KR20180086128A - Photosensitive composition, cured film and method for producing same, display device, light emitting element, and light receiving element - Google Patents

Abstract

Provided is a photosensitive composition which has good storage stability or developing properties and is capable of forming a cured film with excellent solvent resistance although the photosensitive composition is post-baked at low temperatures. The photosensitive composition comprises a compound [A] having an acidic functional group and an alicyclic epoxy group in the same molecule or different molecules and a photosensitizer [B]. The compound [A] includes a polymer (a1) which has the acidic functional group and the alicyclic epoxy group in the same molecule, or includes a combination of a polymer (a2) and a polymer (a3), wherein the polymer (a2) has the acidic functional group, but does not have the alicyclic epoxy group and the polymer (a3) has the alicyclic epoxy group, but does not have the acidic functional group.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive composition, a cured film, a method for producing the same, a display device, a light emitting device, and a light receiving device,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition, a cured film and a manufacturing method thereof, and a display device, a light emitting device and a light receiving device, and more particularly to a transmissive or reflective color liquid crystal display device, A light-emitting element, and a light-receiving element having the cured film, a cured film formed using the photosensitive composition, a method of producing the same, and a display device, a light-emitting element, and a light-

As a manufacturing method of a color filter, for example, an inkjet method, an electrodeposition method, a printing method, a photolithography method and the like are known, but in recent years, a photolithography method has become mainstream. In the case of manufacturing a color filter by photolithography, for example, a colored photosensitive composition is coated on a substrate to form a coated film, and then the radiation is exposed through a photomask having a predetermined opening pattern, followed by development A method of dissolving and removing unexposed portions to form a pattern has been employed (Patent Document 1). After the pattern formation, post-baking is carried out at a temperature of 200 to 250 캜 for 30 to 60 minutes in order to ensure reliability such as heat resistance, solvent resistance, adhesion to the substrate, electric characteristics, It is normal.

Japanese Unexamined Patent Application Publication No. 2-144502

In recent years, the color filter tends to be used not only as a monitor in a liquid crystal display (LCD) application but also as a television. [0003] Along with the tendency of this application to be widened, color filters are required to have high color characteristics in chromaticity, contrast, and the like. In addition, color filters for use in image sensors (solid-state image pickup devices) are required to further improve color characteristics, such as reduction in color unevenness and improvement in color resolution. However, when a pigment is used as a coloring agent, problems such as occurrence of scattering due to coarse particles of the pigment and viscosity increase due to poor stability at low temperature storage tends to occur, and there is a limit to further improve the contrast and luminance. Therefore, when a dye is used as the colorant, it is considered that the color and brightness when the image is displayed due to the color purity of the dye itself and the sharpness of the color thereof are increased, and coarse particles are eliminated. However, since dyes generally have poor heat resistance, it is difficult to heat a coating film formed using a photosensitive composition containing a dye to a post-baking temperature of 200 to 250 캜.

In the technical field of color filters, the colorant concentration tends to increase for high color purity of the display element and for high color resolution of the light receiving element. However, in the development, There is a tendency that a residue or scum is likely to be generated. In order to avoid the generation of scum and scum, it is effective to lengthen the development time. However, if the development time is long, the tact time is long.

[0003] Among display devices, flexible display devices have attracted attention, and substitution from a conventional glass substrate to a flexible plastic substrate has been studied. However, since the plastic substrate generally has low heat resistance, the plastic substrate tends to elongate or shrink at post baking temperatures of 200 to 250 캜.

With respect to such a problem, it is conceivable to perform the post-baking at a lower temperature. However, since the durability and strength of the cured film become insufficient, problems such as warping of the plastic substrate, cracking of the cured film and deterioration of the solvent resistance occur. For this reason, there is a demand for a photosensitive composition capable of forming a cured film excellent in storage stability and developability and excellent in solvent resistance even at post-baking at a low temperature.

Disclosure of the Invention An object of the present invention is to provide a photosensitive composition capable of forming a cured film excellent in storage stability and developability and excellent in solvent resistance even at post-baking at a low temperature. In addition, an object of the present invention is to provide a cured film formed using the photosensitive composition, a method for producing the same, and a display element, a light emitting element, and a light receiving element including the cured film.

In view of the above circumstances, the present inventors have conducted intensive studies and found that a cured film having excellent storage stability and developability and excellent solvent resistance even after post-baking at a low temperature is formed by incorporating a polymer having a specific functional group into the photosensitive composition The present invention has been completed.

That is, the present invention relates to a composition comprising:

[A] a compound having an acidic functional group and an alicyclic epoxy group in the same molecule or different molecules, and

[B] Photosensitizer

As a photosensitive composition,

The present invention provides a photosensitive composition comprising [A] a component comprising the following (a1) polymer, or a combination of the following (a2) polymer and the following (a3) polymer.

(a1) Polymer: A polymer having an acidic functional group and an alicyclic epoxy group in the same molecule

(a2) Polymer: A polymer having an acidic functional group and no alicyclic epoxy group

(a3) Polymer: A polymer having an alicyclic epoxy group and no acidic functional group

The present invention also provides a display element, a light emitting element and a light receiving element comprising a cured film as a cured product of the photosensitive composition and the cured film. Here, the "cured film" means each color pixel, a protective film, a black matrix, a spacer, an insulating film, and the like used in a display element or a solid-state image pickup element.

The present invention further provides a process for producing a cured film, which comprises the following steps (1) to (4).

Step (1): a step of forming a coating film on the substrate by applying the photosensitive composition

Step (2): A step of irradiating the coating film obtained in the step (1) with radiation

Step (3): a step of developing the coating film obtained in the step (2)

Step (4): Step of heating the coating film obtained in the step (3) at 70 to 180 캜

By using the photosensitive composition of the present invention, it is possible to form a cured film excellent in solvent resistance even at post-baking at a low temperature. Further, since the photosensitive composition of the present invention is excellent in storage stability and developability and hardly causes problems such as viscosity increase, the contrast and brightness can be further improved. Therefore, the photosensitive composition of the present invention is well suited for the production of various color filters including color filters for color liquid crystal display devices, color filters for color separation of solid-state image pickup devices, color filters for organic EL display devices, and color filters for electronic papers It is very useful as a protective film material, a spacer material, and an insulating film material.

(Mode for carrying out the invention)

Hereinafter, the present invention will be described in detail.

[Photosensitive composition]

Hereinafter, the constituent components of the photosensitive composition of the present invention will be described in detail.

- [A] component -

The component [A] is a compound having an acidic functional group and an alicyclic epoxy group in the same molecule or different molecules, and is preferably a polymer (a1), a polymer (a2) ) Polymer and (a3) polymer as an essential component. Herein, in the present specification, the "acidic functional group" refers to a functional group that functions to exhibit the acidity of the organic acid in the structure, and the "alicyclic epoxy group" refers to a functional group having two carbon atoms And an epoxy group formed by one oxygen atom.

(a1) Polymer: A polymer having an acidic functional group and an alicyclic epoxy group in the same molecule

(a2) Polymer: A polymer having an acidic functional group and no alicyclic epoxy group

(a3) Polymer: A polymer having an alicyclic epoxy group and no acidic functional group

The component [A] is a component which forms a cross-linking structure in the molecule or in the molecule in the exposure and post-baking process when the cured film is formed using the photosensitive composition, thereby enhancing the curability of the coating film. The component [A] may contain a polymer other than the polymer (a1), or a combination of the polymer (a2) and the polymer (a3), and may contain (a1) (A1) may be contained together with the combination of the (a2) polymer and the (a3) polymer. Further, the (a1) polymer, (a2) polymer and (a3) polymer may each contain one kind or two or more kinds.

<(a2) Polymer>

First, the (a2) polymer will be explained. (a2) The polymer is a polymer having an acidic functional group and no alicyclic epoxy group. The acidic functional group is not particularly limited as long as it is a functional group exhibiting acidity, and examples thereof include a carboxyl group, a thiocarboxyl group, a dithiocarbocyl group, a mercapto carbonyl group, a hydroperoxy group, a phenolic hydroxyl group, , A sulfonic acid group, an alcoholic hydroxyl group, a thiol group, a phosphino group, a phosphono group, a selenono group, a selenino group, a seleneno group, an arsino group, an arsono group, a boronic acid group and a boronic acid group . Among them, a carboxyl group is preferable.

The polymer (a2) is not particularly limited as long as it is a polymer having an acidic functional group and not having an alicyclic epoxy group, but an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter also referred to as "unsaturated monomer (α1) (Excluding the polymer (a1), hereinafter also referred to as a "carboxyl group-containing polymer"), or a polysiloxane having a structural unit having at least one carboxyl group, provided that the polymer (a1) is excluded. Hereinafter also referred to as &quot; carboxyl group-containing polysiloxane &quot;).

As the unsaturated monomer (? 1) in the carboxyl group-containing polymer,

Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid,? -Crotonic acid and cinnamic acid;

Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid, or anhydrides thereof;

Mono [(meth) acryloyloxyalkyl] ester of a divalent or higher polyvalent carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] ;

and macromonomers obtained by introducing (meth) acryloyloxy groups and hydroxyl groups into polycaprolactone oligomers such as? -carboxypolycaprolactone mono (meth) acrylate.

The unsaturated monomer (? 1) may be used alone or in combination of two or more.

The carboxyl group-containing polymer is preferably a (meth) acrylic polymer containing (meth) acrylic acid as the unsaturated monomer (? 1). The carboxyl group-containing polymer may have another ethylenic unsaturated monomer copolymerizable with the unsaturated monomer (? 1) (hereinafter also referred to as "unsaturated monomer (? 2)") as a structural unit. The unsaturated monomer (? 2) may be used alone or in combination of two or more.

As the unsaturated monomer (? 2), for example,

N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- N-substituted maleimides such as 6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (acridinyl) maleimide;

Styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Aromatic vinyl compounds such as ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

Indene compounds such as indene and 1-methylindene;

Acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (Polymerization degree: 2 to 10) Methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) Methyl ether (meth) acrylate, polyethylene glycol (Meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan- (Meth) acrylate, 3 - [(meth) acryloyloxymethyl] oxetane, 3 - [(meth) acrylate, ) Acryloyloxymethyl] -3-ethyloxetane as well as ( L) acrylic acid ester;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) The same vinyl ether;

And macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.

 The copolymer of the unsaturated monomer (α1) and the unsaturated monomer (α2) can be produced by, for example, providing an unsaturated monomer (α1) and an unsaturated monomer (α2) to a known polymerization reaction. The copolymerization ratio of the unsaturated monomer (? 1) in the copolymer is preferably 5 to 40% by mass, more preferably 10 to 30% by mass. With such an embodiment, since the crosslinking structure is easily formed in the intermolecular or molecular way in the exposure and post-baking steps, the curability of the coating film can be further enhanced even at post-baking at a low temperature.

As specific examples of the copolymer of the unsaturated monomer (? 1) and the unsaturated monomer (? 2), for example, JP-A 7-140654, JP 8-259876, JP 10-31308 Japanese Unexamined Patent Application Publication Nos. 10-300922, 11-174224, 11-258415, 2000-56118, 2004-101728, etc. Include the disclosed copolymers.

Further, in the present invention, for example, Japanese Unexamined Patent Application Publication No. 5-19467, Japanese Unexamined Patent Publication No. 6-230212, Japanese Unexamined Patent Publication No. 7-207211, Japanese Unexamined Patent Publication No. 09-325494 , Japanese Unexamined Patent Application Publication Nos. 11-140144 and 2008-181095 disclose a method in which a carboxyl group-containing polymer having a polymerizable unsaturated bond, such as a (meth) acryloyl group, ) Polymer.

Examples of the structural unit having at least one carboxyl group in the carboxyl group-containing polysiloxane include structural units represented by the following general formulas (1-1) to (1-4). From the viewpoints of improvement of storage stability and improvement of curability in low-temperature post-baking, at least one of the structural units having at least one carboxyl group may be contained, It is preferable to have the structural unit appearing.

[In the formulas (1-1) to (1-4)

Z ¹ represents a group having a carboxyl group,

And Y represents a monovalent hydrocarbon group.

Examples of the group having a carboxyl group according to Z ¹ include groups represented by the following (a) or (b).

[In the formulas (a) and (b)

X ¹ represents a single bond or a divalent hydrocarbon group,

* Indicates a combined hand.]

Examples of the divalent hydrocarbon group according to X ¹ include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. Herein, in the present specification, the "alicyclic hydrocarbon group" is a concept excluding an aliphatic hydrocarbon group having no cyclic structure. In the present specification, the terms &quot; alicyclic hydrocarbon group &quot; and &quot; aromatic hydrocarbon group &quot; include not only a group consisting of a ring structure but also a structure in which a bivalent aliphatic hydrocarbon group is substituted for the ring structure. It may contain at least an alicyclic hydrocarbon or an aromatic hydrocarbon. The divalent aliphatic hydrocarbon group may be any of a straight chain and a branched chain, and the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group may be an unsaturated hydrocarbon group or a saturated hydrocarbon group.

The divalent aliphatic hydrocarbon group includes, for example, an alkanediyl group and an alkenediyl group, and the number of carbon atoms thereof is preferably from 1 to 20, more preferably from 1 to 12, still more preferably from 1 to 6 . Specific examples include methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane- A butane-1,3-diyl group, a butane-1, 4-diyl group, a pentane-1, 4-diyl group, A pentane-1,5-diyl group, a hexane-1,5-diyl group, a hexane-1,6-diyl group, a 2-methylpropane- Diyl group, an ethene-1,1-diyl group, an ethene-1,2-diyl group, a propene-1,2-diyl group, a propene- Butene-1, 3-diyl group, 1-butene-1, 4-diyl group, 2-pentene-1,5-diyl group, 3-hexene- , 6-diyl group, and the like.

The bivalent alicyclic hydrocarbon group includes, for example, a cycloalkylene group and a cycloalkenylene group, and the number of carbon atoms thereof is preferably 3 to 20, and more preferably 3 to 12. Specific examples thereof include monocyclic hydrocarbon ring groups such as cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclobutenylene group, cyclopentenylene group and cyclohexenylene group, 1,4-nor A norbornylene group such as a norbornylene group and a 2,5-norbornylene group, a crosslinked ring hydrocarbon group such as a 1,5-adamantylene group and a 2,6-adamantylene group, and the like.

The bivalent aromatic hydrocarbon group includes, for example, an arylene group, and a monocyclic to tricyclic arylene group having 6 to 14 carbon atoms is preferable. Specific examples thereof include a phenylene group, a biphenylene group, a naphthylene group, a phenanthrene group, and an anthrylene group.

Examples of the monovalent hydrocarbon group according to Y include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

The aliphatic hydrocarbon group may be any of a straight chain and a branched chain, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group and an alkynyl group. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and still more preferably an alkyl group having 1 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, , A 2-ethylhexyl group, a decyl group, and a dodecyl group. The alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 15 carbon atoms, and still more preferably an alkenyl group having 2 to 10 carbon atoms. The alkynyl group is preferably an alkynyl group having 2 to 20 carbon atoms, more preferably an alkynyl group having 2 to 15 carbon atoms, and still more preferably an alkynyl group having 2 to 10 carbon atoms. Specific examples include ethynyl, 1-propynyl, 1-butynyl, 1-pentynyl, 3-pentynyl, 4-ethynyl) -5-hexynyl, 2-decynyl and the like.

Examples of the alicyclic hydrocarbon group include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a crosslinked ring hydrocarbon group, a spiro hydrocarbon group, and a cyclic terpene hydrocarbon group. The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 30 carbon atoms, more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, t-butylcyclohexyl, cycloheptyl, cyclooctyl, tricyclodecanyl, decahydro-2-naphthyl , Tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, pentacyclopentadecanyl group, isobonyl group, adamantyl group, dicyclopentanyl group, dicyclopentenyl group, tricyclopentanyl group, tricyclopentenyl group And the like.

The aromatic hydrocarbon group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Herein, in the present specification, the "aryl group" refers to a monocyclic to tricyclic aromatic hydrocarbon group, and examples thereof include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, A thienyl group, a thienyl group, a thienyl group, a thienyl group, a thienyl group, a thienyl group, a thienyl group, a thienyl group,

The divalent hydrocarbon group and the monovalent hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom is preferable. The alkoxy group may be straight-chain or branched, but preferably has 1 to 6 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. The position and the number of the substituent are arbitrary. For example, when the substituent has a fluorine atom as the substituent, it may be a perfluoroalkyl group. When two or more substituents are present, the substituents may be the same or different.

The divalent hydrocarbon group and the monovalent hydrocarbon group may have at least one linking group containing an atom other than a carbon atom and a hydrogen atom at the carbon-carbon bond or at the terminal thereof. Examples of such linking groups include -O-, -S-, -SO ₂ -, -CO-, -COO-, -OCO-, -CONR ^a - (wherein R ^a represents a hydrogen atom or a C 1-6 An alkyl group), and -NR ^a - (wherein R ^a has the same meaning as described above). The linking groups may be one or more. The hydrocarbon group and the linking group may combine to form a ring structure. The carbon number of the above-mentioned hydrocarbon group means the total carbon number of the part excluding the carbon atoms constituting the linking group.

Examples of the silane compound imparting the structural unit represented by the above general formula (1-1) include carboxy-substituted alkyltrialkoxysilane and the like. Specific examples include, for example, carboxymethyltrimethoxysilane, carboxyethyltrimethoxysilane, 2-carboxyethyltrimethoxysilane, carboxypropyltrimethoxysilane, carboxymethyltriethoxysilane, carboxymethyltri- Carboxymethyltriacetoxysilane, carboxymethyltri (methoxyethoxy) silane, and the like can be given.

Examples of the silane compound imparting the structural unit represented by the general formula (1-2) include di (carboxy-substituted alkyl) dialkoxysilane and the like.

Examples of the silane compound imparting the structural unit represented by the general formula (1-3) include a carboxy-substituted alkylalkyl dialkoxy silane, a carboxy-substituted alkylaryl dialkoxy silane, and the like. Specific examples include, for example, carboxymethylmethyldimethoxysilane, carboxymethylmethyldiethoxysilane, carboxymethylmethyldiacetoxysilane, carboxymethylethyldimethoxysilane, 2-carboxyethylmethyldimethoxysilane, carboxymethylphenyldimethoxysilane, , Carboxymethylphenyldiethoxysilane, and 2-carboxyethylphenyldimethoxysilane.

Examples of the silane compound imparting the structural unit represented by the general formula (1-4) include carboxy-substituted alkyldialkylalkoxysilane, carboxy-substituted alkylalkylarylalkoxysilane, and carboxy-substituted alkyldiarylalkoxysilane. have.

The structural unit having at least one carboxyl group may have one or more kinds of structural units and may have structural units other than the structural units. Examples of other structural units include structural units represented by the following general formulas (2-1) to (2-4). The structural units represented by the general formulas (2-1) to (2-4) may have one or more kinds of structural units.

[In formulas (2-1) to (2-4), Y is the same as Y in (1-3) and (1-4) above.]

Examples of the silane compound giving the structural unit represented by the general formula (2-1) include alkyltrialkoxysilane, alkenyltrialkoxysilane, alkynyltrialkoxysilane, cycloalkyltrialkoxysilane, aryltrialkoxysilane , (Meth) acryloyloxy-substituted alkyltrialkoxysilane, and the like. Specific examples include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, phenyltrimethoxy Silane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, styryltrialkoxysilane, and the like.

Examples of the silane compound giving the structural unit represented by the general formula (2-2) include dialkyldialkoxysilane, alkylphenyldialkoxysilane, diphenyldialkoxysilane, divinyldialkoxysilane, vinylalkyldi Alkoxysilane, allylalkyldialkoxysilane, styrylalkyldialkoxysilane, and the like. Specific examples include dimethyldimethoxysilane, dibutyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, 3- (meth) acryloylpropylmethyldimethoxysilane, 3- (meth) Acryloyloxypropyldimethoxysilane, 3,3'-di (meth) acryloyloxypropyldimethoxysilane, 3,3'-di (meth) acryloyloxypropyldiethoxysilane, etc. .

Examples of the silane compound imparting the structural unit represented by the general formula (2-3) include trialkylalkoxysilane, dialkylarylalkoxysilane, alkyldiarylalkoxysilane, and the like. Specific examples thereof include, for example, trimethylmethoxysilane, trimethylethoxysilane, tributylmethoxysilane, tributylethoxysilane, triphenylmethoxysilane, 3,3 ', 3 "-tri (meth) acryloyl 3,3 ', 3 "-tri (meth) acryloyloxypropylethoxysilane, and the like can be given.

As the silane compound giving the structural unit represented by the above general formula (2-4), tetraalkoxysilane can be mentioned, for example. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropyloxysilane, tetraisopropyloxysilane, tetrabutoxysilane, and the like.

The carboxyl group-containing polysiloxane can be produced, for example, by hydrolysis and condensation of a raw material silane compound. The hydrolysis and condensation reaction can be carried out by a known method. For example, a method of mixing a raw silane compound in a solvent and adding water to the mixed solution to hydrolyze and condense can be mentioned. The hydrolysis and condensation reaction may be carried out by adding an acid catalyst. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and polyphosphoric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethane An organic acid such as a sulfonic acid, and an acidic ion exchange resin. Examples of the solvent include hydrocarbons, ketones, esters, ethers, and alcohols. The amount of water to be used is preferably 0.1 to 3 moles, more preferably 0.3 to 2 moles, and still more preferably 0.5 to 1.5 moles, per 1 mole of the sum of the hydrolyzable groups of the raw material silane compound.

The proportion of the structural unit having at least one carboxyl group in the carboxyl group-containing polysiloxane can be appropriately selected, but is preferably 5 to 40 mass%, more preferably 10 to 30 mass%, in the total structural units. The upper limit of the ratio is not particularly limited, and may be 100% by mass.

Among them, as the polymer (a2), a polymer containing an ethylenically unsaturated monomer having at least one carboxyl group as a monomer unit is preferable, and a (meth) acrylic compound having a carboxyl group represented by the formula (a) or (b) (Meth) acrylic polymer as a monomer unit is more preferable, and a (meth) acrylic polymer containing (meth) acrylic acid as a monomer unit is more preferable.

The acid value of the (a2) polymer is preferably 10 to 200 mgKOH / g, more preferably 50 to 160 mgKOH / g, and even more preferably 70 to 120 mgKOH / g. Here, in the present specification, the "acid value" means the number of mg of KOH required to neutralize 1 g of non-volatile matter excluding the solvent of the polymer solution. In the present specification, the "nonvolatile matter" is a component other than the solvent described later.

The polymer (a2) has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC, elution solvent: tetrahydrofuran) of usually 1,000 to 50,000, 30,000.

<(a3) Polymer>

Next, the (a3) polymer will be described.

(a3) The polymer is a polymer having an alicyclic epoxy group and no acidic functional group. The alicyclic epoxy group is preferably an epoxy group formed by two adjacent carbon atoms and one oxygen atom in the alicyclic structure, and examples thereof include a 2,3-epoxycyclobutyl group, a 2,3-epoxycyclopentyl group, Epoxycyclohexyl group, 5,6-epoxy-tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, 2,3-epoxy-tricyclo [4.2.1.0 ^2,5 ] -Yl group, 3- (3,4-epoxycyclohexyl) -9-hydroxy-1,5-dioxaspiro [5.5] undecan- -Hydroxy-2,4-dioxaspiro [5.5] undecan-8-yl group and the like. Among them, a 3,4-epoxycyclohexyl group is preferable.

The polymer (a3) is not particularly limited as long as it is a polymer having an alicyclic epoxy group and no acidic functional group, but an ethylenically unsaturated monomer having at least one alicyclic epoxy group (hereinafter also referred to as "unsaturated monomer (? 3)") (Excluding a polymer (a1), hereinafter also referred to as "an alicyclic epoxy group-containing polymer"), or a polysiloxane having a structural unit having at least one alicyclic epoxy group, provided that (a1) (Hereinafter also referred to as &quot; alicyclic epoxy group-containing polysiloxane &quot;) is preferred.

Examples of the unsaturated monomer (? 3) in the alicyclic epoxy group-containing polymer include a vinyl compound having an alicyclic epoxy group and a (meth) acrylate having an alicyclic epoxy group. Examples of the vinyl compound having an alicyclic epoxy group include 1,2-epoxy-4-vinylcyclohexane and the like.

The alicyclic epoxy group-containing polymer is preferably a (meth) acrylic polymer containing (meth) acrylate having an alicyclic epoxy group as the unsaturated monomer (? 3).

As the (meth) acrylate having an alicyclic epoxy group, compounds represented by the following general formulas (3) to (5) are preferable.

[In formulas (3) to (5)

R ¹ independently represents a hydrogen atom or a methyl group,

X ² represents, independently of each other, a single bond or a divalent hydrocarbon group.

The divalent hydrocarbon group according to X ² has the same meaning as X ^{1 in the} above formulas (a) and (b), and its specific structure is as described in the above formulas (a) and (b).

X ² is preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably a methylene group, an ethylene group, an ethane-1,1-diyl group, Propyl-1,2-diyl group, propane-1,3-diyl group and propane-2,2-diyl group are more preferable.

Formula (3) include compounds represented by 3,4-epoxycyclohexylmethyl methacrylate (trade name as commercially available products production cycle macromer M100, die POV Chemical Industries Co., Ltd.; the R ¹ group in the formula (3), X ² (Commercially available from Cyclomer A400, manufactured by Dai-ichi Kogaku Kogyo Kabushiki Kaisha; a compound in which R ¹ is a hydrogen atom and X ² is a methylene group in the formula (3)), and 3,4-epoxycyclohexylmethacrylate Compounds).

Examples of the compound represented by the formula (4) include compounds represented by the formulas (4-1) to (4-8).

Examples of the compound represented by the formula (5) include compounds represented by the formulas (5-1) to (5-8).

Among the compounds represented by the formula (4), compounds represented by the formulas (4-1), (4-4), (4-5) and (4-8) are preferable, and among the compounds represented by the formula (5) , (5-1), (5-4), (5-5) and (5-8) are preferable.

The unsaturated monomer (? 3) may be used alone or in combination of two or more, and may contain another ethylenic unsaturated monomer capable of copolymerizing with the unsaturated monomer (? 3) as a structural unit. As the other ethylenic unsaturated monomer, for example, the above-mentioned unsaturated monomer (? 2) can be mentioned.

(a3) In the case where the polymer is a copolymer of an unsaturated monomer (? 3) and an unsaturated monomer (? 2), for example, it can be produced by providing an unsaturated monomer (? 3) and an unsaturated monomer (? . The copolymerization ratio of the unsaturated monomer (? 3) in the copolymer is preferably from 20 to 99% by mass, more preferably from 50 to 95% by mass. With such an embodiment, since the crosslinking structure is easily formed in the intermolecular or molecular way in the exposure and post-baking steps, the curability of the coating film can be further enhanced even at post-baking at a low temperature.

Examples of the structural unit having at least one alicyclic epoxy group in the alicyclic epoxy group-containing polysiloxane include structural units represented by the following general formulas (6-1) to (6-4). From the viewpoints of improvement of storage stability and improvement of curability in low-temperature post-baking, it is preferable that at least one of structural units having at least one alicyclic epoxy group is used, Is preferred.

[In formulas (6-1) to (6-4)

Z ² represents a group having an alicyclic epoxy group,

And Y represents a monovalent hydrocarbon group.

As the alicyclic epoxy group according to Z ² , for example, the above-mentioned alicyclic epoxy group can be mentioned. Among them, as the group having an alicyclic epoxy group, groups represented by the following (c) to (e) are preferable.

[In the formulas (c) to (e)

X ² is as defined above formula (3) ~ X ² in (5),

* Indicates a combined hand.]

The specific constitution of X ^{2 in} the formulas (c) to (e) is as described in the above formulas (a) and (b).

As the silane compound giving the structural unit represented by the general formula (6-1), for example, an alicyclic epoxy-substituted alkyltrialkoxysilane can be cited. Specific examples include, for example, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4- Hexyl) ethyltri n-propoxysilane, and? - (3,4-epoxycyclohexyl) ethyltriisopropoxysilane.

Examples of the silane compound imparting the structural unit represented by the above general formula (6-2) include di (alicyclic epoxy-substituted alkyl) dialkoxysilane. Specific examples thereof include di (? - (3,4-epoxycyclohexyl) ethyl) dimethoxysilane and di (? - (3,4-epoxycyclohexyl) ethyl) diethoxysilane.

Examples of the silane compound imparting the structural unit represented by the general formula (6-3) include an alicyclic epoxy-substituted alkyl-alkyl dialkoxy silane and an alicyclic epoxy-substituted alkyl aryl dialkoxy silane. Specific examples thereof include, for example, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, β- (3,4- (3,4-epoxycyclohexyl) ethylmethyldiisopropoxysilane,? - (3,4-epoxycyclohexyl) ethylethyldimethoxysilane,? - 4-epoxycyclohexyl) ethylethyldiethoxysilane, and the like.

Examples of the silane compound imparting the structural unit represented by the general formula (6-4) include alicyclic epoxy-substituted alkyldialkylalkoxysilanes, alicyclic epoxy-substituted alkylalkylarylalkoxysilanes, alicyclic epoxy-substituted alkyldiaryls And alkoxysilane. Specific examples include, for example, β- (3,4-epoxycyclohexyl) ethyldimethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethylethoxysilane, β- (3,4- Hexyl) ethyldimethylpropoxysilane, and? - (3,4-epoxycyclohexyl) ethyldimethylisopropoxysilane.

The structural unit having at least one alicyclic epoxy group may have one or more structural units and may have structural units other than the structural units. Examples of other structural units include the structural units represented by the general formulas (2-1) to (2-4). The structural units represented by the general formulas (2-1) to (2-4) may have one or more structural units, and the specific structure thereof is the same as described for the polymer (a2) .

The alicyclic epoxy group-containing polysiloxane can be produced, for example, by hydrolysis and condensation of a raw material silane compound, and specific examples of the hydrolysis and condensation reaction are as described in the above-mentioned (a2) polymer.

The proportion of the structural unit having at least one alicyclic epoxy group in the alicyclic epoxy group-containing polysiloxane can be appropriately selected, but is preferably 20% by mass or more, more preferably 50% by mass or more, and more preferably 70% % Or more. The upper limit of the ratio is not particularly limited and may be 100% by mass. From the viewpoint of further improving the solvent resistance, the upper limit is preferably 99% by mass or less, and more preferably 95% by mass or less.

Among them, as the polymer (a3), a polymer containing a polysiloxane having a structural unit represented by the general formula (6-1) and an ethylenically unsaturated monomer having at least one alicyclic epoxy group as a monomer unit is preferable, A polysiloxane having a structural unit represented by the formula (6-1), wherein the polysiloxane in which the alicyclic epoxy group is at least one of the groups represented by the above formulas (c) to (e), the alicyclic (Meth) acrylic polymer having a (meth) acrylic compound having at least one of a hydroxyl group and an epoxy group as a monomer unit is more preferable, and a polysiloxane having a structural unit represented by the general formula (6-1) A polysiloxane which is at least one of the groups represented by the formulas (c) to (e), a (meth) acrylic acid containing at least one of the compounds represented by the above general formulas (3) to (5) Based polymer is more preferred.

The epoxy equivalent of the (a3) polymer is preferably 100 to 10,000 g / mol, more preferably 150 to 1,000 g / mol. The epoxy equivalent can be measured in accordance with JIS K 7236.

The polymer (a3) preferably has a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (dissolution solvent: tetrahydrofuran) of 500 to 100,000, more preferably 1,000 to 50,000, and 1,500 to 30,000 Is more preferable.

<(a1) Polymer>

Next, the (a1) polymer will be described. (a1) The polymer is a polymer having an acidic functional group and an alicyclic epoxy group in the same molecule.

The polymer (a1) is preferably a copolymer having the above-mentioned unsaturated monomer (? 1) and an unsaturated monomer (? 3) as a structural unit (hereinafter also referred to as an "acidic functional group and an alicyclic epoxy group-containing copolymer"), (Hereinafter also referred to as &quot; acid functional group and alicyclic epoxy group-containing polysiloxane &quot;) having a structural unit having one or more alicyclic epoxy groups and a structural unit having at least one alicyclic epoxy group are preferable.

The acidic functional group and alicyclic epoxy group-containing copolymer can be produced by providing an unsaturated monomer (? 1) and an unsaturated monomer (? 3) to a known polymerization reaction, and may be a block copolymer or a random copolymer. Further, a carboxyl group may be introduced by reacting a part of the alicyclic epoxy group of the alicyclic epoxy group-containing polymer (a3) described above with a polyvalent carboxylic acid or an acid anhydride thereof. Examples of the polyvalent carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, butane tetracarboxylic acid, and cyclohexanetetracarboxylic acid. The specific constitution of the unsaturated monomer (? 1) and the unsaturated monomer (? 3) is the same as described for the (a2) polymer and the (a3) polymer.

The unsaturated monomer (? 1) and the unsaturated monomer (? 3) can each have one or more kinds of unsaturated monomers (? 1) and? 3 and other ethylenically unsaturated monomers copolymerizable with the unsaturated monomers You do not mind. As the other ethylenic unsaturated monomer, for example, the above-mentioned unsaturated monomer (? 2) can be mentioned. The specific constitution of the unsaturated monomer (? 2) is as described for the (a2) polymer.

The copolymerization ratio of the unsaturated monomer (α1) to the unsaturated monomer (α3) in the acidic functional group and the alicyclic epoxy group-containing copolymer is preferably in the range of from 1 to 10 0.02 to 0.9, more preferably 0.05 to 0.5. With such an embodiment, since the crosslinking structure is easily formed in the intermolecular or molecular way in the exposure and post-baking steps, the curability of the coating film can be further enhanced even at post-baking at a low temperature.

When the acidic functional group and alicyclic epoxy group-containing copolymer have an unsaturated monomer (? 2), the copolymerization ratio of the unsaturated monomer (? 2) in the copolymer is preferably 10 to 90% by mass, 70% by mass.

Examples of the structural unit having at least one carboxyl group in the acidic functional group and the alicyclic epoxy group-containing polysiloxane include structural units represented by the general formulas (1-1) to (1-4) Lt; / RTI &gt; Among them, those having at least a structural unit represented by the above general formula (1-1) are preferable from the viewpoints of improvement of storage stability and improvement of curability in low-temperature post-baking. Examples of the structural unit having at least one alicyclic epoxy group include structural units represented by the above general formulas (6-1) to (6-4), and they may have one kind or two or more kinds. Among them, it is preferable to have at least a structural unit represented by the above general formula (6-1) from the viewpoints of improvement of storage stability and improvement of curability in low-temperature post-baking. Specific examples of the structural units represented by the general formulas (1-1) to (1-4) and the structural units represented by the general formulas (6-1) to (6-4) (a3) polymer.

The structural unit having a carboxyl group and an alicyclic epoxy group may have a structural unit represented by the following general formula (7-1) or general formula (7-2).

[Formula (7-1), according to (7-2), Z ^1, (1-3) in the Z ^1, Z ² and Y are, respectively, the formula (1-1) to (1-4) And Y in (1-4), and Z ² in the formulas (6-1) to (6-4)).

Specific structures of Z ¹ , Z ² and Y according to formulas (7-1) and (7-2) are the same as described for the above-mentioned (a2) polymer and (a3) polymer.

The acidic functional group and alicyclic epoxy group-containing polysiloxane may have a structural unit having at least one carboxyl group, a structural unit having at least one alicyclic epoxy group, and a structural unit other than a structural unit having a carboxyl group and alicyclic epoxy group It does not matter. Examples of other structural units include the structural units represented by the general formulas (2-1) to (2-4). The structural units represented by the general formulas (2-1) to (2-4) can have one or more kinds of structural units, and its specific structure is as described in the above-mentioned (a2) polymer .

The acidic functional group and the alicyclic epoxy group-containing polysiloxane can be produced, for example, by hydrolysis and condensation of a raw material silane compound, and specific examples of the hydrolysis and condensation reaction are as described in the above-mentioned (a2) polymer.

Further, a carboxyl group may be introduced by reacting a part of the alicyclic epoxy group of the alicyclic epoxy group-containing polysiloxane described in the above (a3) polymer with a polyvalent carboxylic acid or an acid anhydride thereof. The specific constitution of the structural unit having at least one carboxyl group and the structural unit having at least one alicyclic epoxy group is the same as described for the polymer (a2) and the polymer (a3).

The ratio of the structural unit having at least one carboxyl group and the structural unit having at least one alicyclic epoxy group in the acidic functional group and the alicyclic epoxy group-containing polysiloxane can be suitably selected, but the ratio of the carboxyl group-containing structural unit / alicyclic epoxy group- Unit is preferably 0.02 to 1.0, more preferably 0.05 to 1.0. With such an embodiment, since the cross-linking structure is easily formed in the molecule or in the molecule, the curing property of the coating film can be further enhanced even at post-baking at a low temperature.

The proportion of the other structural units in the acidic functional group and the alicyclic epoxy group-containing polysiloxane is preferably 5 to 90 mass%, more preferably 5 to 80 mass%, with respect to the total structural units. The lower limit of the mass ratio is not particularly limited and may be 0 mass%.

Among them, the polymer (a1) is preferably a polymer comprising an ethylenic unsaturated monomer having at least one carboxyl group and at least one ethylenic unsaturated monomer having at least one alicyclic epoxy group as a monomer unit, (meth) acrylic polymer containing a (meth) acrylic compound having a carboxyl group represented by the formula (b) and a (meth) acrylic compound having at least one alicyclic epoxy group represented by the above formulas (Meth) acrylic polymer containing at least one of (meth) acrylic acid and the compound represented by any one of the formulas (3) to (5) as a monomer unit is more preferable.

The acid value of the (a1) polymer is preferably 10 to 200 mgKOH / g, more preferably 50 to 160 mgKOH / g, and even more preferably 70 to 120 mgKOH / g.

The epoxy equivalent of the (a1) polymer is preferably 100 to 10,000 g / mol, more preferably 150 to 1,000 g / mol.

The polymer (a1) has a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably 3,000 to 50,000.

Among them, the component (A) preferably contains a polymer (a1) from the viewpoint of achieving balanced storage stability, developability and solvent resistance at a high level. In the case of containing a polymer (a1), from the viewpoint of developability, it is more preferable to further contain a polymer (a2) or a polymer (a3), and furthermore preferably a polymer (a2). When the polymer (a1) and the polymer (a2) are used in combination, the total content of the polymer (a1) and the polymer (a2) is preferably 75 mass% or more in the component [A].

When the combination of the polymer (a2) and the polymer (a3) is contained as the component [A], the mass ratio of the polymer (a2) and the polymer (a3) is improved by improving the storage stability and improving the curability during low temperature postbaking (A3) polymer is preferably from 20:80 to 80:20, more preferably from 25:75 to 75:25, and even more preferably from 30:70 to 70:30.

The content of the component [A] in the photosensitive composition is preferably 5 to 90 mass%, more preferably 10 to 85 mass%, and still more preferably 15 to 80 mass%, based on the solid content of the photosensitive composition. By virtue of this structure, the storage stability is good, and the crosslinking structure is easily formed in the molecule or in the molecule, so that the curing property of the coating film can be further enhanced even at post-baking at a low temperature. Herein, in the present specification, the term &quot; solid component &quot; means a component other than the solvent described later.

- [B] Photosensitizer -

[B] As the photosensitizer, a compound capable of generating radicals in response to radiation to initiate polymerization (that is, a [B-1] photo radical generator) or a compound capable of generating an acid in response to radiation -2] photo acid generator). The photosensitive composition of the present invention can have a radiation-sensitive property by containing a [B] photosensitive agent. For example, it may have a negative radiation-sensitive property by containing a [B-1] photo-radical generator and a positive radiation-sensitive property by containing a [B-2] photo acid generator.

Examples of the photo radical generator [B-1] include a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, an O-acyloxime compound, an onium salt compound, Benzophenone compounds,? -Diketone compounds, polynuclear quinone compounds, diazo compounds, imidosulfonate compounds, and the like. The photo-radical generator may contain one or more species. Among them, at least one kind selected from the group of a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, and an O-acyloxime compound is preferable as the photo radical generator.

Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- Oxalone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone.

Examples of the acetophenone-based compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- -Morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2' Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

When a non-imidazole-based compound is used as the [B-1] photo-radical generator, it is preferable to use a hydrogen donor in combination because it can improve the sensitivity. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a nonimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (Diethylamino) benzophenone, and the like. The hydrogen donor may be used alone or in combination of two or more, but it is preferable to use one or more kinds of mercaptan-based hydrogen donors and one or more amine-based hydrogen donors in combination in order to further improve the sensitivity.

Specific examples of the triazine compound include the compounds described in paragraphs [0063] to [0065] of Japanese Patent Publication Nos. 57-6096 and 2003-238898.

Examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzoyloxime), ethanone, 1- [ (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O- -9H-carbazol-3-yl] -, 1- (O-acetyloxime), ethanone, 1- [ -Dimethyl-1,3-dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -, 1- (O-acetyloxime) or Compound No. 1 described in WO2014 / 187170 pamphlet And compounds of No.52. As commercially available products of O-acyloxime compounds, NCI-831, NCI-930 (manufactured by ADEKA Corporation), DFI-020, DFI-091 (manufactured by Daito Kikusui Co., Ltd.) have.

Further, when a photo-radical generator other than a non-imidazole-based compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. Examples of the sensitizer include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone , Ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino- ) Coumarin, and 4- (diethylamino) chalcone.

The content of the [B-1] photo-radical generator in the photosensitive composition is preferably 0.01 to 30 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the polymerizable compound [E] described later. With such an embodiment, since the cross-linking structure is easily formed in the molecule or in the molecule, the curing property of the coating film can be further enhanced even at post-baking at a low temperature.

Examples of the photoacid generator include [B-2] oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, Quinone diazide compounds and the like. Further, the [B-2] photoacid generator may contain one kind or two or more kinds thereof.

As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the following formula (8) is preferable.

[In the formula (8), R ^a represents an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, A group wherein some or all of the hydrogen atoms contained in the formula hydrocarbon group and the aryl group are substituted with substituents]

As the alkyl group according to R ^a , a linear or branched alkyl group having 1 to 12 carbon atoms is preferable. The straight or branched alkyl group having 1 to 12 carbon atoms may be substituted by a substituent. Examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and a 7,7-dimethyl-2-oxononorbornyl group And alicyclic groups including bridged alicyclic groups. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptylfluoropropyl group.

As the alicyclic hydrocarbon group according to R ^a , an alicyclic hydrocarbon group having 4 to 12 carbon atoms is preferable. The alicyclic hydrocarbon group having 4 to 12 carbon atoms may be substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom.

The aryl group according to R ^a is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group may be substituted by a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom. For example, specific examples of the substituted aryl group include a tolyl group and a xylyl group.

Examples of the oxime sulfonate compound include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino- Thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (5-p-toluenesulphonyl) 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, and the like can be given. These are available as commercial products.

Examples of the onium salts include diphenyl iodonium salts, triphenylsulfonium salts, sulfonium salts, benzothiazonium salts, tetrahydrothiophenium salts and benzylsulfonium salts. Among them, as the onium salt, a tetrahydrothiophenium salt or a benzylsulfonium salt is preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, benzyl- -Hydroxyphenylmethylsulfonium hexafluorophosphate is more preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is more preferable.

Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide , N- (2-trifluoromethylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- - (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- Methylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, and N- (4-methylphenylsulfonyloxy) diphenylmaleimide.

Suitable examples of the sulfonic acid ester compound include haloalkylsulfonic acid esters, and more preferred examples thereof include N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester.

As the quinone diazide compound, for example, a phenolic compound or an alcoholic compound (hereinafter also referred to as &quot; mother nucleus &quot;), a 1,2-naphthoquinone diazide sulfonic acid halide or a 1,2-naphthoquinone diazide sulfonic acid amide Can be used.

Examples of the mother nucleus include, but are not limited to, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, .

As specific examples of the nuclei, for example,

As the trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone and the like;

As the tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxy Benzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone and the like;

As the pentahydroxybenzophenone, 2,3,4,2 ', 6'-pentahydroxybenzophenone and the like;

As the hexahydroxybenzophenone, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone and the like;

(P-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (dihydroxyphenyl) methane, (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris 4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethyl] (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobindene- 7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan and the like;

.

Examples of the other parent nuclei other than the above-mentioned parental bone include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) Methylethyl] -3- (1- (3- {1- (2-methylphenyl) -1,3-dihydroxyphenyl) (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, } -1,3-dihydroxybenzene, and the like.

Among them, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4 '- [1- [4- [ - [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferable.

As the 1,2-naphthoquinonediazide sulfonic acid halide, 1,2-naphthoquinonediazide sulfonic acid chloride is preferable, and 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide sulfonic acid chloride, Quinonediazide-5-sulfonic acid chloride is more preferable, and 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferable.

As the 1,2-naphthoquinonediazide sulfonic acid amide, 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid amide is preferable.

In the condensation reaction of the phenolic compound or the alcoholic compound (mother cell) with 1,2-naphthoquinonediazidesulfonic acid halide, the condensation reaction is preferably carried out in an amount of 30 mol% or more and 85 mol or more per mol of the OH group in the phenolic compound or the alcoholic compound Or less, more preferably 50 mol% or more and 70 mol% or less, based on the total amount of the 1,2-naphthoquinonediazide sulfonic acid halide. The condensation reaction can be carried out by a known method.

Among them, oxime sulfonate compounds, onium salts, sulfonimide compounds and quinone diazide compounds are preferable as the [B-2] photoacid generator, and oxime sulfonate compounds and quinone diazide compounds are more preferable . [B-2] By containing such a compound as the photo acid generator, the crosslinking structure is easily formed in the molecule or in the molecule, so that the curing property of the coating film can be further enhanced even at post-baking at low temperature.

The content of [B-2] photo acid generator in the photosensitive composition is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the component [A]. [B-2] By setting the content of the photoacid generator within the above range, the cross-linking structure is easily formed in the molecule or in the molecule, so that the curing property of the coating film can be further enhanced even at post-baking at low temperature.

- [C] Colorant -

The photosensitive composition of the present invention may further contain a [C] colorant. Thus, for example, a colored photosensitive composition for forming a coloring layer of a color filter can be used. Here, the &quot; colored layer &quot; means each color pixel, a black matrix, a black spacer, etc. used in the color filter. [C] The colorant can be used without particular limitation as far as it has colorability, and the color and the material can be appropriately selected depending on the use of the photosensitive composition.

When the photosensitive composition of the present invention is used for forming each color pixel constituting a color filter, at least one kind selected from pigments and dyes is preferably used as a coloring agent in view of high color purity, brightness, contrast, And more preferably at least one kind selected from organic pigments and organic dyes. Among them, it is more preferable to contain at least a dye in order to enjoy the effect of the present invention. The pigments and dyes may each contain one or more species.

Examples of the organic pigment include a compound classified as a pigment in a color index (CI, published by The Society of Dyers and Colourists), and among them, a color index (CI) number Can be preferably used.

C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Red pigments such as Pigment Red 279;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Green pigments such as Pigment Green 59;

C.I. Pigment Blue 15: 6, C.I. Pigment Blue 16, C.I. Pigment Blue 79, C.I. Blue pigments such as Pigment Blue 80;

C.I. Pigment Yellow 83, C.I. Pigment Yellow 129, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 179, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 211, C.I. Pigment Yellow 215, C.I. Yellow pigments such as Pigment Yellow 231;

C.I. Orange pigments such as Pigment Orange 38;

C.I. Pigment Violet 19, C.I. Violet pigment such as Pigment Violet 23

In addition, a diketopyrrolopyrrole bromide pigment represented by the formula (Ic) of Japanese Laid-Open Patent Publication No. 2011-523433 is also preferably used.

Examples of the inorganic pigments include carbon black and titanium black. In addition, JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-237384, JP-A-2010-237569, JP-A-2011-006602, And a rake pigment described in Patent Publication No. 2011-145346.

In the present invention, the pigment may be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. The pigment may be used by modifying its particle surface with a resin, if desired. Further, the organic pigment can be used by finely grinding primary particles by so-called salt milling. As a method of the salt milling, for example, a method disclosed in Japanese Laid-Open Patent Publication No. 08-179111 can be adopted.

The dyes are not particularly limited, and for example, known dyes other than the compounds classified by the color index (CI., Published by The Society of Dyers and Colourists) can be used. Examples of such dyes include triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, coumarin dyes, Pyrazolone dyes, quinoline dyes, nitro dyes, quinone imine dyes, phthalocyanine dyes, and squarylium dyes. Among them, triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, dipyrromethene dyes and phthalocyanine dyes are preferable from the viewpoint of heat resistance.

The dye may be composed of a cation portion and an anion portion, for example, a salt of a cationic chromophore and a counter anion, or an anionic chromophore and a salt of a counter cation. In the present specification, the term &quot; anionic dye &quot; means an ionic dye having a chromophore having an acidic group, and an ionic dye forming a salt with the acidic group is also an anionic dye. In the present specification, the term &quot; cationic dye &quot; means an ionic dye having no acidic group in the ionic dye, and usually a dye having a basic group. In addition, "nonionic dye" means a dye other than a cationic dye and an anionic dye.

Examples of cationic chromophores include triarylmethane chromophore, cyanine chromophore, xanthophore, polymethine chromophore, azo chromophore, diarylmethane chromophore, quinone imine chromophore, anthraquinone chromophore, phthalocyanine chromophore, squarylium chromophore, Talon chromophore, and the like. Among them, a triarylmethane chromophore, a cyanine chromophore, a xanthophore, a polymethine chromophore, and an azo chromophore are preferable, and a triaryl methane chromophore and a cyanine chromophore are more preferable. As the cationic chromophore, in the color index (CI .; published by The Society of Dyers and Colourists), the cation portion of the dye classified as C. I. Basic may be used.

The counter anion is not particularly limited, and examples thereof include the anions described in paragraph [0034] of Japanese Laid-Open Patent Publication No. 2015-129263, among which sulfonate anion, imide anion and carboxylate anion are preferable, An imide anion is more preferable, and a sulfonyl imide anion is more preferable.

Examples of the anionic chromophore include triarylmethane chromophore, polymethine chromophore, azo chromophore, diarylmethane chromophore, quinoneimine chromophore, anthraquinone chromophore, phthalocyanine chromophore, xanthone chromophore, squarylium chromophore, quinophthalone chromophore, etc. . Among them, a triarylmethane chromophore, an azo chromophore, a phthalocyanine chromophore, or a triarylmethane chromophore having at least one substituent selected from -SO ₃ ^- and -CO ₂ ^- are preferable, and triarylmethane chromophore, azo chromophore, phthalocyanine chromophore, Xanthate chromophore is more preferable. As the anionic chromophore, an anion portion of the dye classified as CI acid in the color index may be used.

Examples of the counter cation include an ammonium cation, a phosphonium cation, a sulfonium cation, an iodonium cation, and a diazonium cation. Among these, an ammonium cation and a phosphonium cation are preferable, and an ammonium cation is more preferable.

When a pigment is used as a colorant, it can be used together with a dispersant and a dispersion aid if desired. As the dispersing agent, for example, a basic dispersing agent and an acidic dispersing agent can be appropriately selected. Here, in the present specification, the term "basic dispersant" refers to a pigment having a basic group as a adsorption site. The "acidic dispersant" refers to a pigment adsorbing site having an acidic group, with the proviso that component (A) is excluded. Among them, an acidic dispersant is preferable from the viewpoint of improvement of storage stability. When a basic dispersing agent is used, the content of the basic dispersing agent is preferably 20% by mass or less, more preferably 5% by mass or less, and more preferably 1% by mass or less based on the total amount of the dispersing agent from the viewpoint of storage stability desirable.

The dispersant may be selected from known materials. Examples of the basic dispersant include Solsperse 11200, Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 16000, Solsperse 17000, Solsperse 18000, Sol Sprass 32000, Sol Sprass 32000, Sol Sprass 33000, Sol Sprass 34000, Sol Sprass 35000, Sol Sprass 35000, Sol Sprass 32000, Sol Sprass 32000, (Manufactured by RUBY RESIN CO., LTD.), DISPERBYK-3 (manufactured by RUBYRESOL CO., LTD.), And SUN SPRUS 37500, SOR SPARSE 38500, SOR SPARSE 39000, SOR SPARSE 56000, SOR SPARSE 71000, SOR SPARS 76400, SOR SPARS 76500, SOR SPARSE X300, DISPERBYK-168, DISPERBYK-167, DISPERBYK-168, DISPERBYK-163, DISPERBYK-163, DISPERBYK-166, DISPERBYK- DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBYK DISPERBYK-2064, DISPERBYK-2050, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164, and BYK-9077 (manufactured by BICKEMISA), azisper PB821, PB822, PB823, PB824, and PB827 (manufactured by Ajinomoto Fine Techno Co., Ltd.).

Further, as the acidic dispersing agent, there were used Sol Sparse 3000, Sol Spurs 21000, Sol Spurs 26000, Sol Spurs 36600, Sol Spurs 41000, Sol Spurs 41090, Sol Spurs 43000, Sol Spurs 44000, Sol Spurs 46000, Sol Spurs 47000, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-2096, BYK-P104, BYK-P104S, BYK-P105, BYK- Manufactured by BICKEMIS Co., Ltd.).

The content of the [C] coloring agent in the photosensitive composition can be appropriately selected according to the application or the like. However, from the viewpoint of forming a pixel excellent in luminance, heat resistance and solvent resistance, or a black matrix and black spacer excellent in light- Preferably 5 to 70 mass%, and more preferably 10 to 60 mass%.

When the dye as the [C] colorant is contained, the content of the dye is preferably 5% by mass or more, more preferably 20% by mass or more, more preferably 50% by mass or more, By mass or more, and particularly preferably 90% by mass or more. As described above, since dyes generally have inferior heat resistance and the like, it has been common that it is difficult to heat a coating film formed using a photosensitive composition containing a dye to a post-baking temperature of 200 to 250 캜, The photosensitive composition can form a cured film having excellent solvent resistance even after post-baking at a low temperature. Therefore, the photosensitive composition of the present invention can be suitably used for producing various color filters even if the content of the dye is large.

- [D] Curing accelerator

The [D] curing accelerator is not particularly limited as long as it is a curing accelerator having a hydrogen donor and is capable of exhibiting catalytic activity with respect to the alicyclic epoxy group in the component [A]. Examples of the [D] curing accelerator include a compound having a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group or the like, or a carbonic acid anhydride. Among them, a compound having a phenol group, a compound having a silanol group, a compound having a carboxyl group, and a carbonic acid anhydride are preferable, and a compound having a carboxyl group, a compound having a silanol group, and a carbonic acid anhydride are more preferable.

As the compound having a carboxyl group, a compound having two or more carboxyl groups is preferable. Examples of such compounds include anhydrides of unsaturated dicarboxylic acids and anhydrides of polyvalent carboxylic acids having three or more valences. Examples of the unsaturated dicarboxylic acid and trivalent or more polyvalent carboxylic acid include the same ones described in the above-mentioned (a2) polymer and (a1) polymer. Of these, anhydrides of polyvalent carboxylic acids having three or more hydroxyl groups are preferable.

Examples of the compound having a phenol group include compounds represented by the following formulas.

Examples of the silanol group-containing curing accelerator include trimethylsilanol, triethylsilanol, 1,1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis (hydroxydimethylsilyl) Benzene, and a silanol compound such as a compound represented by the following formula (9).

(In the formula (9)

R ²² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom, a halogen atom, NO ₂ or CN, and R ²² may be bonded to a phenyl group as -COOR ²⁴ or SO ₂ OR ²⁴ . Provided that R ²⁴ is an alkyl group having 1 to 4 carbon atoms.

R ²³ represents an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group.

l and n are independently an integer of 1 to 3;

m is an integer of 0 to 2; However, l + n + m satisfies the condition of 4.

v is an integer of 0 to 5; Provided that when plural R &lt; ²² &gt; s are present, plural R &lt; ²² &gt; s may be the same or different.

Examples of the alkyl group having 1 to 4 carbon atoms according to R ²² to R ²⁴ include a methyl group, an ethyl group and a propyl group. The alicyclic hydrocarbon group according to R ²³ is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms.

The silanol group-containing curing accelerator is preferably a compound represented by the formula (9), n is 2 or 3, R ²² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom, (Compounds represented by the following formulas (9-1) to (9-8)), more preferably n is 3, and R ²² is an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydrogen atom or a fluorine atom (9-1) to (9-4) are more preferable, and compounds represented by the following formulas (9-1) and (9-2) are even more preferable.

Examples of the silanol group-containing curing accelerator include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, trimethylisobutoxysilane, trimethyl-1-methyl But are not limited to, propoxysilane, trimethylbutoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, di But are not limited to, phenyldimethoxysilane, diphenylmethylethoxysilane, methylphenyldiethoxysilane, methyldimethoxysilane, trimethoxysilane, triethoxysilane, dimethylethoxysilane, diethoxysilane, tetramethoxysilane, vinyltrimethoxy Silane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, ethyltrimethoxysilane, methyldiethoxysilane, butyltrimethoxysilane, trimethylphenoxysilane, trimethyl-3-hydroxy But are not limited to, phenoxysilane, methyl-2-hydroxyphenoxytrisilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, trimethylcyclohexyloxysilane, allyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane , Hexyloxytrimethylsilane, propyltriethoxysilane, hexyltrimethoxysilane, dimethylphenylethoxysilane, tripropylmethoxysilane, methyltripropoxysilane, octyloxytrimethoxysilane, benzyltriethoxysilane, di (Trimethylsiloxy) benzene, 1,3-bis (trimethylsiloxy) benzene, 1,4-bis (trimethylsiloxy) benzene, 1,4-butanedimethoxy silane, triphenylmethoxy silane, And hydrolytic condensation products such as bis (trimethylsiloxy) benzene, 1,3-dimethoxytetramethyldisiloxane, and 1,3-diethoxytetramethyldisiloxane.

Further, with respect to the compound having a phenol group and the curing accelerator containing a silanol group, the phenol group or the silanol group may be protected with, for example, a protecting group represented by the following formula. By introducing a protecting group, the storage stability at room temperature can be improved while maintaining the catalytic activity.

The content of the [D] curing accelerator in the photosensitive composition is preferably 0.5 to 70 parts by mass, more preferably 0.5 to 50 parts by mass, further preferably 1 to 20 parts by mass, per 100 parts by mass of the component [A].

- [E] polymerizable compound -

In the present specification, the [E] polymerizable compound means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenic unsaturated group and an N-alkoxymethylamino group. As the [E] polymerizable compound, a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.

Specific examples of the compound having two or more (meth) acryloyl groups include a reaction product (multifunctional (meth) acrylate) of aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional (meth) acrylate modified with caprolactone, (Meth) acrylate having a hydroxyl group and a reaction product of a (meth) acrylate having a hydroxyl group and a polyfunctional isocyanate [a polyfunctional urethane (meth) acrylate] (A multifunctional (meth) acrylate having a carboxyl group).

Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol; And tri- or higher-valent aliphatic polyhydroxy compounds such as glycerin, trimethylol propane, pentaerythritol, and dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Penta (meth) acrylate, and glycerol dimethacrylate. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, anhydrous glutaric acid, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, anhydride pyromellitic acid, biphenyltetracarboxylic acid dianhydride , Tetrabasic acid dianhydride such as benzophenone tetracarboxylic acid dianhydride.

Examples of the caprolactone-modified polyfunctional (meth) acrylate include the compounds described in paragraphs [0015] to [0018] of Japanese Laid-Open Patent Publication No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include bisphenol A di (meth) acrylate modified with at least one member selected from ethylene oxide and propylene oxide, at least one member selected from ethylene oxide and propylene oxide Trimethylolpropane tri (meth) acrylate modified with at least one member selected from isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one member selected from the group consisting of ethylene oxide and propylene oxide At least one member selected from pentaerythritol tetra (meth) acrylate modified with at least one member selected from the group consisting of pentaerythritol tri (meth) acrylate, ethylene oxide and propylene oxide, modified with at least one member selected from ethylene oxide and propylene oxide Denatured by And dipentaerythritol hexa (meth) acrylate modified with at least one member selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide.

Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as basic skeletons, and also include melamine, benzoguanamine, or condensates thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N '', N '' - hexa (alkoxymethyl) N, N ', N'-tetra (alkoxymethyl) glycoluril, and the like.

Among them, the [E] polymerizable compound is preferably a reaction product of a trifunctional or higher aliphatic polyhydroxy compound with (meth) acrylic acid [multifunctional (meth) acrylate], caprolactone modified multifunctional (meth) N, N ', N', N ', N' '- hexa (alkoxymethyl) melamine, N, N', N ' -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the reactants of the tri- or higher aliphatic polyhydroxy compound and the (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Among the polyfunctional (meth) acrylates having a group, a reaction product of pentaerythritol triacrylate and succinic anhydride, a reaction product of dipentaerythritol pentaacrylate and succinic anhydride has a high cross-linking density in the molecule or in the molecule , And furthermore, the curability of the coating film can be further improved even at low temperature post-baking.

The content of the [E] polymerizable compound in the photosensitive composition is preferably 5 to 600 parts by mass, more preferably 5 to 60 parts by mass, per 100 parts by mass of the component [A], in the case of constituting the colored photosensitive composition comprising the [C] 20 to 400 parts by mass. The content of the [E] polymerizable compound in the case of constituting the photosensitive composition containing no [C] colorant is usually from 10 to 500 parts by mass, preferably from 50 to 300 parts by mass, per 100 parts by mass of the polymer [A] Mass part. With this structure, the cross-linking density in the intermolecular or molecular interior is further increased, so that the curing property of the coating film can be further improved even at low temperature post-baking.

- [F] metal chelate compound -

The [F] metal chelate compound acts as a catalyst to accelerate the crosslinking reaction, and can form a cured film having excellent adhesion to the base film and film hardness even at a low temperature and a short time of heat treatment.

Examples of the [F] metal chelate compound include a zirconium compound, a titanium compound, and an aluminum compound.

The structures of the zirconium compound, the titanium compound and the aluminum compound can be represented by, for example, the following formulas (10-1) to (10-4), respectively.

(Of the formulas (10-1) to (10-3)

R ¹³ , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁹ and R ²⁰ independently represent an alkyl group, an aryl group, a cycloalkyl group or an alkoxy group having 1 to 6 carbon atoms,

R ¹⁵ , R ¹⁸ and R ²¹ independently represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an aryl group, a cycloalkyl group or an alkoxy group,

R ^A represents a hydrogen atom or a methyl group,

p and p 'independently represent an integer of 0 to 3,

p "represents an integer of 0 to 2. However, R ¹³ ~R ²¹ is, in the case where plural, respectively, a plurality of R ¹³ ~R ²¹ is may be each the same or different.

In Equation (10-4)

R ^B represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, a cycloalkyl group or an alkoxy group,

Ar represents an aryl group. However, R ^B, and Ar is, in the case where plural, respectively, a plurality of R ^B and Ar may be the same or different, respectively.

R ^e represents an alkyl group, an aryl group, a cycloalkyl group or an alkoxy group having 1 to 6 carbon atoms,

p '''represents an integer of 0 to 2; However, if a plurality of R ^e, a plurality of R ^e may be the same or different.

Examples of the alkyl group having 1 to 6 carbon atoms include an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group and an n-pentyl group. Examples of the alkoxy group having 1 to 16 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec- , Stearyloxy group, and the like. As the aryl group, for example, a phenyl group and the like can be mentioned. Examples of the cycloalkyl group include a cyclohexyl group and the like. Examples of the aryl group include a benzyl group and the like.

Examples of the aluminum compound include diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetyl acetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris Ethyl acetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate-bis (ethyl acetoacetate) aluminum, and compounds represented by the following formulas.

Examples of the zirconium compound include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, Propyl acetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, and the like.

Examples of the titanium compound include titanium compounds such as diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetate) titanium, diisopropoxybis (acetylacetone) titanium and the like .

Among them, an aluminum compound is preferable as the [F] metal chelate compound, and diisopropoxyethylacetoacetate aluminum, tris (acetylacetonate) aluminum and tris (ethyl acetoacetate) aluminum are more preferable.

The [F] metal chelate compound may contain one kind or two or more kinds. As the [F] metal chelate compounds, partial hydrolyzates of these metal chelate compounds may also be used.

The content of the [F] metal chelate compound in the photosensitive composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the [A] component. By setting the content of the [F] metal chelate compound to the above-specified range, the crosslinking reaction is promoted, so that a cured film can be formed even at a low temperature and a short time of heat treatment, and storage stability can be well maintained.

- [G] Solvent -

The photosensitive composition of the present invention contains [A] and [B] components and optionally other components, but is generally formulated as a liquid composition by blending an organic solvent.

The organic solvent can be appropriately selected and used as long as it is dispersible or dissolves the [A] and [B] components constituting the photosensitive composition or other components, does not react with these components, and has appropriate volatility. [G] The solvent may contain one kind or two or more kinds.

As such an organic solvent, for example,

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono- Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol and cyclohexanol;

Ketoalcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate;

Glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate and 1,6-hexanediol diacetate;

Alkoxycarbonic acids such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate and 3-methyl- ester;

Amyl acetate, n-butyl acetate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, propyl acetate, isopropyl acetate, n- , Fatty acid alkyl esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone,

And the like.

Among them, as the [G] solvent, (poly) alkylene glycol monoalkyl ether and (poly) alkylene glycol monoalkyl ether acetate are preferable from the viewpoint of solubility, pigment dispersibility, coating property and the like. When the [G] solvent is used in combination, it is preferable to use at least a mixture of (poly) alkylene glycol monoalkyl ether and (poly) alkylene glycol monoalkyl ether acetate.

The content of the [G] solvent in the photosensitive composition is not particularly limited, but in the case of the colored photosensitive composition comprising the [C] colorant, the total concentration of each component except for the [G] solvent of the photosensitive composition is preferably 5 to 50 mass %, More preferably 10 to 40% by mass. In the case of a photosensitive composition containing no [C] coloring agent, the total amount of each component excluding the solvent of the photosensitive composition is preferably from 10 to 75 mass%, more preferably from 15 to 70 mass% More preferable. By such an embodiment, a photosensitive composition having good coating properties and storage stability can be obtained.

-additive-

The photosensitive composition of the present invention may contain various additives, if necessary.

Examples of the additive include fillers such as glass and alumina; High molecular compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); Surfactants such as fluorine-based surfactants and silicone-based surfactants; Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like Adhesion promoters; Thermal radical initiators such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile); A thermal acid generator having a structure represented by the following formula (11); Di-t-butylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl- -2,4,8,10-tetraoxaspiro [5.5] undecane and thiodiethylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] ; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; An anti-aggregation agent such as sodium polyacrylate; Amino-1-pentanol, 3-amino-1,2-propane, 3-amino-1-pentanol, Diol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like; A developing agent such as mono [2- (meth) acryloyloxyethyl succinate], mono [2- (meth) acryloyloxyethyl] phthalate, and ω-carboxypolycaprolactone mono (meth) .

[In the formula (11)

R ^b and R ^c independently represent a monovalent hydrocarbon group,

R ^d represents an alkyl group, an alkoxycarbonyl group or an alkoxycarbonylalkyl group having 1 to 12 carbon atoms.

The monovalent hydrocarbon groups according to R ^b and R ^c have the same meanings as Y in the formulas (1-3) and (1-4), and specific examples thereof are as described above. Among them, the monovalent hydrocarbon group according to R ^b and R ^c is preferably an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and the alkyl group, alicyclic hydrocarbon group And a part or all of hydrogen atoms contained in the aryl group may be substituted with a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a 7,7-dimethyl-2-oxononorbornyl group. Specific examples thereof include the same ones as R ^a in the formula (8).

As the alkoxycarbonyl group according to R ^d , a C _1-4 alkoxycarbonyl group is preferable, and specific examples include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group and the like. have. As the alkoxycarbonylalkyl group, an alkoxycarbonylalkyl group having a total carbon number of 3 to 9 is preferable, and specific examples thereof include methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group , An isopropoxycarbonylethyl group, a phenoxycarbonylmethyl group, and a phenoxycarbonylethyl group. Among them, R ^d is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

The photosensitive composition of the present invention can be prepared by an appropriate method. For example, the components [A] and [B] can be prepared by mixing and dispersing the components together with a solvent or other components to be optionally added, using a bead mill, roll mill or the like.

[Cured film and manufacturing method thereof]

The cured film of the present invention is formed using the photosensitive composition of the present invention and includes the steps (1) to (4). Examples of the cured film include a bank (partition wall) defining a region for forming each color pixel, an interlayer insulating film, a planarizing film, and a light emitting layer used in a display element and a light receiving element, a black matrix, a spacer and a protective film. Examples of the display element include a color liquid crystal display element, an organic EL element, and an electronic paper. Examples of the light receiving element include a CCD image sensor and a CMOS image sensor.

- Process (1) -

Step (1) is a step of forming a coating film on the substrate by applying the photosensitive composition of the present invention.

<Substrate>

As the substrate, there can be mentioned a transparent substrate having a high transmittance with respect to visible light. Specific examples thereof include glass substrates such as borosilicate glass, aluminoborosilicate glass, alkali-free glass, quartz glass, synthetic quartz glass, soda lime glass and white sapphire; Examples of the substrate include resin substrates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyether sulfone, and polyimide.

Further, as the substrate, a substrate on which the light emitting element is mounted may be used. Examples of the light-emitting element include a solid light-emitting element such as a light-emitting diode, a semiconductor laser, and an organic EL light-emitting element, and the surface of the solid light-emitting element may be covered with a transparent resin or a sheet. As the substrate, the aforementioned transparent substrate is usually used, and it may be a glass substrate or a resin substrate. The bonding form of the light emitting element and the substrate is not particularly limited, and for example, a conductive paste, a thermally conductive sheet, a thermally conductive adhesive, a double-sided tape, solder, or the like can be appropriately selected.

Among them, a resin substrate and a substrate on which a light emitting element is mounted are preferable as the substrate because it is easy to enjoy the effect of the present invention.

The substrate may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum deposition or the like, For light emission, a transparent electrode made of indium oxide, tin oxide, or the like may be formed. Further, a light-shielding layer (black matrix) may be formed on the substrate so as to partition a portion forming the pixel. Examples of the light-shielding layer include inorganic films such as chromium and titanium nitride, multilayer films of chromium / chromium oxide, and resin films in which a light shielding agent is dispersed. Further, a black radiation sensitive composition may be coated on a substrate, and a desired pattern may be formed by photolithography. The thickness of the light-shielding layer is usually 0.1 to 0.2 mu m.

<Application>

As a method of applying the photosensitive composition, a known method can be employed. For example, a spray coating method, a roll coating method, a rotation coating method (spin coating method), a slit die coating method, a bar coating method and the like can be given. From the viewpoint of obtaining a coating film having a uniform film thickness, , Slit die coating method is preferable.

After application, drying under reduced pressure can be carried out. The reduced-pressure drying is usually carried out at room temperature for about 1 to 15 minutes, preferably for 1 to 10 minutes, usually until 50 to 200 Pa is reached. The thickness of the coated film is usually 0.6 to 8 占 퐉, preferably 1.2 to 5 占 퐉, after the drying.

As another example of forming a coating film of a photosensitive composition on a substrate, an inkjet method may be employed. For example, the methods described in Japanese Unexamined Patent Application Publication No. 7-318723, Japanese Unexamined Patent Application Publication No. 2000-310706, . In this method, a partition wall serving also as a shielding function is first formed on a substrate, and then the radiation sensitive composition is ejected by the ink jet apparatus in this partition wall. Thereafter, drying is performed under reduced pressure to evaporate the solvent to form a film.

As another example of forming a coating film of a photosensitive composition on a substrate, a dry film method can be employed. For example, a method described in Japanese Laid-Open Patent Publication No. 9-5991 can be used. In this method, a photosensitive composition is coated on a film-shaped support, and the film is prebaked to evaporate the solvent, thereby producing a dry film on which a photosensitive composition layer is formed on the support. Then, the support on which this photosensitive composition layer is formed is laminated to the substrate using a laminator. Thereafter, the photosensitive composition layer is peeled from the support, and the photosensitive composition layer is transferred onto the substrate. The method of applying the photosensitive composition on the support, and the method and conditions of prebaking are the same as described above.

- Process (2) -

Step (2) is a step of irradiating the coating film obtained in the step (1) with radiation.

In step (2), usually, at least a part of the coating film obtained in step (1) may be exposed through a photomask having a predetermined pattern, or may be subjected to scanning exposure. The pattern shape on the photomask is not particularly limited, and a pattern shape according to the intended use is used.

Examples of radiation include ultraviolet rays of g line, h line, i line and j line, and ultraviolet rays of g line, h line, i line and j line are preferable. In the spectral distribution, the peak at 436 nm is g-line, the peak at 405 nm is h-line, the peak at 365 nm is i-line, and the peak at 313 nm is j-line.

As the light source, various visible and non-visible lasers such as ultrahigh pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halides and the like can be used.

The exposure dose is usually 1 to 1,000 mJ / cm 2, but is preferably 5 to 500 mJ / cm 2, more preferably 10 to 200 mJ / cm 2, and still more preferably 30 to 100 mJ / cm 2 in order to enhance the desired effect.

- Process (3) -

Step (3) is a step of developing the coating film obtained in the step (2).

The development is carried out by dissolving and removing the exposed portion in the case of the positive type and the non-visible portion in the case of the negative type, using the developer.

As the developing solution, any of those which dissolve the exposed portion in the case of the positive type and do not dissolve the non-visible portion, and those which dissolve the non-visible portion and not the exposed portion in the case of the negative type, can be used. For example, a combination of various organic solvents and an aqueous alkali solution may be used. Among them, an aqueous alkali solution is preferable. Examples of the alkali aqueous solution include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7- undecene, Cyclo [4.3.0] -5-nonene and the like. A water-soluble organic solvent such as methanol or ethanol, a defoaming agent, or a surfactant may be added to the developer in an appropriate amount.

As the developing method, for example, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (drilling) developing method and the like can be applied. The development conditions can be, for example, 5 to 300 seconds at room temperature.

When an alkaline aqueous solution is used as the developing solution, it is usually rinsed with water after development. After the cleaning, for example, the coated film may be air-dried with compressed air or compressed nitrogen.

- Process (4) -

Step (4) is a step of heating the coating film obtained in step (3) at 70 to 180 캜.

The step (4) is a step of post-baking, and the post-baking is carried out by heating the patterned coated film at 70 to 180 캜, but from the standpoint of curability, solvent resistance and adhesion to the substrate, The heating temperature can be set in accordance with the application such as 80 to 120 ° C and 120 to 180 ° C. The heating time can be appropriately set according to the heating temperature, but is usually 5 to 120 minutes, preferably 30 to 100 minutes at a low temperature of 80 to 120 占 폚.

Thus, the cured film of the present invention can be produced.

The film thickness of the cured film is usually 0.5 to 5 占 퐉, preferably 1 to 4 占 퐉. The obtained cured film is excellent in solvent resistance and adhesion to the substrate, and can effectively suppress peeling.

In the case of forming each color pixel constituting the color filter, the photosensitive composition of the present invention containing a blue, green or red coloring agent is used for the above-mentioned method of forming a cured film of the present invention, , A green pixel pattern and a red pixel pattern are sequentially formed on the same substrate. Thereby, a color filter in which pixel patterns of three primary colors of blue, green, and red are arranged on a substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

Further, in the case of a liquid crystal display element, for example, (a) an interlayer insulating film is formed on one surface side of a first substrate, (B) a step of forming a liquid crystal alignment film on the outer surface side of the interlayer insulating film and one surface side of the second substrate, (c) a step of forming a liquid crystal alignment film on the first substrate and the second substrate And (d) a step of forming a liquid crystal layer by light irradiation on the polymerizable liquid crystal composition. As a result, the photosensitive composition of the present invention is used for forming an interlayer insulating film , And can be formed according to the above-described method of forming a cured film of the present invention. The formation on one surface side or the outer surface side means not only the formation in direct contact with the surface but also the formation in the other surface through another layer.

[Display device]

The display element of the present invention comprises the cured film of the present invention.

Examples of the display element include a color liquid crystal display element, an organic EL display element, and an electronic paper. The color liquid crystal display element having the cured film of the present invention may be of a transmissive type or of a reflective type and may adopt a suitable structure. For example, a color filter is formed on a substrate different from a substrate on which a thin film transistor (TFT) is disposed, and a substrate on which a driving substrate and a color filter are formed faces the liquid crystal layer A substrate on which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate on which an ITO (indium oxide doped with indium) electrode is formed, But it is also possible to adopt a structure in which opposing faces are used. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a liquid crystal display element which is bright and has high precision can be obtained. When adopting the latter structure, the black matrix or the spacer may be formed on either the substrate on which the color filter is formed or the substrate on which the ITO electrode is formed. The cured film of the present invention can also be applied as an interlayer insulating film constituting a driving substrate on which thin film transistors (TFTs) are arranged.

[Light Emitting Element]

The light emitting element of the present invention comprises the cured film of the present invention.

The light emitting device of the present invention can adopt a suitable structure. For example, in an organic EL light emitting device having a structure in which a transparent conductive layer made of a transparent electrode, a light emitting layer, and a cathode layer made of a metal electrode are stacked , A protective film, an insulating film, and a light-emitting wavelength selecting member. The light emitting layer can be formed using the photosensitive composition of the present invention in accordance with the above-described method for forming a cured film of the present invention.

[Light receiving element]

The light receiving element of the present invention comprises the cured film of the present invention.

The light receiving element of the present invention can employ a suitable structure. For example, the color cured film of the present invention may be a color filter constituting a solid-state image pickup element and combined with a photodiode to form an image pickup element such as a solid- Can be configured. Further, by using the cured film of the present invention as an infrared light transmission filter and combining it with a photodiode, it is possible to constitute a pixel for infrared light detection.

[Example]

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

Synthesis of polymer

Polymer Synthesis Example 1

To a flask equipped with a cooling tube and a stirrer, 80 parts by mass of propylene glycol monomethyl ether acetate was charged and replaced with nitrogen. The mixture was heated to 80 DEG C, and 50 parts by mass of propylene glycol monomethyl ether acetate, 12 parts by mass of methacrylic acid, 88 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate, and 2,2'-azobis And 6 parts by mass of 2,4-dimethylvaleronitrile) was added dropwise over 2 hours, and the temperature was maintained and maintained for 1 hour. Thereafter, the temperature of the reaction solution was raised to 90 占 폚 and further polymerized for 1 hour to obtain a solution containing the polymer (a1-1). This was subjected to reprecipitation using diisoamyl ether, and the precipitate was washed with n-hexane and then dried to obtain a solid (powder) of the polymer (a1-1). The polymer (a1-1) corresponds to the (a1) polymer.

Polymer Synthesis Examples 2 to 5 and 8

Polymer (a1-2), polymer (? 1) and polymer (a2-1) were obtained in the same manner as in Polymer Synthesis Example 1, except that the kinds and amounts of the monomers used were changed as shown in Table 1, ), A polymer (a2-2) and a polymer (? 2). The polymer (a1-2) corresponds to the polymer (a1), and the polymer (a2-1) and the polymer (a2-2) correspond to the polymer (a2). On the other hand, the polymer (? 1) and the polymer (? 2) do not correspond to any of the polymer (a1), the polymer (a2) and the polymer (a3).

Polymer Synthesis Example 6

In a nitrogen atmosphere, 121 parts by mass of? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane was added to a three-necked flask, and 100 parts by mass of ethoxypropanol was added to dissolve the mixture. The resulting mixed solution was stirred by a magnetic stirrer While it was heated to 70 ° C. To this solution was added 40.4 parts by mass of an oxalic acid aqueous solution containing 1% by mass of oxalic acid, and the reaction was carried out at 70 占 폚 for 3 hours. Thereafter, water, methanol and ethoxypropanol were distilled off under reduced pressure to obtain a solid of the polymer (a3-1). The polymer (a3-1) corresponds to the (a3) polymer.

Polymer Synthesis Examples 7 and 9

Polymer (a3-2) and polymer (3) were obtained in the same manner as in Polymer Synthesis Example 6, except that the kinds and amounts of the monomers used were changed as shown in Table 1. The polymer (a3-2) corresponds to the (a3) polymer. On the other hand, the polymer (? 3) does not correspond to any of the (a1) polymer, (a2) polymer and (a3) polymer.

In Table 1, &quot; monomer A &quot; is 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate, and the compound represented by the following formula (4-1) and the compound represented by the following formula (Molar ratio) mixture of compounds.

Synthesis of dispersant

Dispersant Synthesis Example 1

80 parts by mass of n-butyl acrylate, 60 parts by mass of methyl methacrylate, 20 parts by mass of methacrylic acid, and 20 parts by mass of car lens MOI-BM (manufactured by Showa Denko Kogyo Co., Ltd.) were added to a reaction vessel equipped with a stirrer, a thermometer, 20 parts by mass) and 20 parts by mass of ETERNACOLL OXMA (manufactured by Ube Chemical Industries, Ltd.) were charged and substituted with nitrogen gas. After heating the reaction vessel to 80 캜, a solution obtained by mixing 14 parts by mass of 2-mercapto-2-methyl-1,3-propanediol with 0.1 part by mass of 2,2'-azobisisobutyronitrile was placed in a reaction vessel And reacted for 10 hours. It was confirmed that 95% was reacted by the measurement of the solid content. Next, 39 parts by weight of 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (trade name BPAF (manufactured by JFE Chemical Co., Ltd.)), 40 parts by weight of C-1015N (bifunctional polycarbonate polyol, 106 parts by mass of L-polyol C-1015N (having a hydroxyl value of 112 mg KOH / g, manufactured by Kuraray Co., Ltd.), 33 parts by mass of trimellitic anhydride, 392 parts by mass of cyclohexanone and 1,8-diazabicyclo - [5.4.0] -7-undecene was added, and the reaction was carried out at 100 ° C for 7 hours. The acid value measurement confirmed that at least 98% of the acid anhydride was half-esterified, and the reaction was terminated. Thus, a dispersant A having an amine value of 0 mg KOH / g, an acid value of 73 mg KOH / g and a weight average molecular weight of 25,000 was obtained.

Dispersant Synthesis Example 2

62.6 parts by mass of 1-dodecanol, 287.4 parts by mass of? -Caprolactone and 0.1 part by mass of monobutyltin (IV) oxide as a catalyst were fed into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a stirrer, After substitution, the mixture was heated and stirred at 120 DEG C for 4 hours. After confirming that 98% of the reaction was carried out by measuring the solid content, 73.3 parts by mass of pyromellitic anhydride was added and the reaction was carried out at 120 ° C for 2 hours. The acid value measurement confirmed that at least 98% of the acid anhydride was half-esterified, and the reaction was terminated. Thus, a dispersant B having an amine value of 0 mg KOH / g and an acid value of 49 mg KOH / g was obtained.

Preparation of pigment dispersion

Pigment dispersion Preparation Example 1

As a colorant, C.I. 12 mass parts of Pigment Violet 23 as a dispersant, 12 mass parts of BYK-LPN21116 (solid content concentration of 40 mass%, amine value 29 mgKOH / g, acid value 0 mgKOH / g, manufactured by BYK) 12.5 parts by mass of a solution (solid content concentration: 40% by mass) as a solvent, 12 parts by mass of methoxypropanol as a solvent, and 51.5 parts by mass of propylene glycol monomethyl ether acetate, -1) was prepared.

Pigment dispersion Preparation Example 2

Pigment Dispersion A pigment dispersion (p-2) was prepared in the same manner as in Preparation Example 1 except that a mixture of 3.36 parts by mass of Dispersant A and 1.44 parts by mass of Dispersant B was used in place of 12 parts by mass of BYK-LPN21116. .

Preparation of dye solution

Preparation of dye solution Example 1

10 parts by mass of the dye (1) and 90 parts by mass of propylene glycol monomethyl ether were mixed to prepare a dye solution (C1). The dye (1) is as described below.

Preparation of dye solution Examples 2 to 5

The dye solutions (C2) to (C5) were prepared in the same manner as in Preparation Example 1 of the dye solution except that the dyes (2) to (5) were used in place of the dye (1). The dyes (2) to (5) are as described below.

Dye (1): A triarylmethane dye, which is an acrylic polymer having a repeating unit having a triarylmethane skeleton, obtained according to Synthesis Example 6 of JP-A No. 2016-505655.

Dye (2): Compound represented by the formula (1-8) obtained according to Synthesis Example 3 of JP-A-2013-050693. (Xanthine dye)

Dye (3): &quot; Polymer F &quot; described in Table 1 of JP-A No. 2014-194007 (an acrylic polymer having a repeating unit having an imide anion and a cyanine dye as a conditioning compound of CI Basic Red 12)

Dye (4): "Prepared compound ZC-38" described in Table 2 of JP-A No. 2015-118268. (Cyanine dye having imide anion)

Dye (5): The dyestuff dye represented by the following formula (12)

Preparation and evaluation of photosensitive composition

Example 1

As the component [A], a polymer (a1-1), a polymer (a2), a polymer (a2-1), and a polymer (B) , 5 parts by mass of &quot; Compound No. 42 &quot; described in &quot; Compound No. 42 &quot; , 25 parts by mass of a mixture of hexaacrylate and dipentaerythritol pentaacrylate), 25 parts by mass of Aronix M-510 (manufactured by Toagosei Co., Ltd.), and 200 parts by mass of Megapac F-554 , And 0.5 parts by mass of a photopolymerization initiator (trade name, manufactured by Shimadzu Seisakusho Co., Ltd.) and Z mass parts of a mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether = 80/20 (volume ratio) S-1) was prepared. At this time, the values of W, X, Y, and Z were set so as to satisfy the following conditions A1 to A4. In the present embodiment, X = W = 25 parts by mass, Y = 21.1 parts by mass, and Z = 717 parts by mass.

Condition (A1): The polymer (a1-1) as the polymer (a1): the polymer (a2-1) as the polymer (a2) in the photosensitive composition (S-1) was 50:50 (by mass ratio).

Condition A2: The total content of the polymer and the [E] polymerizable compound in the photosensitive composition (S-1) is 100 parts by mass. The term &quot; polymer &quot; refers to the component [A] and other polymers (excluding the [A] component and the dispersant).

Condition A3: The solid content concentration in the photosensitive composition (S-1) is 16 mass%.

Condition A4: The content ratio of the [C] coloring agent in the photosensitive composition (S-1) is 20% by mass.

Evaluation of storage stability

The viscosity immediately after the preparation of the photosensitive composition (S-1) was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Next, the photosensitive composition (S-1) was filled in a light-shielding glass container and allowed to stand at 5 캜 for 14 days in a sealed state, and then the viscosity was measured again using an E-type viscometer (manufactured by Tokyo Keiki). The rate of increase in viscosity after storage for 14 days against viscosity immediately after preparation was calculated. The evaluation criteria are as follows, and the results are shown in Table 2.

(Evaluation standard)

○: Growth rate less than 5%

Δ: Increase rate from 5% to less than 10%

X: Increase rate of 10% or more

Evaluation of Developability

The resulting photosensitive composition (S-1) was coated on the surface of a glass substrate using a spin coater, and then dried under reduced pressure at room temperature to form a coating film having a thickness of 2.5 탆. Subsequently, the coating film on the substrate was exposed to light at an exposure dose of 600 J / m &lt; 2 &gt; through a 90 mu m line-and-space photomask using a high-pressure mercury lamp. Thereafter, a shower phenomenon was carried out by discharging a 0.04 mass% aqueous potassium hydroxide solution at 23 占 폚 to a coating film on the substrate at a developing pressure of 1.5 kgf / cm2 (nozzle diameter of 1 mm). Thereafter, it was washed with ultra pure water and air dried. Post baking was performed at 100 占 폚 for 30 minutes to form a 90 占 퐉 stripe-shaped cured film pattern on the substrate.

Here, in the shower phenomenon, the time required for the development of the unexposed portion was measured, and the evaluation was made based on the following evaluation criteria.

(Evaluation standard)

◎: The time required for development is less than 45 seconds

○: The time required for development is 45 seconds or more but less than 60 seconds

B: Time required for development is 60 seconds or more and less than 120 seconds

X: Even after developing for 120 seconds, a residual film can be confirmed on the unexposed portion

Evaluation of solvent resistance

The photosensitive composition (S-1) was applied on a soda glass substrate having a SiO ₂ film formed on its surface to prevent elution of sodium ions using a spin coater, and then dried under reduced pressure at room temperature to obtain a coating film .

Subsequently, using a high-pressure mercury lamp, the coating film was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 600 J / m 2 through a photomask. Subsequently, a developer comprising 0.04 mass% potassium hydroxide aqueous solution at 23 캜 was ejected onto the substrate at a developing pressure of 1.5 kgf / cm 2 (nozzle diameter of 1 mm) for 120 seconds. Thereafter, this substrate was washed with ultrapure water, air-dried, and further baked in a 100 ° C clean oven for 30 minutes to form a rectangular pattern on the substrate. The chromaticity coordinate value (x, y) and the magnetic pole value (Y) in the CIE colorimetric system in the C light source and in the 2-degree field of view were measured for this rectangular pattern using a color analyzer (MCPD2000 manufactured by Otsuka Denshi Co., .

Next, the substrate was immersed in propylene glycol monomethyl ether acetate at 80 캜 for 3 minutes. The chromaticity coordinate value (x, y) and the magnetic pole value (Y) in the CIE colorimetric system in the C light source and in the 2-degree field of view were measured using a color analyzer (MCPD2000 manufactured by Otsuka Denshi Co., Ltd.) ) Were measured. The color change before and after the immersion, that is,? E ^* ab was calculated and evaluated according to the following criteria. The results are shown in Table 2. The smaller the value of? E ^* ab, the better the solvent resistance.

(Evaluation standard)

?: The value of? E ^* ab is 1.0 or less

?: The value of? E ^* ab is greater than 1.0 and not more than 2.0

DELTA: value of DELTA E ^* ab is greater than 2.0 and not more than 3.0

×: value of ΔE ^* ab is greater than 3.0

Examples 2 to 19, 23 to 24 and Comparative Examples 1 to 6

A photosensitive composition was prepared in the same manner as in Example 1 except that the kind and amount of each component in Example 1 were changed as shown in Table 2, and evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

In Table 2, the numerical values in parentheses in the column of "Polymer (content of polymer)" (column) and "[C] colorant (content of colorant)" indicate the content ratio in the polymer and the content ratio in the colorant Mass ratio. The numerical values in parentheses in the "[F] metal chelate compound" column and the "[H] additive" column refer to the "[D] curing accelerator" (Parts by mass). The numerical value in the column "[G] solvent" represents the volume ratio of the mixed solvent. The amounts of the [A] component, the [C] colorant and the [G] solvent were determined so as to satisfy the conditions A2 to A4 similarly to the photosensitive composition (S-1) of Example 1 in these photosensitive compositions. Condition A1 differs for each photosensitive composition.

Example 20

(A3) as a polymer (A3-1), (B) a polymeric material (a2-2) as a component (A2) , 5 parts by mass of &quot; Compound No. 42 &quot;, [D] 5 parts by mass of trimellitic anhydride as a curing accelerator, and [E] 5 parts by mass of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol 25 parts by mass of Aronix M-510 (a mixture of lithol hexaacrylate and dipentaerythritol pentaacrylate), 25 parts by mass of Aronix M-510 (manufactured by Toagosei Co., Ltd.), and 200 parts by mass of Megafac F-554 , And 0.5 parts by mass of a photopolymerization initiator (trade name, manufactured by Mitsubishi Chemical Co., Ltd.) and Z mass parts of a mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether = 80/20 (volume ratio) (S-20) was prepared. At this time, the values of W, X, and Z were set so as to satisfy the following conditions B1 to B3. In the present embodiment, X = 35 parts by mass, W = 15 parts by mass, and Z = 554 parts by mass.

Condition (B1): The polymer (a2-2) as the polymer (a2): the polymer (a3-1) as the polymer (a3-1) in the photosensitive composition (S-20) is 30:70 (by mass ratio).

Condition B2: The total content of the polymer and the [E] polymerizable compound in the photosensitive composition (S-20) is 100 parts by mass. The term &quot; polymer &quot; refers to the component [A] and other polymers (excluding the [A] component and the dispersant).

Condition B3: The solid content concentration in the photosensitive composition (S-20) is 16 mass%.

The storage stability and the developability of the photosensitive composition (S-20) were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2. Further, instead of evaluating the solvent resistance in Example 1, the following rigid pendulum test was carried out.

Rigid pendulum test

The photosensitive composition (S-20) was coated on an aluminum plate with a bar coater so that the application amount was 70 mg / dm 2, thereby forming a liquid film. A pendulum of FRE-160 type was placed on the liquid film, and the curing temperature was measured using a rigid pendulum viscoelasticity measuring device (RPT-3000 W type: A &amp; D company). More specifically, the curing temperature of the liquid film was set at the time when the logarithmic decrement of the shaking motion of the pendulum became 0.1 under the condition of a temperature rise temperature of 5 ° C / min. The evaluation criteria are as follows, and the results are shown in Table 2. The lower the temperature is, the more the photosensitive composition exhibits sufficient curability at post-baking at a lower temperature.

(Evaluation standard)

○: Curing temperature is below 100 ° C

?: Curing temperature is 101 to 150 占 폚 or less

X: Curing temperature was 151 DEG C or higher

Examples 21 to 22 and Comparative Example 7

A photosensitive composition was prepared in the same manner as in Example 20 except that the kind and the amount of each component in Example 20 were changed as shown in Table 2, and evaluation was carried out in the same manner as in Example 20. The evaluation results are shown in Table 2.

In Table 2, the parentheses in the "polymer (content ratio)" column are values indicating the content ratio in the polymer by mass ratio. The "[B] photosensitizer" refers to the content (parts by mass) in parentheses in the "[E] polymerizable compound" column and the "[H] additive" column. The term "[G] solvent" refers to the volume ratio of the mixed solvent. Also in these photosensitive compositions, the amounts of the [A] component and the [G] solvent were determined so as to satisfy the conditions B2 to B3 in the same manner as in the photosensitive composition (S-20) The condition B1 is different for each photosensitive composition.

In Table 2, the abbreviations are as follows.

B-1: "Compound No. 42" described in International Publication No. 2014/187170 pamphlet

· D-1: Anhydrous trimellitic acid

· D-2: tris (4-methylphenyl) silanol

E-1: KAYARAD DPHA (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

E-2: ARONIX M-510 (Toagosei Co., Ltd.)

· F-1: Tris (acetylacetonate) aluminum

G-1: Propylene glycol monomethyl ether acetate

G-2: Propylene glycol monomethyl ether

H-1: Megapack F-554 (manufactured by DIC Corporation)

H-2: Compound obtained in Example 1 of International Publication No. 2012/101245, represented by the following formula (13)

Claims (12)

The following components;
[A] a compound having an acidic functional group and an alicyclic epoxy group in the same molecule or different molecules, and
[B] Photosensitizer
As a photosensitive composition,
Wherein the component [A] comprises the following (a1) polymer, or the combination of the following (a2) polymer and the following (a3) polymer.
(a1) Polymer: A polymer having an acidic functional group and an alicyclic epoxy group in the same molecule
(a2) Polymer: A polymer having an acidic functional group and no alicyclic epoxy group
(a3) Polymer: A polymer having an alicyclic epoxy group and no acidic functional group The method according to claim 1,
Further comprising at least a dye as a [C] coloring agent, wherein the content of the dye is at least 5% by mass based on the total amount of the [C] coloring agent. The method according to claim 1,
Further comprising at least a dye as a [C] coloring agent, wherein the content of the dye is at least 90% by mass based on the total amount of the [C] coloring agent. The method according to claim 1,
Wherein the polymer (a1) to (a3) is a polymer selected from a polysiloxane and a (meth) acrylic polymer. The method according to claim 1,
Wherein the component [A] comprises a combination of the polymer (a2) and the polymer (a3), and the content ratio thereof is (a2) polymer: (a3) polymer = 20:80 to 80:20. The method according to claim 1,
Further, a photosensitive composition comprising at least one member selected from the group consisting of a curing accelerator having a [D] hydrogen donor, a [E] polymerizable compound and a [F] metal chelate compound. The method according to claim 6,
At least the [D] component,
Wherein the component [D] comprises at least one compound selected from the group consisting of a compound having a silanol group and an acid anhydride having a carboxyl group. A cured film which is a cured product of the photosensitive composition according to any one of claims 1 to 7. A display element comprising the cured film according to claim 8. A light emitting device comprising the cured film according to claim 8. A light-receiving element comprising the cured film according to claim 8. A process for producing a cured film, which comprises the following steps (1) to (4).
Process (1): A process for forming a coating film by applying the photosensitive composition described in any one of claims 1 to 7 on a substrate
Step (2): A step of irradiating the coating film obtained in the step (1) with radiation
Step (3): a step of developing the coating film obtained in the step (2)
Step (4): Step of heating the coating film obtained in the step (3) at 70 to 180 캜