblet cellophane tape peel test, and a cured coating film of 90% or more remains ○
A cured film with a residual rate of less than 90% x
As evaluated.

<Refractive index>
The refractive index of the coated product was measured using an Abbe refractometer (Atago Co., Ltd.).
○ with a refractive index of 1.50 or more
Less than 1.50 x
It was determined.

<Surface resistance value>
The surface resistance value of the coated material was measured using a digital ultrahigh resistance / microammeter R8340 (manufactured by Advantest Co., Ltd.). Note that 6 × 10 ¹⁰ (Ω / □) is expressed as “6E + 10”.
○ When the surface resistance is 10 ¹¹ Ω / □ or less
Higher than 10 ¹¹ Ω / □
It was determined.

<Curing property>
When you touch the coated material with your finger,
○ that has no tack
What has tack ×
It was determined.

Claims (7)

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, a polyalkyleneoxy group, and an unsaturated double bond;
Comprising a compound (C) obtained by reacting
A photosensitive composition having a surface resistance value lower than 10 ¹¹ Ω / □ when a coating film is photocured.
(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.) 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, a polyalkyleneoxy group, and an unsaturated double bond;
Compound (C) obtained by reacting
Reacting with a compound (D) having a functional group capable of reacting with a carboxyl group,
A photosensitive composition comprising a compound (E) having a surface resistance value lower than 10 ¹¹ Ω / □ when a coating film is photocured.
(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.) Furthermore, the photosensitive composition of Claim 1 or 2 containing a photopolymerizable initiator. Furthermore, the photosensitive composition in any one of Claims 1-3 containing a pigment. Furthermore, the photosensitive composition in any one of Claims 1-4 containing an ionic compound. The laminated body formed by laminating | stacking the photosensitive composition in any one of Claims 1-5 on a base material. A step of laminating the photosensitive composition according to any one of claims 1 to 5 on a substrate;
The manufacturing method of a laminated body including the process of irradiating the said photosensitive composition with light.