JP7096772B2 - Water-soluble composition, pattern-forming agent, method for producing cured product using these, and cured product - Google Patents

Description

The present invention relates to a water-soluble composition, a pattern-forming agent, a method for producing a cured product using these, and a cured product. The present invention relates to a water-soluble composition, a pattern-forming agent, a method for producing a cured product using these, and a cured product.

Polyvinyl alcohol is used in various applications such as paints, inks, adhesives, and optical films. For example, Patent Document 1 proposes a resin composition having excellent gas barrier properties and water resistance, which contains a resin such as polyvinyl alcohol and a metal organic compound such as a titanium organic compound and a zirconium organic compound. Further, Patent Document 2 proposes a heat-sensitive recording material having excellent chemical resistance and sticking property, which contains acetacetyl-modified polyvinyl alcohol and a silane coupling agent having an amino group as a cross-linking agent. Further, Patent Document 3 proposes a method for producing a polyvinyl alcohol-based resin crosslinked product, which is obtained by cross-linking an acetoacetic ester group-containing polyvinyl alcohol-based resin with a glyoxylate, which has less discoloration with time due to ultraviolet rays and has excellent weather resistance. ing.

Japanese Unexamined Patent Publication No. 11-310712 Japanese Unexamined Patent Publication No. 2009-0398774 Japanese Unexamined Patent Publication No. 2013-028697

For applications such as pattern forming agents, inks, various resists, optical films for flat panel displays, coating materials and adhesives for optical films, curing with increasingly high-definition patterns and excellent heat resistance, water resistance, and moisture heat resistance. A water-soluble composition from which a product can be obtained is required. In such a situation, the water-soluble composition as proposed in Patent Documents 1 to 3 cannot always achieve both at a high level required by the market, and further improvement of the water-soluble composition is required. The current situation is that.

Therefore, an object of the present invention is a water-soluble composition, a pattern forming agent, a method for producing a cured product using these, and a cured product, which can obtain a cured product having a high-definition pattern and excellent heat resistance, water resistance, and moisture heat resistance. Is to provide.

As a result of diligent studies to solve the above problems, the present inventors have solved the above problems by using a water-soluble photosensitive polymer having a photosensitive group and a hydroxyl group and a water-soluble photosensitive polymer having a predetermined structure. We have found that we can do this, and have completed the present invention.

（一般式（Ｉ）中、＊は結合手を意味する。）で表される構成単位を有する化合物（Ｂ）、および架橋剤（Ｃ）を含有し、
前記化合物（Ｂ）が、下記一般式（ＩＩＩ）、

（一般式（ＩＩＩ）中、＊は結合手を意味する。）で表される構成単位を有する化合物であることを特徴とするものである。 That is, the water-soluble composition of the present invention is other than the water-soluble photosensitive polymer (A) having a photosensitive group and a hydroxyl group and the water-soluble photosensitive polymer (A), and has the following general formula (I).

(In the general formula (I), * means a bond), which contains the compound (B) having a structural unit represented by the compound (B) and the cross-linking agent (C).
The compound (B) has the following general formula (III),

(In the general formula (III), * means a bond), which is characterized by having a structural unit represented by the compound.

（一般式（ＩＩα）、（ＩＩβ）および（ＩＩγ）中、Ｙ^１、Ｙ^２およびＹ^３は、それぞれ独立に直接結合または２価の連結基を表し、Ｑ^１、Ｑ^２およびＱ^３は、それぞれ独立に感光基を表し、＊は結合手を意味する。）からなる群より選ばれる構成単位を一つ以上有することが好ましい。また、本発明の水溶性組成物においては、前記感光基は、スチルバゾリウム基、シンナモイル基、アクリル基、メタクリル基、アクリルアミド基またはメタアクリルアミド基であることが好ましい。さらに、本発明の水溶性組成物においては、前記水溶性感光重合体（Ａ）が、下記一般式（ＩＩδ）または（ＩＩε）、

（一般式（ＩＩδ）、（ＩＩε）中、Ａｎ^ｑ－はｑ価のアニオンを表し、ｑは１または２を表し、ｐは電荷を中性に保つ係数を表し、＊は結合手を意味する。）で表される構成単位を含有することが好ましい。さらにまた、本発明の水溶性組成物においては、さらに、前記水溶性感光重合体（Ａ）以外であって、下記一般式（ＩＶ）、

（一般式（ＩＶ）中、Ｒ^１は水素原子またはメチル基を表し、Ｘ^１は酸素原子または－ＮＲ^２－を表し、Ｒ^２は、水素原子または炭素原子数１～２０の炭化水素基を表し、Ｘ^２は炭素原子数１～６のアルキレン基を表し、Ｘ^２で表される炭素原子数１～６のアルキレン基の水素原子は、ハロゲン原子または水酸基で置換されていてもよく、ｎは、０～３０の数を表し、＊は結合手を意味し、一般式（ＩＶ）で表される基を複数有する場合、複数存在するＲ^１、Ｘ^１、Ｘ^２、ｎは、それぞれ同一であっても異なっていてもよい）で表される基を一つ以上有する化合物（Ｄ）を含有することが好ましい。さらにまた、本発明の水
溶性組成物においては、前記架橋剤（Ｃ）は、ジルコニウム化合物またはチタン化合物であることが好ましい。 In the water-soluble composition of the present invention, the water-soluble photosensitive polymer (A) has the following general formulas (IIα), (IIβ) and (IIγ),

In the general formulas (IIα), (IIβ) and (IIγ), Y1 ^, Y2 and Y3 ^each independently represent a direct bond or a ^divalent linking group, where ^Q1 , ^Q2 and ^Q3 are Each of them independently represents a photosensitive group, and * means a bond.) It is preferable to have one or more structural units selected from the group consisting of). Further, in the water-soluble composition of the present invention, the photosensitive group is preferably a stillvazolium group, a cinnamoyl group, an acrylic group, a methacrylic group, an acrylamide group or a metaacrylamide group. Further, in the water-soluble composition of the present invention, the water-soluble photosensitive polymer (A) has the following general formula (IIδ) or (IIε),

(In the general formulas (IIδ) and (IIε), An ^q- represents a q-valent anion, q represents 1 or 2, p represents a coefficient that keeps the charge neutral, and * means a bond. It is preferable to contain the structural unit represented by.). Furthermore, in the water-soluble composition of the present invention, other than the water-soluble photosensitive polymer (A), the following general formula (IV),

(In the general formula (IV), R ¹ represents a hydrogen atom or a methyl group, X ¹ represents an oxygen atom or ^{−NR2-, and R 2 represents} a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Represented, X ² represents an alkylene group having 1 to 6 carbon atoms, and the hydrogen atom of the alkylene group having 1 to 6 carbon atoms represented by X ² may be substituted with a halogen atom or a hydroxyl group, and n Represents a number from 0 to 30, * means a bond, and when there are a plurality of groups represented by the general formula (IV), the plurality of R ¹ , X ¹ , X ² , and n are the same. However, it may be different), and it is preferable to contain the compound (D) having one or more groups represented by. Furthermore, in the water-soluble composition of the present invention, the cross-linking agent (C) is preferably a zirconium compound or a titanium compound.

Further, the pattern-forming agent of the present invention is characterized by comprising the water-soluble composition of the present invention.

Further, the method for producing a cured product of the present invention is characterized in that the water-soluble composition of the present invention is used.

Further, the cured product of the present invention is characterized by being composed of the water-soluble composition of the present invention.

INDUSTRIAL APPLICABILITY According to the present invention, there are provided a water-soluble composition, a pattern forming agent, a method for producing a cured product using these, and a cured product, which can obtain a cured product having a high-definition pattern and excellent heat resistance, water resistance, and moisture heat resistance. can do. The water-soluble composition of the present invention can be suitably used for applications such as a pattern forming agent, an optical film for a flat panel display, a coating material for an optical film, or an adhesive.

で表される構成単位を有する化合物（Ｂ）（以下、「（Ｂ）成分」とも称す）、および架橋剤（Ｃ）（以下、「（Ｃ）成分」とも称す）を含有する。ここで、一般式（Ｉ）中、＊は結合手を意味する。本発明の水溶性組成物は、保存安定性に優れ、一液で存在できる為、硬化物を簡便に作成することができる。以下、各成分について順に説明する。First, the water-soluble composition of the present invention will be described. The water-soluble composition of the present invention is other than the water-soluble photosensitive polymer (A) having a photosensitive group and a hydroxyl group (hereinafter, also referred to as “component (A)”) and the water-soluble photosensitive polymer (A). The following general formula (I),

It contains a compound (B) having a structural unit represented by (hereinafter, also referred to as “(B) component”) and a cross-linking agent (C) (hereinafter, also referred to as “(C) component”). Here, in the general formula (I), * means a bond. Since the water-soluble composition of the present invention has excellent storage stability and can exist as a single liquid, a cured product can be easily prepared. Hereinafter, each component will be described in order.

<Ingredient (A)>
The component (A) according to the water-soluble composition of the present invention may have a photosensitive group and a hydroxyl group, and is not particularly limited. Preferred components (A) include compounds having the following general formulas (IIα) to (IIε) as constituent units because the cured product has high heat resistance, water resistance and moisture heat resistance, and among them, (IIδ). And the compound having (IIε) as a constituent unit is based on the fact that a water-soluble composition having excellent curability and a cured product having excellent heat resistance, water resistance and moisture heat resistance can be obtained even when an LED light source (365 nm) is used. preferable.

ここで、Ｙ^１、Ｙ^２およびＹ^３は、それぞれ独立に直接結合または２価の連結基を表し、Ｑ^１、Ｑ^２およびＱ^３は、それぞれ独立に感光基を表し、＊は結合手である。

ここで、一般式（ＩＩδ）、（ＩＩε）中、Ａｎ^ｑ－はｑ価のアニオンを表し、ｑは１または２を表し、ｐは電荷を中性に保つ係数を表し、＊は結合手を意味する。

Here, Y ¹ , Y ² and Y ³ each independently represent a direct-bonded or divalent linking group, Q ¹ , Q ² and Q ³ each independently represent a photosensitive group, and * is a binding hand. be.

Here, in the general formulas (IIδ) and (IIε), An ^q− represents a q-valent anion, q represents 1 or 2, p represents a coefficient that keeps the charge neutral, and * represents a bond. means.

The divalent linking group represented by Y ¹ , Y ² and Y ³ in the general formulas (IIα), (IIβ) and (IIγ) is not particularly limited, and is, for example, a methylene group, an ethylene group and a trimethylene. An alkylene group having 1 to 10 carbon atoms such as a group, a propylene group and a butylene group, an arylene group having 6 to 30 carbon atoms such as a phenylene group and a naphthalene group, a heterocyclic linking group, -CH = CH-, -O- , -S-, -C (= O)-, -CO-, -NR-, -CONR-, -OC-, -SO-, _-SO2- and a linking group in which two or more of these are combined are preferably mentioned. Can be done. Here, R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Examples of the photosensitive group represented by Q ¹ , Q ² and Q ³ in the general formulas (IIα), (IIβ) and (IIγ) include a cinnamyl group, a cinnamoyle group, a cinnamylden group, a cinnamyldenacetyl group and a chalcone. Group, coumarin group, isocoumarin group, 2,5-dimethoxystylben group, maleimide group, α-phenylmaleimide group, 2-pyrone group, azido group, timine group, quinone group, uracil group, pyrimidine group, stillvazolium group, styrylpyridinium Examples include a group, a tyrylquinolium group, an epoxy group, an oxetane group, a vinyl ether group, an allyl ether group, an acrylic group, a methacryl group, an acrylamide group, a methacrylamide group, a vinyl group, an allyl group, a styryl group and the like. When it is contained in the water-soluble composition as the component (A), a water-soluble composition having high photosensitivity and high liquid stability (without thickening, gelation, precipitation, etc.) can be obtained. A cinnamoyl group, an acrylic group, a methacrylic group, an acrylamide group or a methacrylamide group can be preferably used.

Among these photosensitive groups, the stillvazolium group has a high solubility in water and has an absorption band near 365 nm, so that it has a water-soluble composition that exhibits photosensitivity even in a light source having a long wavelength such as an LED light source (365 nm). You get things. From this water-soluble composition, a cured product having a high-definition pattern can be obtained in addition to heat resistance, water resistance and moisture heat resistance, and thus it can be particularly preferably used.

Specific examples of the preferred component (A) include water-soluble photosensitive polymers represented by the following general formula (V) and the following general formula (VI).

ここで、式（Ｖ）中、Ｙ^１およびＱ^１は上記一般式（ＩＩα）と同一であり、Ｙ^３およびＱ^３は上記一般式（ＩＩγ）と同一であり、ａ、ｂ、ｃ、およびｄは０～５０００までの数であり、ａおよびｄは、同時に０となることは無く、１００＜ａ＋ｂ＋ｃ＋ｄ＜５０００であり、＊は結合手である。

Here, in the formula (V), Y ¹ and Q ¹ are the same as the general formula (IIα), and Y ³ and Q ³ are the same as the general formula (IIγ), and a, b, c, and d is a number from 0 to 5000, a and d are never 0 at the same time, 100 <a + b + c + d <5000, and * is a bond.

ここで、式（ＶＩ）中、ａ、ｂ、ｃおよびｄは、一般式（Ｖ）と同一であり、ａおよびｄは、同時に０となることは無く、１００＜ａ＋ｂ＋ｃ＋ｄ＜５０００であり、＊は結合手である。

Here, in the formula (VI), a, b, c and d are the same as the general formula (V), and a and d are never 0 at the same time, and 100 <a + b + c + d <5000, *. Is a joiner.

Since the cured product obtained from the water-soluble composition of the present invention has good heat resistance and adhesion, preferable values of a, b, c and d (molar ratio) in the general formulas (V) and (VI) are set. a: b: c: d = 0.1 to 4: 5 to 30: 5 to 70: 0.1 to 4, and the weight average molecular weight is 15,000 to 5,000,000, preferably 100,000 to 1,000,000. Some are preferred.

The polymer represented by the general formula (VI) is obtained by acetalizing an aldehyde having a photosensitive group with a butenediol / polyvinyl alcohol copolymer under the conditions of pH 1 to 4. It can also be produced by using a commercially available product. For example, aldehyde having a photosensitive group in G polymer (butenediol vinyl alcohol copolymer) OKS-1081, OKS-1083, OKS-1109 manufactured by Nippon Synthetic Chemical Co., Ltd. is pH 1 It can also be obtained by carrying out an acetalization reaction under the conditions of -4.

The component (A) is preferably 1 to 99 parts by mass, more preferably 5 to 95 parts by mass, and 10 to 90 parts by mass in terms of solid content with respect to 100 parts by mass of the total of the components (A) and (B). It is most preferable because a cured product having a high-definition pattern and excellent heat resistance, water resistance and moisture heat resistance can be obtained by mass.

<Ingredient (B)>
The component (B) according to the water-soluble composition of the present invention may not have the above-mentioned photosensitive group in the structure and may have a structural unit represented by the following general formula (I), particularly. Not limited.

ここで、一般式（Ｉ）中、＊は結合手である。

Here, in the general formula (I), * is a bond.

The component (B) has the same main chain as that of conventionally known polyvinyl alcohol, and is generally polymerized with polyvinyl alcohol obtained by polymerizing vinyl alcohol, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, or vinyl acetate. Examples thereof include a saponified product of a copolymer with a monomer having a property. The polyvinyl alcohol constituting the component (B) may be a homopolymer or a copolymer containing vinyl alcohol as an essential monomer.

The method for producing the component (B) is not particularly limited, but for example, a method of reacting polyvinyl alcohol with diketene, a method of reacting polyvinyl alcohol with an acetoacetate ester to transesterify, vinyl acetate and acetoacetic acid. Examples thereof include a method of saponifying a vinyl copolymer. Among these, since the production process is simple and polyvinyl alcohol having a high-quality acetoacetic ester group can be obtained, it is preferable to produce by a method of reacting polyvinyl alcohol with diketene.

Examples of the monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, acrylic acid and methacrylic acid, and esters thereof, ethylene, and the like. Α-olefins such as propylene, allylsulfonic acid, metharylsulfonic acid, sodium allylsulfonic acid, sodium methallylsulfonic acid, sodium sulfonic acid, sodium sulfonate monoalkylmalate, sodium disulfonic acid alkylmalate, N-methylolacrylamide , Acrylalkylsulfonic acid alkali salt, N-vinylpyrrolidone, N-vinylpyrrolidone derivative and the like, and these monomers are preferably 10 mol% or less, particularly 5 mol% of the total structural unit. If it is too much, the water solubility may be lowered, or the compatibility with the component (C) described later may be lowered.

The polystyrene-equivalent weight average molecular weight (Mw) by gel permeation chromatography (GPC) is 10,000 to 200,000, and the saponification degree (hydrolysis rate) is 85 to 100. The component (B) has water resistance. It is preferable because it improves and the durability of the film is improved, and the component (B) having a saponification degree of 95 to 100 is more preferable because the water resistance is further improved.

で表される構成単位を有する化合物を用いた場合、本発明の水溶性組成物より得られる硬化物の耐熱性、耐水性および耐湿熱性が特に優れることからより好ましい。As the component (B), the following general formula (III),

When a compound having a structural unit represented by is used, it is more preferable because the cured product obtained from the water-soluble composition of the present invention is particularly excellent in heat resistance, water resistance and moisture heat resistance.

The content of the structural unit represented by the general formula (III) is usually 0.1 to 20 mol%, further 0.2 to 15 mol%, and particularly 0.3 to 10 mol%. However, it is preferable from the viewpoints of water resistance, cross-linking rate, water solubility, and stability of the aqueous solution of the cured product.

As the component (B), a commercially available product can also be used, and examples thereof include Gosenex Z-100, Z-200, Z-220, Z-300 and Z-410 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

The component (B) is preferably 1 to 99 parts by mass, more preferably 5 to 95 parts by mass, and most preferably 10 to 90 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). preferable. When the content of the component (B) is in the above range, it is preferable because a cured product having a high-definition pattern and excellent heat resistance, water resistance and moisture heat resistance can be obtained.

<Ingredient (C)>
The component (C) contained in the water-soluble composition of the present invention can be used without limitation as long as it can crosslink the component (B). As the component (C), for example, a conventionally known organic cross-linking agent, a metal chelate complex having a chelating agent, a zirconium compound, and a titanium compound can be preferably used.

As the organic cross-linking agent, any of those commonly used as cross-linking agents can be selected and used, for example, a bisdiazide compound, an amino resin having a hydroxyl group or an alkoxyl group, for example, a melamine resin, a urea resin, and the like. Examples thereof include guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, ethyleneurea-formaldehyde resin and the like. These can be melamine, urea, guanamine, glycoluril, succinylamide, or ethyleneurea reacted with formalin in boiling water to form methylol, or further reacted with a lower alcohol to form an alkoxyl.

Examples of the chelating agent include hydroxycarboxylic acid or a salt thereof, glyoxylic acid or a salt thereof, amino alcohol, aminocarboxylic acid, alanine, arginine, leucine, isoleucine, dihydroxypropylglycine, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, and nitrilotriacetic acid. Examples thereof include β-diketone, dimethylglioxime, citric acid, tartrate acid, maleic acid, polyhydrazide, phosphate ester and the like, and these can be used alone or in combination of two or more.

When a metal chelate complex having a chelating agent capable of coordinating one metal atom in two or more loci by a covalent bond or a hydrogen bond is used, the cross-linking reaction rate Is preferable because it is appropriately adjusted. Specific examples of the chelate-type ligand include hydroxycarboxylic acid or a salt thereof, amino alcohol, β-diketone and the like.

Examples of the zirconium compound include zirconium halides such as zirconium oxychloride, zirconium hydroxychloride, zirconium tetrachloride, and zirconium bromide; Zirconium salt; zirconium salt of organic acids such as zirconium formate, zirconium acetate, zirconium propionate, zirconium caprylate, zirconium stearate, zirconium lactate, zirconium nitrate, zirconium carbonate, zirconium octylate, zirconium citrate, zirconium phosphate; Zirconium complex salts such as ammonium zirconium, sodium zirconium sulfate, ammonium zirconium acetate, ammonium zirconium carbonate, potassium zirconium carbonate, sodium zirconium oxalate, sodium zirconium citrate, ammonium zirconium citrate, ammonium zirconium lactate, as well as one or more. Examples thereof include a zirconium chelate complex having a chelating agent as a ligand. Among these, water-soluble zirconium is preferable, and zirconium oxyhalogenate, zirconium oxyacetate, zirconium sulfate and zirconium oxynitrate are more preferable.

Examples of the zirconium chelate complex include zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium oxyhalogen, zirconium oxynitrite, zirconium lactateammonium, zirconium sulfate and zirconium oxyacetate, zirconium bisacetylacetonate, and zirconium monoethylacetate. Examples thereof include acetate and zirconium acetate.

Among zirconium compounds, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium oxyhalogenate, zirconium oxynitrite, zirconium lactateammonium, zirconium sulfate, zirconium oxyacetate, etc. have high stability, water solubility, and reactivity. preferable. These can be used as one or a mixture of two or more.

Commercially available products can also be used as the zirconium compound, and for example, zirconium acidified, zirconium ZC-2, zirconium ZN, zirconol HA, zirconium AC-7, zircozol ZK-10, zirconium ZN, zircozol ZA-10, zircozol ZA- 20, Zirconium octylate, Zirconyl carbonate, (manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.), Organix ZA-45, Organix ZA-65, Organix ZB-126, Organix ZC-126, Organix ZC-150, Olga Examples thereof include Chix ZC-200, Olga Chix ZC-300, Olga Chix ZC-320, Olga Chix ZC-540, Olga Chix ZC-580, Olga Chix ZC-700, ZC-300 (manufactured by Matsumoto Fine Chemical Co., Ltd.).

Examples of titanium compounds include tetramethyl titanate, tetraethyl titanate, tetranormal propyl titanate, tetraisopropyl titanate, tetranormal butyl titanate, tetraisobutyl titanate, tetra-t-butyl titanate, tetraoctyl titanate, tetra (2-ethylhexyl) titanate, and tetra. Titanium alkoxides such as methyl titanate; oligomers and polymers obtained by the hydrolysis decomposition reaction of titanium alkoxides such as titanium butyl dimer and titanium butyl tetramer and their derivatives; titanium acetylacetonate, titanium octylene glycolate, titanium tetraacetylacetonate , Titanium ethyl acetoacetate, Titanium triethanolalkoxide, Titanium chelate complex such as titanium oxalate; Titanium acylate such as polyhydroxytitanium stearate; Titanium tetrachloride, Titanium alkoxide, Titanium triethanolaminate, Diisopropoxytitanium bis ( Triethanolamineate) and the like, which can be used as one or a mixture of two or more.

Commercially available products can also be used as the titanium compound, for example, Organix TA-8, Organix TA-10, Organix TA-12, Organix TC-100, Organix TC-120, Organix TC-300, Examples thereof include Organix TC-310, Organix TC-315, Organix TC-335, Organix TC-401, Organix TC-800 (manufactured by Matsumoto Fine Chemical Co., Ltd.) and the like.

Among the components (C), a zirconium compound or a titanium compound is particularly preferable because the cured product obtained from the water-soluble composition of the present invention has good moisture and heat resistance.

The amount of the component (C) is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (B) because there is no change in precipitation or thickening and the water-soluble composition is stable.

The water-soluble composition of the present invention contains a metal content derived from the component (C), and the metal content is preferably 0.01 to 3% by mass, more preferably, in the components of the water-soluble composition excluding the solvent. It is preferably 0.01 to 1% by mass.

で表される化合物を含有していてもよい。ここで、一般式（ＩＶ）中、Ｒ^１は水素原子またはメチル基を表し、Ｘ^１は酸素原子または－ＮＲ^２－を表し、Ｒ^２は、水素原子または炭素原子数１～２０の炭化水素基を表し、Ｘ^２は炭素原子数１～６のアルキレン基を表し、Ｘ^２で表される炭素原子数１～６のアルキレン基の水素原子は、ハロゲン原子または水酸基で置換されていてもよく、ｎは、０～３０の数を表し、＊は結合手を意味し、複数の一般式（ＩＶ）で表される基を複数有する場合、複数存在するＲ^１、Ｘ^１、Ｘ^２、ｎは、それぞれ同一であっても異なっていてもよい。<(D) component>
The water-soluble composition of the present invention has the following general formula (IV) as the component (D).

It may contain a compound represented by. Here, in the general formula (IV), R ¹ represents a hydrogen atom or a methyl group, X ¹ represents an oxygen atom or −NR2 −, and R ² represents a hydrogen atom or a hydrocarbon having 1 to ²⁰ carbon atoms. The group represents a group, X ² represents an alkylene group having 1 to 6 carbon atoms, and the hydrogen atom of the alkylene group having 1 to 6 carbon atoms represented by X ² may be substituted with a halogen atom or a hydroxyl group. , N represents a number from 0 to 30, * means a bond, and when there are a plurality of groups represented by a plurality of general formulas (IV), there are a plurality of R ¹ , X ¹ , X ² , n. May be the same or different.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ² in the general formula (IV) is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms and a carbon atom number. 2 to 20 alkenyl groups, 3 to 20 carbon atoms cycloalkyl group, 4 to 20 carbon atoms cycloalkylalkyl group, 6 to 20 carbon atoms aryl group and 7 to 20 carbon atoms arylalkyl group And so on. (B) Since the sensitivity when used as a component is good, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a carbon atom number More preferably, a cycloalkylalkyl group having 4 to 10, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms and the like are more preferable.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, and isooctyl. Examples thereof include 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and icosyl, and examples of the above-mentioned alkyl group having 1 to 10 carbon atoms include methyl and ethyl. , Vryx, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl and isodecyl, etc. Can be mentioned.

Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-. Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4, Examples thereof include 8,12-tetradecatrienylallyl and the like, and examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl and 3-pentenyl. , 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl and the like.

The cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo [1.1.1] pentanyl and tetradecahydroanthrasenyl, etc. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene and bicyclo. [1.1.1] Pentanyl and the like can be mentioned.

The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is substituted with the cycloalkyl group. For example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2- Cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-Cyclononylpropyl, 3-Cyclodecylpropyl, 4-Cyclobutylbutyl, 4-Cyclopentylbutyl, 4-Cyclohexylbutyl, 4-Cycloheptylbutyl, 4-Cyclooctylbutyl, 4-Cyclononylbutyl, 4-Cyclodecyl Examples thereof include butyl, 3-3-adamantylpropyl, decahydronaphthylpropyl and the like, and examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl and cycloheptyl. Methyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3 -Cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl and the like can be mentioned.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl and the like, the above-mentioned alkyl group, the above-mentioned alkenyl group, the carboxyl group, the halogen atom and the like. Examples thereof include 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like, and the number of carbon atoms is 6 as described above. Examples of the aryl group to 10 include phenyl, tolyl, xylyl, ethylphenyl, naphthyl and the like, phenyl, biphenylyl, naphthyl and the like substituted with one or more of the above alkyl group, the above alkenyl group, the carboxyl group, a halogen atom and the like. Anthrill and the like, for example, 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like can be mentioned.

The arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 30 carbon atoms in which the hydrogen atom of the alkyl group is substituted with an aryl group. For example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, naphthylpropyl and the like can be mentioned. The arylalkyl group having 7 to 20 carbon atoms is an aryl group in which the hydrogen atom of the alkyl group is an aryl group. It means a group having 7 to 20 substituted carbon atoms. For example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like can be mentioned.

Examples of the alkylene group having 1 to ⁶ carbon atoms represented by X2 in the general formula (IV) include a linear chain such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group. Examples thereof include an alkylene group and a branched alkylene group such as an isopropylene group and an isobutylene group.

As the component (D), for example, an alkylene oxide-modified acrylate compound, an alkylene oxide-modified methacrylate compound, an acrylamide compound and a methacrylamide compound can be preferably used.

In the general formula (IV), the alkylene oxide-modified acrylate compound is a compound in which R ¹ is a hydrogen atom, X ¹ is an oxygen atom, and n is 1 to 30, and the alkylene oxide-modified methacrylate compound is a general formula. In (IV), R ¹ is a methyl group, X ¹ is an oxygen atom, and n is a compound of 1 to 30.

Examples of the alkylene oxide-modified acrylate compound include diethylene oxide-modified neopentyl glycol diacrylate, dipropylene oxide-modified neopentyl glycol diacrylate, diethylene oxide-modified 1,6-hexanediol diacrylate, and dipropylene oxide-modified 1,6-hexane. Examples of the alkylene oxide-modified methacrylate compound include diol diacrylate, and examples thereof include diethylene oxide-modified neopentyl glycol dimethacrylate, dipropylene oxide-modified neopentyl glycol dimethacrylate, diethylene oxide-modified 1,6-hexanediol dimethacrylate, and diethylene oxide. Examples thereof include propylene oxide-modified 1,6-hexanediol dimethacrylate.

As the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound, commercially available products can also be preferably used. For example, NK ester A-600, A-GLY-20E, NK economyr A-PG5054E (above, Shin Nakamura Chemical Industry Co., Ltd.) Industrial) and the like.

Among the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound, those in which X2 in the general formula (IV) is an ethylene group or a propylene group are preferable because ^they are excellent in water solubility, and the ethylene group is particularly water-soluble. It is preferable because it is excellent in

When the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound have one group represented by the general formula (IV), it is particularly preferable that n is 6 or more because it is excellent in water solubility. When the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound have a plurality of groups represented by the general formula (IV), they are excellent in water solubility. preferable.

The acrylamide compound is a compound in the general formula (IV) in which R ¹ is a hydrogen atom, X ¹ is NR ^2- , and n is 1 to 0, and the methacrylamide compound is the general formula (IV). ), R ¹ is a methyl group, X ¹ is a compound of NR ^2- , and n is a compound of 0.

Examples of the acrylamide compound include hydroxyacrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-butylacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N. -Dipropylacrylamide, acrylic loylmorpholine, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide and the like can be mentioned. Examples of the methacrylamide compound include hydroxymethacrylate and N-methylmethacrylate. , N-Ethylmethacrylamide, N-isopropylmethacrylate, N-butylmethacrylate, diacetonemethamide, N, N-dimethylmethacrylate, N, N-diethylmethacrylate, N, N-dipropylmethacrylate, methacryl Examples thereof include loylmorpholin, Nn-butoxymethylmethacrylate, N-isobutoxymethylmethacrylate, N-methoxymethylmethacrylate and the like.

As the acrylamide compound and the methacrylamide compound, commercially available products can also be preferably used, and examples thereof include FFM-2, FFM-3, FFM-4 and FFM-5 (manufactured by FUJIFILM Corporation).

When the component (D) is contained, the content of the component (D) is 1 to 50 parts by mass with respect to 100 parts by mass of the total of the components (A), (B) and (D), and (D). ) When the content of the component is in this range, a water-soluble composition having good curability is obtained, and a cured product having a finer pattern than this water-soluble composition and having excellent heat resistance, water resistance and moist heat resistance is obtained. It is preferable because it can be obtained.

The water-soluble composition of the present invention may be used in combination with an organic solvent as long as it contains water as a solvent, but when it is applied on an organic material with a low environmental load, it is possible to use only water as a solvent. It is preferable because it does not attack organic materials.

As the organic solvent, a solvent capable of dissolving or dispersing each of the above components ((A) component, (B) component, (C) component and (D) component) and the like when used in combination with water, for example, methyl ethyl ketone. , Methylamylketone, diethylketone, acetone, methylisopropylketone, methylisobutylketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and Ethereal solvents such as dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, -n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and texanol; ethylene glycol monomethyl Cellosolve solvents such as ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol and amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, Ether ester solvents such as propylene glycol-1-monomethyl ether (PGM), propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate. Aromatic solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene hydrocarbons such as terepine oil, D-lymonen and pinen; mineral spirit, swazole # Paraffinic solvents such as 310 (above, Cosmo Matsuyama Petroleum); and Solbesso # 100 (above, Exxon Chemical); halogenated fatty groups such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane. Hydrocarbon-based solvent; Halogenized aromatic hydrocarbon-based solvent such as chlorobenzene; Carbitol-based solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, Examples thereof include N-methylpyrrolidone, dimethylsulfoxide and water, and an alcohol solvent is preferable because it has good compatibility with water.

The water-soluble composition of the present invention contains water as a solvent. Although it can be used in combination with an organic solvent, it is preferable to use only water as a solvent because it does not attack the organic material when it is applied on an organic material and has a low environmental load.

In the water-soluble composition of the present invention, the amount of the solvent used is not particularly limited, but is preferably 70 to 95% by mass with respect to the total amount of the water-soluble composition. When the content of the solvent is in the above range, the curable composition and the curable composition having excellent handleability (viscosity and wettability of the curable composition) and liquid stability (without precipitation and precipitation of the components contained in the composition) and curing are excellent. It is preferable because the thickness of the object can be appropriately controlled.

The water-soluble composition of the present invention contains, if necessary, a water-soluble polymer, an organic acid, a coupling agent, a sensitizer, a surfactant, and a basic compound that do not belong to the component (A) and the component (B). , Colorants, radical initiators, water-soluble preservatives, conductive substances and the like can also be added.

Examples of the water-soluble polymer belonging to the component (A) and the component (B) include oxidized starch, etherified / esterified / grafted modified starch, cellulose derivatives such as gelatin, casein and carboxymethyl cellulose, polyvinylpyrrolidone, and water-soluble polymer. Water-soluble polyacrylic acid ester resin such as sex polyester resin, 2-hydroxypropyl acrylate polymer, 4-hydroxybutyl acrylate polymer, water-soluble polycarbonate resin, water-soluble polyvinyl acetate resin, water-soluble styrene acrylicte resin, water-soluble vinyl toluene acrylate Resin, water-soluble polyurethane resin, polyvinylamide / polyacrylamide, water-soluble polyamide resin such as modified acrylamide, water-soluble urea resin, water-soluble polycaprolactone resin, water-soluble polystyrene resin, water-soluble polyvinyl chloride resin, water-soluble polyacrylate resin , Water-soluble resin such as water-soluble polyacrylonitrile resin, styrene / butadiene copolymer, acrylic acid ester copolymer, ethylene / vinyl acetate copolymer and the like.

As the organic acid, any weakly acidic compound having a carboxyl group can be used without limitation, for example, acetic acid, citric acid, malic acid, glycolic acid, lactic acid, carbonic acid, formic acid, oxalic acid, propionic acid, octyl acid, and the like. Examples thereof include capric acid, glycolic acid, stearic acid, benzoic acid, mandelic acid and the like. Among these, lactic acid, acetic acid, citric acid, glycolic acid or malic acid are preferable.

Examples of the coupling agent include alkyl functions such as dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkenyl functional alkoxysilanes such as sex alkoxysilanes, vinyltrichlorosilanes, vinyltrimethoxysilanes, vinyltriethoxysilanes, allyltrimethoxysilanes, 3-methacryloxybropyrriethoxysilanes, 3-methacryloxybropyrtrimethoxysilanes, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β -Epoxy functional alkoxysilanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ -Amino-functional alkoxysilanes such as aminopropyltrimethoxysilane and mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane can be used.

The sensitizer is a compound capable of expanding the applicable wavelength range of light when cured by light irradiation, and examples of the sensitizer include benzophenone, 3-hydroxybenzophenone, and 4-hydroxybenzophenone. , 4,4-Dihydroxybenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone, 4-methoxybenzophenone, 4,4-dimethoxybenzophenone, 3 , 3-dimethyl-4-methoxybenzophenone, benzophenones such as 4-phenylbenzophenone, anthraquinone, 4-methoxyacetophenone, 2,4-dimethoxyacetophenone, 2,5-dimethoxyacetophenone, 2,6-dimethoxyacetophenone, 4,4 -Acetophenones such as dimethoxyacetphenone, 4-ethoxyacetophenone, diethoxyacetophenone, 2,2-diethoxyacetophenone, 2-ethoxy-2-phenylacetophenone, 4-phenylacetophenone, anthraquinone, hydroxyanthraquinone, 1-nitroanthraquinone, amino Anthraquinones such as anthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, anthraquinone sulfonic acid, 1,2-benz anthraquinone, 1,4-hydroxyanthraquinone (kinizarin), anthraquinone, 1,2-benzoanthraquinone. , 9-Cyanoanthraquinone, 9,10-dicyanoanthraquinone, 2-ethyl-9,10-dimethoxyanthraquinone, 9,10-bis (phenylethyl) anthraquinone and other anthraquinones, 2,3-dichloro-6-dicyano-p. -Anthraquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, methoxybenzoquinone, 2,5-dichloro-p-benzoquinone, 2,6-dimethyl-1,4-benzoquinone, 9,10-phenan Anthraquinone, anthraquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinones such as xanthone, thioxanthone, 2-methylthioxanson, 2,4-dimethylthioxanthone, isopropylthioxanson, 2,4 -Thioxans such as diethylthioxanson and 2,4-isopropylthioxanson, cycloheptanes such as dibenzosverone, dibenzosverene, dibenzosberenol and dibenzosveran, 2-methoxy Aromatic compounds such as naphthalene, benzoin isopropyl ether, 4-benzoyldiphenyl, o-benzoylbenzoic acid, methyl o-benzoylbenzoate, 4-benzoyl-4-methyl-diphenylsulfide, benzyl, benzoinmethyl ether, and dye-based increase. Examples thereof include coumarin-based, thiadin-based, azine-based, aclysine-based, and xanthene-based compounds which are sensitive substances.

Examples of the surfactant include fluorosurfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates, and higher amines. Cationic surfactants such as halides and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

Examples of the basic compound include ammonia, sodium hydroxide, potassium hydroxide, triethylamine, triethanolamine, diethanolamine, monoethanolamine, triisopropanolamine, diisopropanolamine, monoisopropanolamine, N, N-dimethylethanolamine. , Ethyleneimine, pyrrolidine, piperidine, polyethyleneimine and the like, and these can be used alone or in combination of two or more, and a basic compound may be added for the purpose of pH adjustment or the like.

Pigments and dyes can be used as the colorant. As the pigment and the dye, an inorganic color material or an organic color material can be used, respectively, and these can be used alone or in combination of two or more. Here, the pigment refers to a colorant that is insoluble in a solvent, which will be described later, and includes inorganic or organic coloring materials that are insoluble in a solvent, or raked inorganic or organic dyes.

Examples of the pigment include carbon black obtained by a furnace method, a channel method or a thermal method, carbon black such as acetylene black, ketjen black or lamp black, carbon black prepared or coated with an epoxy resin, and carbon black. Was previously dispersed in a resin in a solvent and coated with a resin of 20 to 200 mg / g, the carbon black was subjected to an acidic or alkaline surface treatment, the average particle size was 8 nm or more, and the DBP oil absorption amount was 90 ml / 100 g or less. Carbon black, carbon black, graphite carbon black, graphite, activated carbon, carbon fiber, carbon nanotubes, carbon whose total oxygen content calculated from CO and CO ₂ in the volatile matter at 950 ° C is 9 mg or more per 100 m ² of surface area. Microcoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, black pigment represented by titanium black, chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate Organic or inorganic such as ultramarine, navy blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, synthetic iron black, amber, lake pigment, etc. Examples thereof include pigments, and it is preferable to use a black pigment because of its high light-shielding property, and it is further preferable to use carbon black as the black pigment.

Commercially available products may be used as the pigment, for example, MICROPIGMO WMYW-5, MICROPIGMO WMRD-5, MICROPIGMO WMBN-5, MICROPIGMO WMGN-5, MICROPIGMO WMBK-5, MICROPIGMO WMBE-5, MICROPIGMO. MICROPIGMO WMWE-1, BONJET BLACK CW-1 (above, manufactured by Orient Chemical Industry Co., Ltd.) Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88 , 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217. , 220, 223, 224, 226, 227, 254, 228, 240 and 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61. , 62, 64, 65 and 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100. , 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180 and 185. Pigment Greens 7, 10, 36 and 58; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61 , 62 and 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50 and the like.

Examples of the dye include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindrin compounds, quinacridone compounds, and antanthrone. Examples thereof include a compound, a perinone compound, a perylene compound, a diketopyrrolopyrrole compound, a thioindigo compound, a dioxazine compound, a triphenylmethane compound, a quinophthalone compound, a naphthalenetetracarboxylic acid, an azo dye, and a metal complex compound of a cyanine dye.

Conventionally known compounds can be used as the radical initiator. For example, JP-A-57-197289, JP-A-6-228218, JP-A-2009-12455, JP-A-2012-007071, JP-A-2016-510314, In addition to those described in WO2014 / 050551, JP-A-06-239910, JP-A-2003-192712, and JP-A-2016-185929, benzophenone, carboxybenzophenone and its salt, dicarboxybenzophenone and its salt, thioxanthone, 1-chlor- Hydrogen abstraction type photopolymerization initiators such as 4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethylanthraquinone; phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane (α-hydroxyalkylphenone), benzoin, benzyldimethylketal, 1-benzyl-1-dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholyl-2- (4'-methylmercapto) benzoylpropane, 4-benzoyl-4'-methyldiphenylsulfide, benzoinbutyl ether, 2-Hydroxy-2-benzoylpropane, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyl dichloromethane, methyl benzoylate, 1-hydroxy-cyclohexyl-phenyl-ketone , 2-Hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 1,7-bis (9'-acrydinyl) heptane, 9-n-butyl-3,6-bis (2'-morpholinoisobutyroyl) carbazole, 2-methyl-4,6-bis (trichloromethyl) -s -Triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, 2,2-bis (2-chlorophenyl)- Photodegradable photopolymerization initiators such as 4,5,4', 5'-tetraphenyl-1-2'-biimidazole, acylphosphine oxide, bisacylphosphinoxide, triphenylphosphine oxide can be used, and photo A decomposition type photopolymerization initiator is preferable from the viewpoint of reactivity.

Among the above photodegradable photopolymerization initiators, water-soluble initiators such as Irg2959, Irg819DW (manufactured by BASF), ESACURE ONE, ESACURE 1001M, ESACURE KIP 150, and ESACURE DP 250 (Lamberti) have an affinity for water. It is preferable because it has a high property.

As the above dye, a commercially available product can be used, and as the water-soluble dye, for example, WATER YELLOW 1, WATER YELLOW 2, WATER YELLOW 6C, WATER YELLOW 6CL, WATER ORANGE 18, WATER ORANGE 25, WATER RED 1, RED 2S, WATER RED 3, WATER RED 9, WATER RED 27, WATER PINK 2S, WATER BROWN 16, WATER GREEN 8, WATER BLUE 3, WATER BLUE 9, WATER BLUE 105S, WATER BLUE 106 VIOLET 7, WATER BLACK 31, WATER BLACK 191-L, WATER BLACK 256-L, WATER BLACK R-455, WATER BLACK R-510, BONJET YELLOW 161-L, BONJET MAGENTA XX, BOXJET CYAN (The above is manufactured by Orient Chemical Industry Co., Ltd.) and the like.

As oil-soluble dyes, VALIFAST YELLOW 1101, VALIFAST YELLOW 3150, VALIFAST RED 1308, VALUESTAR RED 2320, VALIFAST PINK 1364, VALIFAST PINK 2310N, VALIFAST PINK 2310N, VALIFAST VIEW VALUE18 VALUESTAB BLACK 3820, VALUESTAR BLACK 3830, VALUESTAR BLACK 3840, VALIFAST BLACK 3866, VALUESTAR BLACK 3870, VALIFAST ORANGE 2210, VALIFAST BROWN 3402, VALIFAST BROWN 3402, VALIFAST

Examples of the water-soluble preservative include those having high solubility in water and having a solubility of 1% or more at room temperature. Specific examples thereof include methylparaben, benzoic acid, benzoate, salicylic acid, and salicylate. Phenoxyethanol, water-soluble cationic antibacterial agent, organic sulfur compound, halogenated compound, cyclic organic nitrogen compound, low molecular weight aldehyde, paraben, propanediol substance, isothiazolinone, quaternary compound, benzoate, low molecular weight alcohol, dehydroacetic acid, ACQ (copper, ACQ) Quaternary ammonium compound), CUAZ (copper / azole compound), AAQ (quaternary ammonium compound), sodium hydrogen sulfite, sodium hydrogen sulfate, sodium thiosulfate, ascorbic acid salt, benzalconium chloride, chlorobutanol, thimerosal, Examples thereof include phenylmercuric acetate, phenylmercury borate, phenylmercurite nitrate, paraben, methylparaben, polyvinyl alcohol, benzyl alcohol, isothiazolone, triazine, bronopol, thiabendazole, zincpyrythion, carbendazim, pyridineoxide thiol sodium salt and phenylethanol.

As the water-soluble preservative, commercially available products can also be used, such as Sun Eye Bag P, Sun Eye Bag 300K, Sun Eye Bag IT-15SA, Sun Eye Bag AS-30, Sun Eye Bag T-10, Sun Eye Bag M-30, and Sun Eye Bag. Sodium omadin (both made by San-Ai Oil) and the like can be mentioned.

Examples of the conductive substance include metals, metal oxides, conductive carbon, and conductive polymers.

Examples of the metal include metals such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead. Examples thereof include alloys composed of two or more kinds of metals such as alloys, tin-copper alloys, tin-silver alloys and tin-lead-silver alloys. Of these, nickel, copper, silver or gold are preferred.

Examples of the conductive carbon include carbon black such as Ketjen black, acetylene black, furnace black, and channel black, fullerene, carbon nanotubes, carbon nanofibers, graphene, amorphous carbon, carbon fiber, natural graphite, and artificial graphite. Examples thereof include graphitized Ketjen black and mesoporous carbon.

Examples of the conductive polymer include polyacetylene, polypyrrol, poly (3-methylpyrol), poly (3-butylpyrol), poly (3-octylpyrol), poly (3-decylpyrol), and poly (3). , 4-dimethylpyrol), poly (3,4-dibutylpyrol), poly (3-hydroxypyrol), poly (3-methyl-4-hydroxypyrol), poly (3-methoxypyrol), poly (3-ethoxy) Pyrol), poly (3-octoxypyrrole), poly (3-carboxypyrol), poly (3-methyl-4-carboxypyrol), poly N-methylpyrol, polythiophene, poly (3-methylthiophene), poly (3) 3-butylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-ethoxythiophene). Octoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3,4-ethylenedioxythiophene), polyaniline, poly (2-methylanilin), poly (2) -Octylaniline), poly (2-isobutylaniline), poly (3-isobutylaniline), poly (2-anilinsulfonic acid), poly (3-anilinsulfonic acid) and polythiophene derivatives (PEDOT: poly (3,4)). -Eethylenedioxythiophene) doped with polystyrene sulfonic acid (PSS) and the like can be mentioned.

In addition to the above, photopolymerization initiators, thermal polymerization initiators, photobase initiators, acid generators, inorganic fillers, organic fillers, defoaming agents, and more, as long as the effects of the present invention are not impaired. Adhesives, Leveling Agents, Organic Metal Coupling Agents, Chixo Agents, Carbon Compounds, Metal Fine Particles, Metal Oxides, Flame Retardants, Plastics, Photo Stabilizers, Heat Stabilizers, Anti-Aging Agents, Polymer Particles, Chain Transfer Agents, Various resins such as polymerization initiators, ultraviolet absorbers, antioxidants, antistatic agents, mold release agents, flow modifiers, adhesion promoters, unsaturated monomers, epoxy compounds, oxetane compounds, vinyl ethers and other cationically polymerizable compounds. Additives and the like can be added.

Next, the pattern-forming agent of the present invention will be described. The pattern-forming agent of the present invention comprises the water-soluble composition of the present invention. The pattern-forming agent of the present invention has photolithographic properties. Specifically, the pattern-forming agent is irradiated with light through a mask and then developed with a developing solution (water, organic solvent, alkaline aqueous solution, etc.). A pattern of 1000 μm or less can be reproducibly formed with an accuracy of ± 10% or less.

The method for producing a cured product of the present invention is carried out using the water-soluble composition or pattern-forming agent of the present invention. The preferred coating method and curing conditions for the method for producing a cured product using the water-soluble composition or pattern forming agent of the present invention are shown below.

Preferred coating methods are known means such as spin coaters, bar coaters, roll coaters, curtain coaters, various types of printing, dipping and the like, and are applied on supporting substrates such as glass, metal, paper and plastic. Further, it is also possible to apply it once on a support substrate such as a film and then transfer it onto another support substrate, and there is no limitation on the application method thereof.

Examples of the material of the transparent support include an inorganic material such as glass; a cellulose ester such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose, and nitro cellulose; polyamide; polycarbonate; polyethylene terephthalate. , Polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyetane-4,4'-dicarboxylate, polyesters such as polybutylene terephthalate; polystyrene; polyethylene, Polyolefins such as polypropylene and polymethylpentene; acrylic resins such as polymethylmethacrylate; polycarbonates; polysulfones; polyethersulfones; polyetherketones; polyetherimides; polymer materials such as polyoxyethylene and norbornene resins can be mentioned. The transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze is preferably 2% or less, more preferably 1% or less. The refractive index is preferably 1.45 to 1.70.

Preferred curing conditions are when light irradiation is performed after applying the water-soluble composition or pattern forming agent of the present invention on a transparent support, and the irradiation conditions such as the wavelength, intensity and irradiation time of the irradiated light are light. It is appropriately adjusted depending on the activity of the initiator, the activity of the photopolymerizable resin used, and the like, but the wavelength of the light is usually preferably one having a wavelength peak of 300 to 500 nm in order to allow sufficient light to penetrate into the interior. A wavelength peak of 350 to 450 nm is more preferable, and a wavelength peak of 360 to 380 nm is most preferable. The light intensity is preferably 10 to 300 mW / cm ² , more preferably 25 to 100 mW / cm ² , and the irradiation time is preferably 5 to 500 seconds, more preferably 10 to 300 seconds.

The cross-linking reaction can also be promoted by applying the water-soluble composition or pattern-forming agent of the present invention on the transparent support and then heating the transparent support. The heating is carried out at 50 to 200 ° C., preferably 70 to 150 ° C. for 10 to 1 hour. If it is lower than 50 ° C., the cross-linking reaction may not proceed, and if it is higher than 200 ° C., the components (A) to (D) may be decomposed or the transparency of the optical film may be lowered.

When creating a pattern of a cured product by photolitho, the water-soluble composition or pattern-forming agent of the present invention is placed on a glass substrate with a stylus type shape measuring instrument (Dektak 150 manufactured by ULVAC) in a film thickness of 5.0 to 5. After applying using a spin coater adjusted to be .5 μm, prebaking was performed for 10 minutes on a hot plate at 90 ° C. After that, the mixture was cooled to room temperature, irradiated with light containing a wavelength of 365 nm at 500 mJ / cm ² via a photomask (LINE / SPACE = 50 μm / 50 μm) using a high-pressure mercury lamp, and immersed in ion-exchanged water at 23 ° C. for 1 minute. After soaking, the water adhering to it is removed with an air gun, and the substrate is dried in an oven at 140 ° C. for 30 minutes. Preferred curing conditions are the same as above.

The cured product of the present invention comprises the water-soluble composition or pattern-forming agent of the present invention. Specific uses of the water-soluble composition and pattern-forming agent of the present invention include eyeglasses, optical materials typified by imaging lenses, paints, various coating agents, lining agents, inks, resists, liquid resists, adhesives, and the like. Sealing agent for liquid crystal dripping method, image forming material, pattern forming material, printing plate, insulating varnish, insulating sheet, laminated board, printed board, for semiconductor devices, for LED packages, for liquid crystal injection port, for organic EL, for optical elements・ Encapsulants for electrical insulation, electronic parts, separation films, molding materials, putty, building materials, siding, glass fiber impregnants, sealants, passivation films for semiconductors, solar cells, etc., interlayer insulating films , A protective film, a prism lens sheet used for the backlight of a liquid crystal display device, a Frenel lens sheet used for a screen of a projection television, a lens part of a lens sheet such as a wrenchular lens sheet, or such a sheet. Protective films and spacers for liquid crystal color filters such as backlights, DNA separation chips, microreactors, nanobiodevices, recording materials for hard disks, solid-state imaging devices, solar cell panels, light emitting diodes, organic light emitting devices, luminescent films, fluorescent films, etc. Examples include optical lenses such as MEMS elements, actuators, holograms, plasmon devices, polarizing plates, polarizing films, microlenses, optical elements, optical connectors, optical waveguides, casting agents for optical modeling, and the like. Examples of applicable base materials include metal, wood, rubber, plastic, glass, and ceramic products.

When the water-soluble composition and pattern-forming agent of the present invention are used for an optical film, the optical film is formed into a film or sheet by a conventional method, and the obtained film or sheet is not stretched (or oriented). It may be manufactured, or it may be manufactured by stretching (or orienting treatment). For film molding, a melt molding method (melt film forming method) such as extrusion molding or blow molding may be used, or a casting method (casting film forming method, solution casting method) may be used. ..

The optical film using the water-soluble composition and the pattern forming agent of the present invention is not particularly limited in terms of shape, but is usually a film having an optical film on a transparent support and used for optical applications. , Protective film for polarizing plates used in liquid crystal displays, retardation films, viewing angle enlargement films, antireflection films used in plasma displays, various functional films such as low reflectance films, and organic EL displays. Various functional films and the like to be used can be mentioned.

The optical film using the water-soluble composition and the pattern forming agent of the present invention is an optical recording layer of a write-once optical disk (CD ± R, DVD ± R, next-generation high-density disk, etc.) to which the optical film is applied to a support. ; Various lenses; Optical filters for image display devices; Various filters typified by color filters and color conversion filters; Alternatively, they can be used as protective sealing films for organic EL light emitting elements, inorganic EL light emitting elements, electronic paper displays, etc. can.

Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to these examples. The solid content described in this example means the mass% occupied by the components excluding the solvent.

[Manufacturing method: (A) Ingredient aqueous solution No. 1 and No. 2]
138 parts of the hydroxyl group-containing polymer shown in [Table 1] was slowly put into a reaction flask containing 1000 parts of ion-exchanged water, stirred for 1 hour, and then heated to 90 ° C. to completely dissolve the polymer. The mixture was cooled to 50 ° C., 2 mol% of hydroxyl groups of N-methylolacrylamide and 0.1 part of p-toluenesulfonic acid were added as a photosensitive imparting agent, and stirring was continued at 50 ° C. for 3 hours. After cooling the solution to room temperature, add ion-exchanged water so that the solid content becomes 15%, stir at room temperature for another 1 hour, filter with a 5 μm filter, and then add ion-exchanged water to add 10 mass of solid content. %, And (A) component aqueous solution No. 1 and No. I got 2. The obtained (A) component aqueous solution No. 1 and No. The combinations of the hydroxyl group-containing polymer and the photosensitive group-imparting agent used for 2 are summarized in [Table 1].

[Manufacturing method: (A) Ingredient aqueous solution No. 3-6]
138 parts of the hydroxyl group-containing polymer shown in [Table 1] was slowly put into a reaction flask containing 1000 parts of ion-exchanged water, stirred for 1 hour, and then heated to 90 ° C. to completely dissolve the polymer. The mixture was cooled to 40 ° C., 2 mol% of hydroxyl groups, the photosensitive group-imparting agent shown in [Table 1], and 0.7 part of phosphoric acid were added, and stirring was continued at 40 ° C. for 2 hours. After cooling the solution to room temperature, add ion-exchanged water so that the solid content becomes 15%, stir at room temperature for another 1 hour, filter with a 5 μm filter, and then add ion-exchanged water to add 10 mass of solid content. %, And (A) component aqueous solution No. 3 to No. I got 6. The obtained (A) component aqueous solution No. 3 to No. The combinations of the hydroxyl group-containing polymer and the photosensitive group-imparting agent used for No. 6 are summarized in [Table 1].

The above (A) component aqueous solution No. 1 to No. The configurations of 6 are summarized in [Table 2].

ここで、表中の○は該当する構成単位を有することを意味し、－は該当する構成単位を有さないことを意味する。

Here, ◯ in the table means that it has a corresponding structural unit, and-means that it does not have a corresponding structural unit.

[Manufacturing method: (B) component aqueous solution]
10.0 g of the hydroxyl group-containing polymer was slowly added to 90.0 g of the stirring ion-exchanged water, and the mixture was stirred as it was at room temperature for 1 hour. Then, the internal temperature was adjusted from 85 ° C. to 90 ° C., and stirring was continued for 2 hours. After confirming the dissolution, the mixture was cooled to room temperature and filtered through a 1 μm filter. 1 to No. I got 3. The obtained (B) component aqueous solution No. 1 to No. The combinations of the hydroxyl group-containing polymers used in 3 are summarized in [Table 3].

The composition of the aqueous component (B) used in the examples is summarized in [Table 4].

ここで、表中の○は該当する構成単位を有することを意味し、－は該当する構成単位を有さないことを意味する。

Here, ◯ in the table means that it has a corresponding structural unit, and-means that it does not have a corresponding structural unit.

[Examples 1 to 36, Reference Examples 1 to 3 and Comparative Examples 1 to 8] Preparation of water-soluble composition According to the formulation of [Table 5] to [Table 10], each component is stirred at room temperature for 1 hour and then filtered through a 1 μm filter. Filtration was performed to obtain water-soluble compositions (Examples 1 to 36, Reference Examples 1 to 3 and Comparative Examples 1 to 8). The numerical values of the formulations in the table represent parts by mass. The reference numerals of the respective components in the table represent the following components.
A-1: (A) component aqueous solution No. 1 [(A) component aqueous solution]
A-2: (A) component aqueous solution No. 2 [(A) component aqueous solution]
A-3: (A) component aqueous solution No. 3 [(A) component aqueous solution]
A-4: (A) component aqueous solution No. 4 [(A) component aqueous solution]
A-5: (A) component aqueous solution No. 5 [(A) component aqueous solution]
A-6: (A) component aqueous solution No. 6 [(A) component aqueous solution]
B-1: (B) component aqueous solution No. 1 [(B) component aqueous solution]
B-2: (B) component aqueous solution No. 2 [(B) component aqueous solution]
B-3: (B) component aqueous solution No. 3 [(B) component aqueous solution]
C-1: Olga Chix TC-335
(Titanium lactate ammonium salt aqueous solution: component concentration 75%, Ti
Content 5%; manufactured by Matsumoto Fine Chemical Co., Ltd.)
C-2: Olga Chix ZC-126
(Aqueous solution of zirconium chloride: component concentration 30%, Zr content 11%;
Made by Matsumoto Fine Chemical)
C-3: Zincozol ZN
(Aqueous solution of zirconium nitrate, component concentration 46%, Zr content 25%;
Daiichi Rare Element Chemical Industry)
C-4: Olga Chix WS-700
(Organic titanium-modified polyethyleneimine, 10% aqueous solution of component concentration;
Made by Matsumoto Fine Chemical)
D-1: NK Ester A-600
(Alkylene oxide-modified acrylate; manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
D-2: NK Ester A-GLY-20E
(Alkylene oxide-modified acrylate; manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
D-3: NK Economer A-PG5054E
(Alkylene oxide-modified acrylate; manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
D-4: FFM-2 (polyfunctional acrylamide compound; manufactured by Fujifilm)
D-5: Acryloylmorpholine D-6: Hydroxyacrylamide E-1: Megafuck F-444 (Fluorine-based leveling agent; manufactured by DIC)
E-2: KP-112 (silicon-based leveling agent; manufactured by Shin-Etsu Chemical Co., Ltd.)
E-3: Sun Eye Bag IT-15SA (preservative; made by San-Ai Oil)
E-4: DL-Lactic Acid E-5: N, N-Bis (2-Hydroxyethyl) Butane-1 Aminium-Fenyl (2,4,6-trimethylbenzoyl) Phosphinate (Radical Initiator)
E-6: 3-((4- (2-Methyl-2-morpholinopropanoyl) phenyl) thio) propanoic acid = sodium salt (radical initiator)
E-7: N, N-bis (2-hydroxyethyl) butane-1 aminium-2
-Carboxybenzophenone (radical initiator)
E-8: Potassium-2-carboxybenzophenone (radical initiator)
E-9: Dipotassium-4,4'-dicarboxybenzophenone (radical initiator)
F-1: BONJET BLACK W-1
(Manufactured by Orient Chemical Industry Co., Ltd., modified carbon black self-dispersion, concentrated
Degree 20%)
F-2: MICROPIGMO WMRD-5
(Manufactured by Orient Chemical Industry Co., Ltd., Pigment Red17 resin dispersion
Body, concentration 20%)
F-3: MICROPIGMO WMGN-5
(Manufactured by Orient Chemical Industry Co., Ltd., Pigment Green7 resin content
Scatter, concentration 21%)
F-4: MICROPIGMO WMBE-5
(Manufactured by Orient Chemical Industry Co., Ltd., Pigment Blue 15: 6 trees
Fat dispersion, concentration 20%)

[Evaluation of water-soluble composition and cured product]
In the water-soluble compositions of Examples 1 to 36, Reference Examples 1 to 3, and Comparative Examples 1 to 8, compatibility, coatability, photolithography, state change of cured product (moisture heat resistance 1) and haze change (moisture heat resistance 2) ) Was evaluated according to the following procedure. The results are also shown in [Table 5] to [Table 10].

(Compatibility)
The state of each water-soluble composition was visually confirmed and evaluated according to the following criteria.
◯: Uniform Δ: Uniform system, but slightly turbid visually ×: Incompatible, gelled or insoluble matter is observed Those with an evaluation of ○ can be preferably used, and those with an evaluation of × Is not suitable for use.

(Applicability)
Each water-soluble composition is applied onto a glass substrate by a stylus type shape measuring instrument (Dektak 150 manufactured by ULVAC) using a spin coater whose conditions are adjusted so that the film thickness is 5.0 to 5.5 μm, and then 90. Prebaking was performed for 10 minutes on a hot plate at ° C. The state of the film at this time was visually confirmed and evaluated according to the following criteria.
◯: The coating film is uniform Δ: The film is uniform, but turbidity is visually observed. ×: Non-uniform state such as unevenness on the surface or deposits are confirmed. , Can be used favorably, and those with a rating of × are not suitable for use.

(Photolithography)
Each water-soluble composition was applied onto a glass substrate using a spin coater whose conditions were adjusted so that the film thickness was 5.0 to 5.5 μm using a stylus type shape measuring instrument (Dektak 150 manufactured by ULVAC), and then applied. Prebaking was performed on a hot plate at 90 ° C. for 10 minutes. After that, the mixture was cooled to room temperature, irradiated with light containing a wavelength of 365 nm at 500 mJ / cm ² via a photomask (LINE / SPACE = 50 μm / 50 μm) using a high-pressure mercury lamp, and immersed in ion-exchanged water at 23 ° C. for 1 minute. After the immersion, the adhering water was removed with an air gun, and the substrate was dried in an oven at 140 ° C. for 30 minutes. The pattern after drying was confirmed with a laser microscope and evaluated according to the following criteria.
◯: The pattern is within 50 ± 3 μm Δ: 50 ± 10 μm or less ×: 50 ± 10 μm or more or the pattern disappears If the evaluation result is ○ or △, it can be used as a pattern forming agent, and among them, ○ is particularly It can be preferably used, and the one of × is not suitable as a pattern forming agent.

(Moisture resistance 1: Change in state of cured product)
Each water-soluble composition was applied onto a glass substrate using a spin coater whose conditions were adjusted so that the film thickness was 5.0 to 5.5 μm using a stylus type shape measuring instrument (Dektak 150 manufactured by ULVAC), and then applied. Prebaking was performed on a hot plate at 90 ° C. for 10 minutes. Then, after cooling to room temperature, the substrate was dried in an oven at 140 ° C. for 30 minutes by irradiating with light containing a wavelength of 365 nm at 3000 mJ / cm ² using a high-pressure mercury lamp. The obtained cured product was left at 85 ° C. and 85% RH for 24 hours, and then the state of the cured product was visually confirmed. The state of the film after the moisture resistance test was evaluated according to the following criteria.
◯: No change such as peeling and color loss as before the test ×: There is a change The cured product with ○ is usable for applications that require moisture resistance, and the cured product with × is evaluated. , Cannot be used for applications that require moisture resistance.

(Moisture resistance 2: haze change)
Each water-soluble composition was applied onto a glass substrate using a spin coater whose conditions were adjusted so that the film thickness was 5.0 to 5.5 μm using a stylus type shape measuring instrument (Dektak 150 manufactured by ULVAC), and then applied. Prebaking was performed on a hot plate at 90 ° C. for 10 minutes. Then, after cooling to room temperature, the substrate was irradiated with light containing a wavelength of 365 nm at 500 mJ / cm2 using a high-pressure mercury lamp, and the substrate was dried in an oven at 140 ° C. for 30 minutes. The haze of the obtained cured product was measured with Nippon Deniro HAZEMETER NDH5000. Further, the obtained cured product was allowed to stand at 85 ° C. and 85% RH for 24 hours, and then the haze of the cured product was measured in the same manner. Before and after the moisture resistance test, evaluation was made according to the following criteria.
⊚: Haze change amount is less than 0.5 ○: Haze change amount is 0.5 or more and less than 1 △: Haze change amount is 1 or more and less than 3 ×: Haze change amount is 3 or more Evaluation results are ◎, ○ The cured products of and Δ can be used in applications that require moisture and heat resistance, and are excellent in moisture and heat resistance in the order of ◎, ○, and Δ. Among them, the cured product of ⊚ is particularly suitable for applications requiring moisture and heat resistance. On the other hand, the cured product having x cannot be used for applications requiring moisture and heat resistance. In Examples 29 to 36 and Comparative Examples 6 to 8, since the colorant was added, the haze was not measured.

From [Table 1] to [Table 10], it is clear that the water-soluble composition of the present invention has high compatibility, excellent coatability, excellent photolithography, and good moisture and heat resistance of the obtained cured product. be. Therefore, the water-soluble composition of the present invention can be suitably used for applications such as inks, image forming materials and pattern forming agents, and the cured product of the present invention can be suitably used for applications such as optical films.

Claims (9)

A water-soluble photosensitive polymer (A) having a photosensitive group and a hydroxyl group, other than the water-soluble photosensitive polymer (A), the following general formula (I),

(In the general formula (I), * means a bond), which contains the compound (B) having a structural unit represented by the compound (B) and the cross-linking agent (C) .
The compound (B) has the following general formula (III),

A water-soluble composition characterized by being a compound having a structural unit represented by (in the general formula (III), * means a bond) . The water-soluble photosensitive polymer (A) has the following general formulas (IIα), (IIβ) and (IIγ),

In the general formulas (IIα), (IIβ) and (IIγ), Y1 ^, Y2 and Y3 ^each independently represent a direct bond or a ^divalent linking group, where ^Q1 , ^Q2 and ^Q3 are The water-soluble composition according to claim 1, wherein each of them independently represents a photosensitive group, and * means a binder.) It has one or more structural units selected from the group consisting of. The water-soluble composition according to claim 1 or 2, wherein the photosensitive group is a stillvazolium group, a cinnamoyl group, an acrylic group, a methacrylic group, an acrylamide group or a metaacrylamide group. The water-soluble photosensitive polymer (A) has the following general formula (IIδ) or (IIε),

(In the general formulas (IIδ) and (IIε), An ^q- represents a q-valent anion, q represents 1 or 2, p represents a coefficient that keeps the charge neutral, and * means a bond. The water-soluble composition according to any one of claims 1 to 3, which contains the structural unit represented by.). Further, other than the water-soluble photosensitive polymer (A), the following general formula (IV),

(In the general formula (IV), R ¹ represents a hydrogen atom or a methyl group, X ¹ represents an oxygen atom or ^{−NR2-, and R 2 represents} a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Represented, X ² represents an alkylene group having 1 to 6 carbon atoms, and the hydrogen atom of the alkylene group having 1 to 6 carbon atoms represented by X ² may be substituted with a halogen atom or a hydroxyl group, and n Represents a number from 0 to 30, * means a bond, and when there are a plurality of groups represented by the general formula (IV), the plurality of R ¹ , X ¹ , X ² , and n are the same. The water-soluble composition according to any one of claims 1 to 4 , which contains a compound (D) having one or more groups represented by). The water-soluble composition according to any one of claims 1 to 5 , wherein the cross-linking agent (C) is a zirconium compound or a titanium compound. A pattern-forming agent comprising the water-soluble composition according to any one of claims 1 to 6 . A method for producing a cured product, which comprises using the water-soluble composition according to any one of claims 1 to 6 . A cured product comprising the water-soluble composition according to any one of claims 1 to 6 .