JPWO2018117138A1 - Water-soluble composition, pattern forming agent, method for producing cured product using these, and cured product - Google Patents

Abstract

Provided are 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 heat and moisture resistance. Other than the water-soluble photosensitive polymer (A) having a photosensitive group and a hydroxyl group and the water-soluble photosensitive polymer (A), the following general formula (I) (in the general formula (I), * means a bond) .) Is a water-soluble composition containing a compound (B) having a structural unit represented by (II) and a crosslinking agent (C).

Description

  The present invention relates to a water-soluble composition, a pattern forming agent, a method for producing a cured product using the same, and a cured product. Specifically, a cured product having a high-definition pattern and excellent in heat resistance, water resistance, and moisture and heat resistance is obtained. 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 excellent in 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. Patent Document 2 proposes a heat-sensitive recording material excellent in chemical resistance and sticking properties, which contains acetoacetyl-modified polyvinyl alcohol and a silane coupling agent having an amino group as a crosslinking agent. Furthermore, Patent Document 3 proposes a method for producing a crosslinked polyvinyl alcohol resin having excellent weather resistance, which is obtained by crosslinking an acetoacetate ester group-containing polyvinyl alcohol resin with glyoxylate, causing little discoloration due to ultraviolet rays. ing.

Japanese Patent Laid-Open No. 11-310712 JP 2009-039874 A JP2013-028697A

  In applications such as pattern forming agents, inks, various resists, optical films for flat panel displays, optical film coating materials, and adhesives, curing with an increasingly fine pattern and excellent heat resistance, water resistance, and moist heat resistance There is a need for a water-soluble composition that provides a product. Under such circumstances, the water-soluble compositions as proposed in Patent Documents 1 to 3 are not necessarily compatible with the high level required by the market, and further improvements of the water-soluble compositions are required. This is the current situation.

  Therefore, an object of the present invention is to provide 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 moist heat resistance. Is to provide.

  As a result of intensive 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. As a result, the present invention has been completed.

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

(In general formula (I), * means a bond.) The compound (B) has a structural unit represented by the formula (I), and a crosslinking agent (C).

（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、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), Y ¹ , Y ² and Y ³ each independently represent a direct bond or a divalent linking group, and Q ¹ , Q ² and Q ³ are It preferably represents at least one constituent unit selected from the group consisting of a photosensitive group and * means a bond. In the water-soluble composition of the present invention, the photosensitive group is preferably a stilbazolium group, a cinnamoyl group, an acrylic group, a methacryl group, an acrylamide group, or a methacrylamide group. Furthermore, in the water-soluble composition of the present invention, the water-soluble photosensitive polymer (A) is represented by the following general formula (IIδ) or (IIε),

(In general formulas (IIδ) and (IIε), An ^q- represents a q-valent anion, q represents 1 or 2, p represents a coefficient for maintaining a neutral charge, and * represents a bond. It is preferable to contain the structural unit represented by. Furthermore, in the water-soluble composition of the present invention, the compound (B) is represented by the following general formula (III),

(In general formula (III), * means a bond.) A compound having a structural unit represented by formula (III) is preferred. Furthermore, in the water-soluble composition of the present invention, in addition to 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 —NR ² —, and R ² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. represents, X ² represents an alkylene group having 1 to 6 carbon atoms, a hydrogen atom of an 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 the general formula (IV), a plurality of R ¹ , X ¹ , X ² and n are the same. It is preferable that the compound (D) which has 1 or more groups represented by these may be different. Furthermore, in the water-soluble composition of the present invention, the crosslinking agent (C) is preferably a zirconium compound or a titanium compound.

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

  Furthermore, the method for producing a cured product of the present invention is characterized by using the water-soluble composition of the present invention.

  Furthermore, the cured product of the present invention is characterized by comprising the water-soluble composition of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the water-soluble composition from which the hardened | cured material which is excellent in heat resistance, water resistance, and heat-and-moisture resistance is obtained, a pattern formation agent, the manufacturing method of hardened | cured material using these, and hardened | cured material are provided. can do. The water-soluble composition of the present invention can be suitably used for applications such as pattern forming agents, optical films for flat panel displays, optical film coating materials, or adhesives.

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 a water-soluble photosensitive polymer (A) having a photosensitive group and a hydroxyl group (hereinafter also referred to as “component (A)”), other than the water-soluble photosensitive polymer (A), The following general formula (I),

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

<(A) component>
The component (A) according to the water-soluble composition of the present invention is not particularly limited as long as it has a photosensitive group and a hydroxyl group. Preferred examples of the component (A) include compounds having the following general formulas (IIα) to (IIε) as structural units because the cured product has high heat resistance, water resistance, and moist heat resistance. Among these, (IIδ) And a compound having (IIε) as a structural unit is obtained from a water-soluble composition having excellent curability even when an LED light source (365 nm) is used, and a cured product having excellent heat resistance, water resistance, and moist heat resistance. 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 bond or a divalent linking group, Q ¹ , Q ² and Q ³ each independently represent a photosensitive group, and * represents a bond. is there.

Here, in general formulas (IIδ) and (IIε), An ^q− represents a q-valent anion, q represents 1 or 2, p represents a coefficient for maintaining a neutral charge, 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 examples thereof include a methylene group, an ethylene group, and trimethylene. Group, an alkylene group having 1 to 10 carbon atoms such as 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—, —SO ₂ — and a linking group in which two or more of these are combined is preferable. Can do. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.

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 cinnamoyl group, a cinnamylidene group, a cinnamylidene acetyl group, a chalcone Group, coumarin group, isocoumarin group, 2,5-dimethoxystilbene group, maleimide group, α-phenylmaleimide group, 2-pyrone group, azide group, thymine group, quinone group, uracil group, pyrimidine group, stilbazolium group, styrylpyridinium Group, tyrylquinolium group, epoxy group, oxetane group, vinyl ether group, allyl ether group, acrylic group, methacryl group, acrylamide group, methacrylamide group, vinyl group, allyl group, styryl group, etc., among these, (A) When incorporated in a water-soluble composition as a component, the photosensitivity is high. Preferably a stilbazolium group, cinnamoyl group, acrylic group, methacryl group, acrylamide group or methacrylamide group is used because a water-soluble composition having high liquid stability (without thickening, gelation, precipitation, etc.) can be obtained. Can do.

  Among these photosensitive groups, the stilbazolium group is highly soluble in water and has an absorption band in the vicinity of 365 nm. Therefore, a water-soluble composition that exhibits photosensitivity even in a light source with a long wavelength such as an LED light source (365 nm). Things are obtained. From this water-soluble composition, a cured product having a high-definition pattern in addition to heat resistance, water resistance and heat-and-moisture resistance can be obtained.

  Specific examples of preferable component (A) include water-soluble photosensitive polymers represented by the following general formula (V) and 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), 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 not simultaneously 0, 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 in the general formula (V), a and d are not 0 simultaneously, and 100 <a + b + c + d <5000, and * Is a bond.

  Since the cured product obtained from the water-soluble composition of the present invention has good heat resistance and adhesion, preferred values of a, b, c and d (molar ratio) in the general formulas (V) and (VI) are as follows: a: b: c: d = 0.1 to 4: 5 to 30: 5 to 70: 0.1 to 4, and a weight average molecular weight of 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 a butenediol-polyvinyl alcohol copolymer with an aldehyde having a photosensitive group under the conditions of pH 1 to 4. Moreover, it can also manufacture by using a commercial item, for example, G polymer (butenediol vinyl alcohol copolymer) OKS-1081, OKS-1083, and OKS-1109 by Nippon Synthetic Chemical Co., Ltd. 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 more preferably 10 to 90 parts by mass in terms of solid content with respect to 100 parts by mass of the sum of the components (A) and (B). The mass part is most preferable because a cured product having a high-definition pattern and excellent in heat resistance, water resistance, and moist heat resistance can be obtained.

<(B) component>
(B) component which concerns on the water-soluble composition of this invention does not have the said photosensitive group in a structure, and should just have the structural unit represented by the following general formula (I), especially It is not limited.

ここで、一般式（Ｉ）中、＊は結合手である。

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

  Component (B) has the same main chain as polyvinyl alcohol known in the art and is generally copolymerized with polyvinyl alcohol obtained by polymerizing vinyl alcohol, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, or vinyl acetate. And 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 having vinyl alcohol as an essential monomer.

  (B) Although it does not specifically limit as a manufacturing method of a component, For example, the method of reacting polyvinyl alcohol and diketene, The method of reacting polyvinyl alcohol and acetoacetic ester, and transesterifying, Vinyl acetate and acetoacetic acid Examples thereof include a method for saponifying a vinyl copolymer. Among these, since the production process is simple and polyvinyl alcohol having a good quality acetoacetate group can be obtained, it is preferable to produce by a method of reacting polyvinyl alcohol and diketene.

  Examples of monomers copolymerizable with vinyl acetate include maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, acrylic acid, methacrylic acid and other unsaturated carboxylic acids and esters thereof, ethylene, Α-olefins such as propylene, allyl sulfonic acid, methallyl sulfonic acid, allyl sulfonic acid soda, methallyl sulfonic acid soda, sulfonic acid soda, sulfonic acid soda monoalkyl malate, disulfonic acid soda alkyl malate, N-methylol acrylamide Acrylamide alkylsulfonic acid alkali salts, N-vinylpyrrolidone, N-vinylpyrrolidone derivatives and the like. These monomers are preferably 10 mol% or less, particularly 5 mol% of all structural units. If the amount is too large, the water solubility may decrease, or the compatibility with the component (C) described later may decrease.

  The component (B) having a polystyrene-reduced weight average molecular weight (Mw) by gel permeation chromatography (GPC) of 10,000 to 200,000 and a saponification degree (hydrolysis rate) of 85 to 100 is water resistant. 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 the compound which has a structural unit represented by this is used, since the heat resistance of the hardened | cured material obtained from the water-soluble composition of this invention, water resistance, and moist heat resistance are especially excellent, it is more preferable.

  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%, particularly 0.3 to 10 mol%. Is preferable from the viewpoints of water resistance of the cured product, crosslinking rate, water solubility, and aqueous solution stability.

  (B) As a component, a commercial item can also be used, for example, Gohsenx Z-100, Z-200, Z-220, Z-300, and Z-410 (made by Nippon Synthetic Chemical Industry) etc. are mentioned.

  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 sum of the components (A) and (B). preferable. When the content of the component (B) is in the above range, a cured product having a high-definition pattern and excellent in heat resistance, water resistance, and moist heat resistance is preferable.

<(C) component>
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 crosslinking agent, a metal chelate complex having a chelating agent, a zirconium compound and a titanium compound can be preferably used.

  The organic crosslinking agent can be arbitrarily selected from those conventionally used as a crosslinking agent, for example, a bisdiazide compound, an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, Examples thereof include guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, and ethylene urea-formaldehyde resin. These may be those obtained by reacting melamine, urea, guanamine, glycoluril, succinylamide, or ethyleneurea with formalin in boiling water to form methylol, or further reacting it with a lower alcohol to produce alkoxylation.

  Examples of chelating agents include hydroxycarboxylic acid or a salt thereof, glyoxylic acid or a salt thereof, amino alcohol, aminocarboxylic acid, alanine, arginine, leucine, isoleucine, dihydroxypropyl glycine, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, β-diketone, dimethylglyoxime, citric acid, tartaric acid, maleic acid, polyhydrazide, phosphate ester and the like can be mentioned, 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 with one or more bidentate by a covalent bond, hydrogen bond, or the like is used, the crosslinking reaction rate Is preferable because it is moderately adjusted. Specific examples of the chelate-type ligand include hydroxycarboxylic acid or a salt thereof, amino alcohol, β-diketone and the like.

  Zirconium compounds include zirconium halides such as zirconium oxychloride, hydroxyzirconium chloride, zirconium tetrachloride and zirconium bromide; mineral acids such as zirconium sulfate, basic zirconium sulfate, zirconium oxynitrate, zirconium oxyacetate and zirconium oxycarbonate. Zirconium salts; zirconium salts 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 ammonium, sodium zirconium sulfate, ammonium zirconium acetate, ammonium zirconium carbonate, zirconium carbonate Bromide potassium, sodium oxalate, zirconium sodium citrate, zirconium ammonium citrate, other zirconium complex salts such as zirconium lactate ammonium, one or two or more chelating agents include zirconium chelate complex having a ligand. Among these, water-soluble zirconium is preferable, and zirconium oxyhalide, zirconium oxyacetate, zirconium sulfate, and zirconium oxynitrate are more preferable.

  Examples of zirconium chelate complexes include zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium oxyhalide, zirconium oxynitrate, zirconium lactate ammonium, zirconium sulfate and zirconium oxyacetate, zirconium bisacetylacetonate, zirconium monoethylacetate. Examples include acetate and zirconium acetate.

  Among the zirconium compounds, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium oxyhalide, zirconium oxynitrate, zirconium lactate ammonium, zirconium sulfate and zirconium oxyacetate have high stability, water solubility and reactivity. preferable. These can be used as one kind or a mixture of two or more kinds.

  Commercially available products can also be used as the zirconium compound, such as zirconium oxychloride, zircozole ZC-2, zircozole ZN, zircozol HA, zircozol AC-7, zircozole ZK-10, zircozole ZN, zircozol ZA-10, zircozol ZA-. 20, zirconyl octylate, zirconyl carbonate (manufactured by Daiichi Kagaku Kagaku Kogyo Co., Ltd.), ORGATIZ ZA-45, ORGATIZ ZA-65, ORGATIZ ZB-126, ORGATIZ ZC-126, ORGATIZ ZC-150, ORGA Chicks ZC-200, Olga Chicks ZC-300, Olga Chicks ZC-320, Olga Chicks ZC-540, Olga Chicks ZC-580, Olga Chicks ZC-700, ZC-300 (manufactured by Matsumoto Fine Chemical Co., Ltd.), etc. And the like.

  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, tetra Titanium alkoxides such as methyl titanate; oligomers and polymers obtained by hydrolysis decomposition of titanium alkoxides such as titanium butyl dimer and titanium butyl tetramer, and derivatives thereof; titanium acetylacetonate, titanium octylene glycolate, titanium tetraacetylacetonate , Titanium chelate complexes such as titanium ethyl acetoacetate, titanium triethanolaluminate, titanium oxalate ; Titanium acylates such as polyhydroxytitanium stearate; titanium tetrachloride, titanium lactate, titanium triethanolamate, diisopropoxytitanium bis (triethanolaminate), etc., which are used alone or as a mixture of two or more thereof Can be used as

  Commercially available products can also be used as the titanium compound, for example, ORGATICS TA-8, ORGATICS TA-10, ORGATICS TA-12, ORGATICS TC-100, ORGATICS TC-120, ORGATICS TC-300, ORGATICS TC-310, ORGATICS TC-315, ORGATICS TC-335, ORGATICS TC-401, ORGATICS 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 wet heat resistance.

  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 such as precipitation or thickening and the water-soluble composition is stable.

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

The compound represented by these may be contained. Here, in general formula (IV), R ¹ represents a hydrogen atom or a methyl group, X ¹ represents an oxygen atom or —NR ² —, and R ² represents a hydrogen atom or a hydrocarbon having 1 to 20 carbon atoms. represents a group, X ² represents an alkylene group having 1 to 6 carbon atoms, a hydrogen atom of an 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), 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 preferably an alkyl group having 1 to 20 carbon atoms and the number of carbon atoms. An alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms Etc. (B) Since the sensitivity when used as a component is good, the alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, the cycloalkyl group having 3 to 10 carbon atoms, the number of carbon atoms A cycloalkylalkyl group having 4 to 10 carbon atoms, 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, isooctyl, Examples include 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and icosyl. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, Propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl and isodecyl All It is.

  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, 8,12-tetradecatrienylallyl and the like are mentioned, 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, - octenyl, 3-nonenyl and 4-decenyl and the like.

  A 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, tetradecahydroanthracenyl, 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.

  The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of the alkyl group is substituted with a 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-cyclodecylbutyl, 3-3-adamantylpropyl, decahydronaphthylpropyl and the like. Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl, Cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, Examples include 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl and 4-cyclohexylbutyl. It is.

  Examples of the aryl group having 6 to 20 carbon atoms include one or more substituted with, for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, the above alkyl group, the above alkenyl group, a carboxyl group, a halogen atom, or the like Phenyl, biphenylyl, naphthyl, anthryl, etc., such as 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, etc. -10 aryl groups include, for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, etc., phenyl, biphenylyl, naphthyl, one or more substituted with one or more of the above alkyl groups, alkenyl groups, carboxyl groups, halogen atoms, etc. Anthril, etc. Rofeniru, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, and the like.

  An arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 30 carbon atoms in which a 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 are mentioned. The arylalkyl group having 7 to 20 carbon atoms is an alkyl group in which a hydrogen atom is an aryl group. By substituted is meant a group having from 7 to 20 carbon atoms. Examples include benzyl, α-methylbenzyl, α, α-dimethylbenzyl and phenylethyl.

Examples of the alkylene group having 1 to 6 carbon atoms represented by X ² in the general formula (IV) include linear chains such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. Examples include alkylene groups and branched alkylene groups such as isopropylene groups and isobutylene groups.

  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.

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 in the general formula (IV), 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 having 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 diethylene oxide-modified neopentyl glycol dimethacrylate, dipropylene oxide-modified neopentyl glycol dimethacrylate, diethylene oxide-modified 1,6-hexanediol dimethacrylate, diethylene oxide, and the like. And propylene oxide modified 1,6-hexanediol dimethacrylate That.

  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 Economer A-PG5054E (hereinafter, Shin-Nakamura Chemical). (Made by industry) etc. are mentioned.

Of the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound, those in which X ² 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 of its excellent resistance.

  When the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound have one group represented by the general formula (IV), the case where n is 6 or more is particularly preferable because of excellent water solubility. In the case where the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound have a plurality of groups represented by the general formula (IV), since the water-solubility is excellent, the case where the sum of the plurality of n presents is 10 or more is particularly preferable. preferable.

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

  Examples of the acrylamide compound include hydroxyacrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-butylacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N, N. -Dipropylacrylamide, acryloylmorpholine, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide and the like. Examples of the methacrylamide compound include hydroxymethacrylamide, N-methylmethacrylamide N-ethylmethacrylamide, N-isopropylmethacrylamide, N-butylmethacrylamide, diacetonemethacrylamide, N, N-dimethyl Methacrylamide, N, N-diethylmethacrylamide, N, N-dipropylmethacrylamide, methacryloylmorpholine, Nn-butoxymethylmethacrylamide, N-isobutoxymethylmethacrylamide, N-methoxymethylmethacrylamide, etc. It is done.

  Commercially available products can also be preferably used as the acrylamide compound and the methacrylamide compound, and examples thereof include FFM-2, FFM-3, FFM-4 and FFM-5 (manufactured by Fuji Film Co., Ltd.).

  When (D) component is contained, content of (D) component is 1-50 mass parts with respect to 100 mass parts of total of (A) component, (B) component, and (D) component, (D ) When the content of the component is within 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 excellent in heat resistance, water resistance, and heat and moisture resistance. Since it is obtained, it is preferable.

  The water-soluble composition of the present invention only needs to contain water as a solvent and can be used in combination with an organic solvent. It is preferable because it does not attack organic materials.

  Examples of the organic solvent include solvents that can dissolve or disperse the above-described components (component (A), component (B), component (C) and component (D)), etc., when used in combination with water, such as methyl ethyl ketone. , Ketones such as methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and Ether solvents such as dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, 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 hydrocarbons such as hexane, heptane, octane and cyclohexane Solvents; Terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; paraffinic solvents such as mineral spirit, Swazol # 310 (above, manufactured by Cosmo Matsuyama Petroleum); and Solvesso # 100 (above, manufactured by Exxon Chemical); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine , Acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water and the like. Alcohol solvents are preferred because they are compatible 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 that the solvent is only one liquid because it does not attack the organic material when it is applied to the organic material with 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 within the above range, the curable composition and the curing excellent in handling properties (viscosity and wettability of the curable composition) and liquid stability (without precipitation or precipitation of components contained in the composition). This is preferable because the thickness of the object can be appropriately controlled.

  If necessary, the water-soluble composition of the present invention includes a water-soluble polymer, an organic acid, a coupling agent, a sensitizer, a surfactant, and a basic compound that do not belong to the components (A) and (B). Coloring agents, radical initiators, water-soluble preservatives, conductive materials, and the like can also be added.

  Examples of the water-soluble polymer not belonging to the component (A) and the component (B) include oxidized starch, etherified / esterified / grafted modified starch, cellulose derivatives such as gelatin, casein, carboxymethylcellulose, polyvinylpyrrolidone, water Water-soluble polyacrylate resin such as water-soluble polyester resin, 2-hydroxypropyl acrylate polymer, 4-hydroxybutyl acrylate polymer, water-soluble polycarbonate resin, water-soluble polyvinyl acetate resin, water-soluble styrene acrylate resin, water-soluble vinyl toluene acrylate Resin, water-soluble polyurethane resin, water-soluble polyamide resin such as polyvinylamide / polyacrylamide, modified acrylamide, water-soluble urea resin, water-soluble polycaprolactone resin, water-soluble polystyrene resin, water-soluble polychlorination Sulfonyl resin, water-soluble polyacrylate resin, a water-soluble resin and a styrene-butadiene copolymer, such as a water soluble polyacrylonitrile resins, acrylic acid ester copolymers, ethylene-vinyl acetate copolymers 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, octylic acid, Examples include caprylic acid, glucuronic acid, stearic acid, benzoic acid, and mandelic acid. Among these, lactic acid, acetic acid, citric acid, glycolic acid or malic acid is preferable.

  Examples of the coupling agent include alkyl functionalities such as dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkenyl functional alkoxysilanes such as functional alkoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxybromotrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ-glycid Epoxy-functional alkoxysilanes such as cyclopropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) -γ-amino Use amino-functional alkoxysilanes such as propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane. Can do.

  The sensitizer is a compound capable of expanding the wavelength range in which light can be applied when cured by light irradiation. 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, Benzophenones such as 1,3-dimethyl-4-methoxybenzophenone, 4-phenylbenzophenone, acetophenone, 4-methoxyacetophenone, 2,4-dimethoxyacetophenone, 2,5-dimethoxyacetophenone, 2,6-dimethoxya Acetophenones such as tophenone, 4,4-dimethoxyacetophenone, 4-ethoxyacetophenone, diethoxyacetophenone, 2,2-diethoxyacetophenone, 2-ethoxy-2-phenylacetophenone, 4-phenylacetophenone, anthraquinone, hydroxyanthraquinone, 1 -Anthraquinones such as nitroanthraquinone, aminoanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, anthraquinonesulfonic acid, 1,2-benzanthraquinone, 1,4-hydroxyanthraquinone (quinizarin), anthracene, 1 , 2-benzoanthracene, 9-cyanoanthracene, 9,10-dicyanoanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9, Anthracene such as 0-bis (phenylethyl) anthracene, 2,3-dichloro-6-dicyano-p-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, methoxybenzoquinone, 2,5- Quinones such as dichloro-p-benzoquinone, 2,6-dimethyl-1,4-benzoquinone, 9,10-phenanthrequinone, camphor-quinone, 2,3-dichloro-1,4-naphthoquinone, xanthone, thioxanthone Thiooxanes such as 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-isopropylthioxanthone, dibenzosuberone, dibenzosuberene , Cycloheptanes such as dibenzosuberenol and dibenzosuberane, 2-methoxy Aromatic compounds such as naphthalene, benzoin isopropyl ether, 4-benzoyldiphenyl, o-benzoylbenzoic acid, methyl o-benzoylbenzoate, 4-benzoyl-4-methyl-diphenyl sulfide, benzyl, benzoin methyl ether, and dye-based compounds Examples thereof include coumarin-based, thiazine-based, azine-based, acridine-based, and xanthene-based compounds.

  Examples of the surfactant include fluorine surfactants 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 halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and 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. These may be used alone or in combination of two or more, and a basic compound may be added for the purpose of pH adjustment.

  As the colorant, pigments and dyes can be used. 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 admixture of two or more. Here, the pigment refers to a colorant that is insoluble in a solvent to be described later, and includes inorganic or organic colorants that are insoluble in a solvent, or those obtained by rake formation of an inorganic or organic dye.

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, a carbon black adjusted or coated with an epoxy resin, and the carbon black In which a resin is dispersed in a resin in advance and coated with 20 to 200 mg / g of resin, the above-mentioned carbon black is subjected to an acidic or alkaline surface treatment, an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less of carbon black, the total amount of oxygen calculated from the CO and CO ₂ in volatiles at 950 ° C. is, carbon black is surface area 100 m ² per 9mg above, graphitized carbon black, graphite, activated carbon, carbon fibers, carbon nanotubes, -Bonn microcoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, black pigments typified by titanium black, chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphorus Organics such as acid salt blue, bituminous, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, brown (red iron (III) oxide), cadmium red, synthetic iron black, amber, lake pigment Or an inorganic pigment is mentioned, It is preferable to use a black pigment from a high light-shielding property, and it is more preferable to use carbon black as a black pigment.

  Commercially available products can also 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, MICROPIGMOWMV, MICROPIGMO WMWE-1, BONJET BLACK CW-1 (above, manufactured by Orient Chemical Industries) 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, 20 215, 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 Green 7, 10, 36 and 58; Pigment Blue 15, 15: 1, 15: 2, 1 5: 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 etc. are mentioned.

  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, isoindoline compounds, quinacridone compounds, anthanthrones. Compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids, azo dyes, metal complex compounds of cyanine dyes, and the like.

  Conventionally known compounds can be used as the radical initiator. For example, JP-A-57-197289, JP-A-6-228218, JP-A-2009-102455, JP-2012-007071, JP-A-2006-510314, In addition to those described in WO2014 / 050551, JP-A-06-239910, JP-A-2003-192712, JP-A-2006-185929, benzophenone, carboxybenzophenone and its salt, dicarboxybenzophenone and its salt, thioxanthone, 1-chloro- Hydrogen abstraction type photopolymerization initiators such as 4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone; phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane (α Roxyalkylphenone), benzoin, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholy-2- (4′-methylmercapto) benzoylpropane, 4-benzoyl -4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, benzoylformic acid Methyl, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2 -Methyl-1-propan-1-one, 1,7-bis (9'-acridinyl) 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) -4,5,4 ′, 5′-tetraphenyl-1-2′-biimidazole, acylphosphine oxide, bisacylphosphine oxide, triphenylphosphine oxide, etc. A photopolymerization initiator can be used, and a photodegradable photopolymerization initiator is preferable from the viewpoint of reactivity.

  Among the photodegradable photopolymerization initiators, water-soluble initiators such as Irg2959, Irg819DW (manufactured by BASF), ESACURE ONE, ESACURE 1001M, ESACURE KIP 150, ESACURE DP 250 (Lamberti), etc. have an affinity for water. It is preferable because of its high properties.

  Commercially available products may be used as the dye, and examples of the water-soluble dye include 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 105S, WATER BLUE 105S VIOLET 7, WATER BLACK 31, WATER B ACK 191-L, WATER BLACK 256-L, WATER BLACK R-455, WATER BLACK R-510, BONJET YELLOW 161-L, BONJET MAGENTA XXX, BONJET Cyan XXX, BONJET BLACK 891-L (above, Orient Chemical Industries, Ltd.) ) And the like.

  Oil soluble dyes include VALIFAST YELLOW 1101, VALIFAST YELLOW 3150, VALIFAST RED 1308, VALIFAST RED 2320, VALIFAST PINK 1364, VALIFAST PINK 2310N, VALIFAST VIOLET 15 VALIFAST BLACK 3820, VALIFAST BLACK 3830, VALIFAST BLACK 3840, VALIFAST BLACK 3866, VALIFAST BLACK 3870, VALIFAST ORANGE 210, VALIFAST BROWN 3402, VALIFAST BLUE 1613, and VALIFAST BLUE 1605 (above, manufactured by Orient Chemical Industries, Ltd.) and the like.

  Examples of the water-soluble preservative include those having a high solubility in water and a solubility at room temperature of 1% or more. Specifically, methylparaben, benzoic acid, benzoate, salicylic acid, 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 Quaternary ammonium compound), CUAZ (copper / azole compound), AAQ (quaternary ammonium compound), sodium hydrogen sulfite, sodium hydrogen sulfate, sodium thiosulfate, ascorbate, benzalkonium chloride, chlorobutanol, thimerosal, Phenylmercuric acetate Acid phenyl mercury phenylmercuric nitrate, parabens, methylparaben, polyvinyl alcohol, benzyl alcohol, isothiazolone, triazine, bronopol, thiabendazole, zinc pyrithione, carbendazim, pyridine oxide thiol sodium salt and phenyl ethanol and the like.

  Commercially available products may be used as the water-soluble preservative, such as Sun Eye Back P, Sun Eye Back 300K, Sun Eye Back IT-15SA, Sun Eye Back AS-30, Sun Eye Back T-10, Sun Eye Back M-30, Sun Eye Back. Examples include sodium omadin (all manufactured by Sanai Oil).

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

  Examples of the metal include gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead. Examples 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 is preferable.

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

  Examples of the conductive polymer include polyacetylene, polypyrrole, poly (3-methylpyrrole), poly (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), and poly (3 , 4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3-hydroxypyrrole), poly (3-methyl-4-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxy Pyrrole), poly (3-octoxypyrrole), poly (3-carboxylpyrrole), poly (3-methyl-4-carboxylpyrrole), polyN-methylpyrrole, polythiophene, poly (3-methylthiophene), poly ( 3-butylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3 Dodecylthiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-octoxythiophene), poly (3-carboxylthiophene), poly (3-methyl-4-carboxylthiophene), poly (3,4-ethylenedioxythiophene), polyaniline, poly (2-methylaniline), poly (2-octylaniline), poly (2-isobutylaniline), poly (3-isobutylaniline), poly (2-aniline) Examples include sulfonic acid), poly (3-aniline sulfonic acid), and polythiophene derivatives (PEDOT: poly (3,4) -ethylenedioxythiophene) doped with polystyrene sulfonic acid (PSS).

  In addition to the above, a photopolymerization initiator, a thermal polymerization initiator, a photobase initiator, an acid generator, an inorganic filler, an organic filler, an antifoaming agent, an increase agent may be used as long as the effects of the present invention are not impaired. Sticky agent, leveling agent, organometallic coupling agent, thixotropic agent, carbon compound, metal fine particle, metal oxide, flame retardant, plasticizer, light stabilizer, heat stabilizer, anti-aging agent, elastomer particle, chain transfer agent, Various resins such as polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, mold release agents, flow regulators, adhesion promoters, unsaturated monomers, and cationically polymerizable compounds such as epoxy compounds, oxetane compounds, and vinyl ethers 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 is composed of the water-soluble composition of the present invention. The pattern forming agent of the present invention has photolithographic properties. Specifically, after light irradiation through a mask, development is performed using a developer (such as water, an organic solvent, and an alkaline aqueous solution). A pattern of 1000 μm or less can be formed with good accuracy within ± 10%.

  The manufacturing method of the hardened | cured material of this invention is performed using the water-soluble composition or pattern formation agent of this invention. A preferable coating method and curing conditions are shown below for a method for producing a cured product using the water-soluble composition or pattern forming agent of the present invention.

  A preferable coating method is applied on a supporting substrate such as glass, metal, paper, and plastic by a known means such as a spin coater, a bar coater, a roll coater, a curtain coater, various types of printing, and dipping. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  Examples of the transparent support material include inorganic materials such as glass; cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; polyamides; polycarbonates; polyethylene terephthalate Polyesters such as polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate, polystyrene, polyethylene, Polyolefins such as polypropylene and polymethylpentene; Acrylic resins such as polymethyl methacrylate; Polycarbonate; Polysulfone; Li ether sulfone; polyether ketone; polyetherimides; polyoxyethylene, and polymer materials such as norbornene resins. The transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze is preferably 2% or less, and more preferably 1% or less. The refractive index is preferably 1.45 to 1.70.

Preferred curing conditions are as follows. When light irradiation is performed after the water-soluble composition or pattern forming agent of the present invention is applied on a transparent support, the irradiation conditions such as the wavelength, intensity, and irradiation time of the irradiated light are light. Although it is appropriately adjusted depending on the activity of the initiator, the activity of the photopolymerizable resin to be used, etc., the light wavelength is preferably one having a wavelength peak of 300 to 500 nm in order to allow light to enter the inside sufficiently. More preferred is a wavelength peak of 350 to 450 nm, and most preferred is a wavelength peak of 360 to 380 nm. And is preferably 10 to 300 mW / cm ² as light intensity, more preferably 25~100mW / cm ^2, time is preferably 5 to 500 seconds irradiation, more preferably 10 to 300 seconds.

  By applying the water-soluble composition or pattern forming agent of the present invention on a transparent support and then heating it, the crosslinking reaction can also proceed. Heating is performed at 50 to 200 ° C., preferably 70 to 150 ° C. for 10 to 1 hour. If the temperature is lower than 50 ° C, the crosslinking reaction may not proceed. If the temperature is higher than 200 ° C, the components (A) to (D) may be decomposed or the transparency of the optical film may be decreased.

When a pattern of a cured product is prepared by photolithography, the water-soluble composition or pattern forming agent of the present invention is formed 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 coating using a spin coater whose conditions were adjusted to 5 μm, pre-baking was performed on a hot plate at 90 ° C. for 10 minutes. Then, it is cooled to room temperature, irradiated with 500 mJ / cm ^{2 of} light containing a wavelength of 365 nm through a photomask (LINE / SPACE = 50 μm / 50 μm) using a high-pressure mercury lamp, and ion-exchanged water at 23 ° C. for 1 minute. After the immersion, the water attached with an air gun is removed, and the substrate is dried in an oven at 140 ° C. for 30 minutes. Preferred curing conditions are the same as described 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 glasses, optical materials represented by imaging lenses, paints, various coating agents, lining agents, inks, resists, liquid resists, adhesives, Sealant for liquid crystal dropping method, image forming material, pattern forming material, printing plate, insulating varnish, insulating sheet, laminated board, printed circuit board, for semiconductor device, LED package, liquid crystal inlet, organic EL, and optical element・ Sealants for electrical insulation, electronic parts, separation membranes, molding materials, putty, building materials, siding, glass fiber impregnating agents, sealants, passivation films for semiconductors and solar cells, interlayer insulation films , Protective film, prism lens sheet used for backlight of liquid crystal display device, Fresnel lens sheet used for screen of projection TV, etc. Lens parts of lens sheets such as lenticular lens sheets, or backlights using such sheets, protective films and spacers for liquid crystal color filters, 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, MEMS elements, actuators, holograms, plasmon devices, polarizing plates, polarizing films, microlenses and other optical lenses, optical elements, optical connectors, optical waveguides Examples of the base material that can be applied as a coating agent include metals, wood, rubber, plastics, 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 a sheet by a conventional method, and the obtained film or sheet is not stretched (or oriented). You may manufacture and you may manufacture by extending | stretching (or orientation processing). 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 (cast 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 as to the shape, but is usually a film having an optical film on a transparent support and used for optical applications. Used in various functional films such as protective films for polarizing plates used in liquid crystal display devices, retardation films, viewing angle widening films, antireflection films used in plasma displays, low reflectivity films, organic EL displays, etc. And various functional films.

  An optical film using the water-soluble composition and pattern forming agent of the present invention is an optical recording layer of a write-once optical disc (CD ± R, DVD ± R, next-generation high-density disc, etc.) in which the optical film is applied to a support. Various lenses; optical filters for image display devices; various filters represented by color filters and color conversion filters; or used as protective sealing films for organic EL light-emitting elements, inorganic EL light-emitting elements, electronic paper display bodies, and the like. it can.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples. In addition, solid content described in a present Example means the mass% which the component except a solvent occupies.

[Production method: (A) Component 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. for complete dissolution. After cooling to 50 ° C., 2 mol% of N-methylol acrylamide and 0.1 part of p-toluenesulfonic acid as a photosensitizer were added, and stirring was continued at 50 ° C. for 3 hours. After cooling the solution to room temperature, ion-exchanged water was added so that the solid content was 15%, and the mixture was further stirred for 1 hour at room temperature, filtered through a 5 μm filter, and then ion-exchanged water was added to bring the solid content to 10 mass. %, Component (A) aqueous solution No. 1 and no. 2 was obtained. The obtained aqueous solution (A) No. 1 and no. For Table 2, the combinations of the hydroxyl group-containing polymer and the photosensitive group imparting agent used are summarized in [Table 1].

[Production method: (A) Component 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. for complete dissolution. It cooled to 40 degreeC, the photosensitive group provision agent shown in [Table 1] for 2 mol% of a hydroxyl group, and 0.7 part of phosphoric acid were thrown in, and stirring was continued at 40 degreeC for 2 hours. After cooling the solution to room temperature, ion-exchanged water was added so that the solid content was 15%, and the mixture was further stirred for 1 hour at room temperature, filtered through a 5 μm filter, and then ion-exchanged water was added to bring the solid content to 10 mass. %, Component (A) aqueous solution No. 3-No. 6 was obtained. The obtained aqueous solution (A) No. 3-No. For Table 6, the combinations of the hydroxyl group-containing polymer and the photosensitive group imparting agent used are summarized in [Table 1].

  The above-mentioned (A) component aqueous solution No. 1-No. The configuration of 6 is 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 the corresponding structural unit is included, and-means that the corresponding structural unit is not included.

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

  The composition of the component (B) aqueous solution 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 the corresponding structural unit is included, and-means that the corresponding structural unit is not included.

[Examples 1 to 39 and Comparative Examples 1 to 8] Preparation of water-soluble composition Each component was stirred at room temperature for 1 hour in accordance with the formulation of [Table 5] to [Table 10], and then filtered through a 1 μm filter. The thing (Examples 1-39 and Comparative Examples 1-8) was obtained. In addition, the numerical value of the mixing | blending in a table | surface represents a mass part. Moreover, the code | symbol of each component in a table | surface represents the following component.
A-1: (A) component aqueous solution No. 1 [(A) component aqueous solution]
A-2: Component (A) 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: Component (A) 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: Component (B) aqueous solution No. 2 [(B) Component aqueous solution]
B-3: Component (B) aqueous solution No. 3 [(B) Component aqueous solution]
C-1: Olga Chicks TC-335
(Titanium lactate ammonium salt aqueous solution: component concentration 75%, Ti
5% content; made by Matsumoto Fine Chemical)
C-2: Olga Chicks ZC-126
(Zirconyl chloride aqueous solution: component concentration 30%, Zr content 11%;
Made by Matsumoto Fine Chemical)
C-3: Zircosol ZN
(Zirconyl nitrate aqueous solution, component concentration 46%, Zr content 25%;
1st rare element chemical industry)
C-4: ORGATICS WS-700
(Organic titanium-modified polyethyleneimine, component concentration 10% aqueous solution;
Made by Matsumoto Fine Chemical)
D-1: NK ester A-600
(Alkylene oxide modified acrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.)
D-2: NK ester A-GLY-20E
(Alkylene oxide modified acrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.)
D-3: NK Economer A-PG5054E
(Alkylene oxide modified acrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.)
D-4: FFM-2 (polyfunctional acrylamide compound; manufactured by Fuji Film)
D-5: Acryloylmorpholine D-6: Hydroxyacrylamide E-1: Megafac F-444 (fluorine leveling agent; manufactured by DIC)
E-2: KP-112 (silicone leveling agent; manufactured by Shin-Etsu Chemical Co., Ltd.)
E-3: Sun eye bag IT-15SA (preservative: Sanai Petroleum)
E-4: DL-lactic acid E-5: N, N-bis (2-hydroxyethyl) butane-1aminium = phenyl (2,4,6-trimethylbenzoyl) phosphinate (radial 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-1aminium-2
-Carboxybenzophenone (radical initiator)
E-8: Potassium-2-carboxybenzophenone (radical initiator)
E-9: Dipotassium-4,4′-dicarboxybenzophenone (radical initiator)
F-1: BONJET BLACK CW-1
(Manufactured by Orient Chemical Industries, modified carbon black self-dispersion, dark
20%)
F-2: MICROPIGMO WMRD-5
(Pigment Red 17 resin dispersion, manufactured by Orient Chemical Co., Ltd.
Body, concentration 20%)
F-3: MICROPIGMO WMGN-5
(Made by Orient Chemical Industries, Pigment Green 7 resin)
Dust, concentration 21%)
F-4: MICROPIGMO WMBE-5
(Oriento Chemical Co., Ltd., Pigment Blue 15: 6 tree
Fat dispersion, concentration 20%)

[Evaluation of water-soluble composition and cured product]
In the water-soluble compositions of Examples 1 to 39 and Comparative Examples 1 to 8, evaluation of compatibility, applicability, photolithography, state change of the cured product (moisture and heat resistance 1) and haze change (wet and heat resistance 2) are as follows. The procedure was performed. 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.
○: Uniformity △: Uniform system, but slightly turbid by visual observation ×: Incompatible, gelled or insoluble substances are evaluated as “good”, and can be preferably used and evaluated as “poor” Is not suitable for use.

(Applicability)
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 profilometer (Dektak 150 manufactured by ULVAC). Pre-baking was performed for 10 minutes on a hot plate at 0 ° C. The state of the film at this time was visually confirmed and evaluated according to the following criteria.
○: Coating film is uniform Δ: Uniform film, but turbidity is observed visually. ×: Uneven state such as unevenness on the surface or evaluation that the deposit is confirmed is ○. Those that can be preferably used and evaluation is x are not suitable for use.

(Photolithography)
After applying each water-soluble composition on 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 profilometer (Dektak 150 manufactured by ULVAC), Pre-baking was performed on a hot plate at 90 ° C. for 10 minutes. Then, it is cooled to room temperature, irradiated with 500 mJ / cm ^{2 of} light containing a wavelength of 365 nm through a photomask (LINE / SPACE = 50 μm / 50 μm) using a high-pressure mercury lamp, and ion-exchanged water at 23 ° C. for 1 minute. After soaking, the water attached with an air gun was removed, and the substrate was dried in an oven at 140 ° C. for 30 minutes. The dried pattern was confirmed with a laser microscope and evaluated according to the following criteria.
○: The pattern is within 50 ± 3 μm Δ: Within 50 ± 10 μm ×: The evaluation result that exceeds 50 ± 10 μm or the pattern disappears is ○ or Δ can be used as a pattern forming agent, and among these, the ○ is particularly It can be preferably used, and those with x are not suitable as pattern forming agents.

(Moisture and heat resistance 1: Change in state of cured product)
After applying each water-soluble composition on 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 profilometer (Dektak 150 manufactured by ULVAC), Pre-baking was performed on a hot plate at 90 ° C. for 10 minutes. Thereafter, after cooling to room temperature, using a high-pressure mercury lamp, light containing a wavelength of 365 nm was irradiated with 3000 mJ / cm ² and the substrate was dried in an oven at 140 ° C. for 30 minutes. The obtained cured product was allowed to stand for 24 hours at 85 ° C. and 85% RH, 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.
○: Same as before testing, no change such as peeling or color loss ×: Evaluation results with changes, ○ cured products can be used for applications that require wet heat resistance, and cured products with evaluation results of × It cannot be used for applications that require heat and moisture resistance.

(Moisture and heat resistance 2: Haze change)
After applying each water-soluble composition on 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 profilometer (Dektak 150 manufactured by ULVAC), Pre-baking was performed on a hot plate at 90 ° C. for 10 minutes. Then, after cooling to room temperature, using a high-pressure mercury lamp, light containing a wavelength of 365 nm was irradiated at 500 mJ / cm ^2, 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 Denshoku HAZEMETER NDH5000. Furthermore, after leaving the obtained hardened | cured material to stand on condition of 85 degreeC and 85% RH for 24 hours, the haze of hardened | cured material was measured similarly. Before and after the moisture resistance test, the evaluation was made according to the following criteria.
◎: Haze change amount less than 0.5 ○: Haze change amount from 0.5 to less than 1 △: Haze change amount from 1 to less than 3 ×: Haze change amount of 3 or more Evaluation result is ◎, ○ The cured products of △ and △ can be used for applications requiring heat and heat resistance, and are excellent in heat and heat resistance in the order of ◎, ○, and Δ. Among these, a cured product that is ◎ is particularly suitable for applications requiring moisture and heat resistance. On the other hand, a cured product that is x cannot be used for applications requiring moisture and heat resistance. In addition, about Examples 32-39 and Comparative Examples 6-8, since the coloring agent is added, the measurement of haze is not performed.

  From [Table 1] to [Table 10], it is clear that the water-soluble composition of the present invention has high compatibility, excellent coating properties, excellent photolithographic properties, and good moist heat resistance of the resulting cured product. is there. 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 (10)

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

(In general formula (I), * means a bond.) A water-soluble composition comprising a compound (B) having a structural unit represented by the formula (B) and a crosslinking agent (C). The water-soluble photosensitive polymer (A) is represented by the following general formulas (IIα), (IIβ) and (IIγ),

(In the general formulas (IIα), (IIβ) and (IIγ), Y ¹ , Y ² and Y ³ each independently represent a direct bond or a divalent linking group, and Q ¹ , Q ² and Q ³ are 2. The water-soluble composition according to claim 1, wherein each of the water-soluble compositions has at least one structural unit selected from the group consisting of a photosensitive group and * means a bond.   The water-soluble composition according to claim 1 or 2, wherein the photosensitive group is a stilbazolium group, a cinnamoyl group, an acrylic group, a methacryl group, an acrylamide group or a methacrylamide group. The water-soluble photosensitive polymer (A) is represented by the following general formula (IIδ) or (IIε),

(In general formulas (IIδ) and (IIε), An ^q- represents a q-valent anion, q represents 1 or 2, p represents a coefficient for maintaining a neutral charge, and * represents a bond. The water-soluble composition as described in any one of Claims 1-3 containing the structural unit represented by this. The compound (B) is represented by the following general formula (III),

The water-soluble composition according to any one of claims 1 to 4, which is a compound having a structural unit represented by (in the general formula (III), * represents a bond). In addition to 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 —NR ² —, and R ² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. represents, X ² represents an alkylene group having 1 to 6 carbon atoms, a hydrogen atom of an 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 the general formula (IV), a plurality of R ¹ , X ¹ , X ² and n are the same. The water-soluble composition as described in any one of Claims 1-5 containing the compound (D) which has one or more groups represented by these may be different.   The water-soluble composition according to any one of claims 1 to 6, wherein the crosslinking agent (C) is a zirconium compound or a titanium compound.   The pattern formation agent which consists of a water-soluble composition as described in any one of Claims 1-7.   The manufacturing method of the hardened | cured material characterized by using the water-soluble composition as described in any one of Claims 1-7.   Hardened | cured material which consists of a water-soluble composition as described in any one of Claims 1-7.