KR20190098746A - Water-soluble composition, pattern forming agent, manufacturing method of hardened | cured material using these, and hardened | cured material - Google Patents

Abstract

(일반식(I) 중, *은 결합손을 의미한다.)으로 표시되는 구성 단위를 가지는 화합물(B), 및 가교제(C)를 함유하는 수용성 조성물이다.A water-soluble composition, a pattern forming agent, a method for producing a cured product using the same, and a cured product obtained by obtaining a cured product excellent in heat resistance, water resistance, and moist heat resistance in a high precision pattern. It is other than the water-soluble photosensitive polymer (A) and water-soluble photosensitive polymer (A) which have a photosensitive group and a hydroxyl group, and is following General formula (I)

(In general formula (I), * means a bond.) It is a water-soluble composition containing the compound (B) which has a structural unit represented by it, and a crosslinking agent (C).

Description

Water-soluble composition, pattern forming agent, manufacturing method of hardened | cured material using these, and hardened | cured material

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 water-soluble composition capable of obtaining a cured product excellent in heat resistance, water resistance, and moist heat resistance in a high precision pattern. The pattern forming agent, the manufacturing method of the hardened | cured material using these, and a hardened | cured material are related.

Polyvinyl alcohol is used for various uses, such as a paint, an ink, an adhesive agent, and an optical film. For example, Patent Document 1 proposes a resin composition excellent in gas barrier properties and water resistance, containing a resin such as polyvinyl alcohol and a metal organic compound such as a titanium organic compound or a zirconium organic compound. Moreover, in patent document 2, the thermal recording material excellent in chemical-resistance and sticking property containing the acetacetyl modified polyvinyl alcohol and the silane coupling agent which has an amino group as a crosslinking agent is proposed. Moreover, in patent document 3, the manufacturing method of the polyvinyl alcohol-type resin crosslinked material which crosslinks acetacetic acid ester group containing polyvinyl alcohol-type resin with glyoxylate has little time-lapse discoloration by ultraviolet-ray, and is excellent in weatherability. Is proposed.

Japanese Patent Laid-Open No. 11-310712 Japanese Laid-Open Patent Publication No. 2009-039874 Japanese Patent Application Laid-Open No. 2013-028697

In applications such as pattern formers, inks, various resists, optical films for flat-panel displays, coating materials and adhesives for optical films, and the like, more precise patterns and excellent heat resistance, water resistance, and moist heat resistance There is a need for a water soluble composition capable of obtaining a cargo. In such a situation, in the water-soluble compositions proposed in Patent Documents 1 to 3, these are not necessarily compatible at the high level required by the market, and the present situation is that further improvement of the water-soluble compositions is required. to be.

Accordingly, 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 the same, and a cured product that can obtain a cured product having a high precision pattern and excellent in heat resistance, water resistance, and moist heat resistance.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that the said subject can be eliminated by using the water-soluble photosensitive polymer which has a photosensitive group and a hydroxyl group, and the water-soluble photosensitive polymer which has a predetermined structure. The present invention has been completed.

That is, the water-soluble composition of this invention has the following general formula (I) other than the water-soluble photosensitive polymer (A) which has a photosensitive group and a hydroxyl group, and the said water-soluble photosensitive polymer (A).

(In general formula (I), * means a bond.) The compound (B) which has a structural unit represented by it, and a crosslinking agent (C) are contained, It is characterized by the above-mentioned.

In the water-soluble composition of the present invention, the water-soluble photosensitive polymer (A) is represented by the following general formula (IIα), general formula (IIβ) and general formula (IIγ).

(In General Formula (IIα), General Formula (IIβ), and General Formula (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. Each independently represents a photosensitive device, and * represents a bonding hand.) It is preferable to have one or more structural units selected from the group consisting of. Moreover, in the water-soluble composition of this invention, it is preferable that the said photosensitive group is a stilbazolium group, a cinnamoyl group, an acryl group, a methacryl group, an acrylamide group, or a methacrylamide group. In the water-soluble composition of the present invention, the water-soluble photosensitive polymer (A) is represented by the following general formula (IIδ) or general formula (IIε).

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

It is preferable that it is a compound which has a structural unit represented by (In general formula (III), * represents a bond.). Moreover, in the water-soluble composition of this invention, as other than the said water-soluble photosensitive polymer (A), following General formula (IV)

(In General Formula (IV), R ¹ represents a hydrogen atom or a methyl group, X ¹ represents an oxygen atom or —NR ² —, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, 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 is 0 to 30 Represents a bond, and in the case where there are a plurality of groups represented by the general formula (IV), a plurality of R ¹ , X ¹ , X ² , and n may be the same or different). It is preferable to contain the compound (D) which has one or more groups represented. Moreover, in the water-soluble composition of this invention, it is preferable that the said crosslinking agent (C) is a zirconium compound or a titanium compound.

Moreover, the pattern forming agent of this invention consists of the water-soluble composition of this invention, It is characterized by the above-mentioned.

Moreover, the manufacturing method of the hardened | cured material of this invention used the water-soluble composition of this invention, It is characterized by the above-mentioned.

Moreover, the hardened | cured material of this invention consists of the water-soluble composition of this invention. It is characterized by the above-mentioned.

ADVANTAGE OF THE INVENTION According to this invention, the water-soluble composition which can obtain the hardened | cured material excellent in heat resistance, water resistance, and moisture and heat resistance with a high precision pattern, a pattern forming agent, the manufacturing method of hardened | cured material using these, and hardened | cured material can be provided. The water-soluble composition of this invention can be used suitably for uses, such as a pattern forming agent, the optical film for flat panel displays, the coating material of an optical film, or an adhesive agent.

First, the water-soluble composition of this invention is demonstrated. The water-soluble composition of this invention has the following general formula (I) other than the water-soluble photosensitive polymer (A) which has a photosensitive group and a hydroxyl group (henceforth "the (A) component), and the said water-soluble photosensitive polymer (A).

The compound (B) (henceforth "the (B) component") which has a structural unit represented by this is contained, and a crosslinking agent (C) (henceforth "the (C) component") is contained. Here, in general formula (I), * means a bond. Since the water-soluble composition of this invention is excellent in storage stability and can exist in 1 liquid, hardened | cured material can be created easily. Hereinafter, each component is demonstrated in order.

<(A) component>

(A) component which concerns on the water-soluble composition of this invention should just have a photosensitive group and a hydroxyl group, and is not specifically limited. As preferable as (A) component, since the heat resistance, water resistance, and damp-heat resistance of hardened | cured material are high, the compound which has following general formula (II (alpha))-general formula (II (epsilon)) as a structural unit is mentioned, Especially, the general formula ( The compound having IIδ) and the general formula (IIε) as the structural unit is more preferable even when an LED light source (365 nm) is used because a water-soluble composition having excellent curability and a cured product excellent in heat resistance, water resistance and heat and moisture resistance can be obtained.

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.

In the formulas (IIδ) and (IIε), An ^{q −} represents a q-valent anion, q represents 1 or 2, p represents a coefficient for maintaining the charge neutral, and * represents a bond. it means.

Although there is no restriction | limiting in particular as bivalent coupling group represented by Y <^1> , Y <^2> and Y <^3> in general formula (II (alpha)), general formula (II (beta)), and general formula (II (gamma)), For example, methylene group, ethylene group, tri An arylene group having 6 to 30 carbon atoms, a heterocyclic linking group such as an alkylene group having 1 to 10 carbon atoms, such as a methylene group, a propylene group and a butylene group, a phenylene group and a naphthalene group, a heterocyclic linking group, and -CH = CH- and -O- , -S-, -C (= O)-, -CO-, -NR-, -CONR-, -OC-, -SO-, -SO ₂ -and the linking group which combines two or more thereof are mentioned as a preferable example. have. Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

As a photosensitive group represented by Q <^1> , Q <^2> and Q <^3> in general formula (II (alpha)), general formula (II (beta)), and general formula (II (gamma)), cinnamil group, cinnamoyl group, cinnamildene group, cinnamil Denacetyl group, chalcone group, coumarin group, isocoumarin group, 2,5-dimethoxystilbene group, maleimide group, α-phenylmaleimide group, 2-pyrone group, azide group, thymine group, quinone group, ura Real group, pyrimidine group, stilbazolium group, styryl pyridinium group, thirylquinolium group, epoxy group, oxetane group, vinyl ether group, allyl ether group, acryl group, methacryl group, acrylamide group, methacrylamide group, Vinyl group, allyl group, styryl group, and the like, and among these, when included in the water-soluble composition as the component (A), the photosensitivity is high and does not involve liquid stability (thickness, gelation, precipitation, etc.). Steel bar solium group, cinnamoyl group, acryl group, methacryl group, Acrylamide group or methacrylamide group can be used preferably.

Among these photosensitive groups, since the steel bar solium group has high solubility in water and an absorption band in the vicinity of 365 nm, a water-soluble composition expressing photosensitivity can be obtained even in a light source having a long wavelength such as an LED light source (365 nm). Since the hardened | cured material which has a high precision pattern is obtained from this water-soluble composition in addition to heat resistance, water resistance, and moisture heat resistance, it can use especially preferably.

As a specific example of a preferable (A) component, the water-soluble photosensitive polymer represented by the following general formula (V) and the following general formula (VI) is mentioned.

In formula (V), Y <^1> and Q <^1> are the same as said general formula (II (alpha)), Y <^3> and Q <^3> are the same as said general formula (II (gamma)), and a, b, c, and d are 0 It is a number from -5000, a and d do not become 0 simultaneously, 100 <a + b + c + d <5000, and * is a bond.

In formula (VI), a, b, c and d are the same as general formula (V), a and d do not become 0 at the same time, 100 <a + b + c + d <5000, and * is a bond. .

Since heat resistance and adhesiveness of the hardened | cured material obtained from the water-soluble composition of this invention are favorable, preferable values of a, b, c, and d (molar ratio) in general formula (V) and general formula (VI) are a: b: c: d = 0.1-4: 5-30: 5-70: 0.1-4, and it is preferable that weight average molecular weights are 1.50,000-5 million, and 100,000-1 million.

The polymer represented by general formula (VI) is obtained by acetalization-reacting the aldehyde which has a photosensitive group to butenediol polyvinyl alcohol copolymer on the conditions of pH 1-4. Moreover, it can also manufacture by using a commercial item, For example, the aldehyde which has a photosensitive group in G polymer (butenediol vinyl alcohol copolymer) OKS-1081, OKS-1083, OKS-1109 manufactured by Nippon Synthetic Chemical Co., Ltd. is made into pH1. It can obtain by making acetalization reaction on condition of -4.

1-99 mass parts is preferable in conversion of solid content with respect to the total amount of 100 mass parts of (A) component and (B) component, and, as for (A) component, More preferably, it is 5-95 mass parts, and 10-90 mass parts In addition, since a hardened | cured material excellent in heat resistance, water resistance, and moisture heat resistance is obtained with a high precision pattern, it is most preferable.

<(B) component>

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

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

Component (B) is polyvinyl alcohol, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol polymerized with vinyl alcohol, generally called poval, as the main chain, as conventionally known polyvinyl alcohol. Or a saponified product of a copolymer of vinyl acetate with a monomer having copolymerizability. The polyvinyl alcohol constituting the component (B) may be either a homopolymer or a copolymer containing vinyl alcohol as an essential monomer.

Although it does not specifically limit as a manufacturing method of (B) component, For example, the method of making polyvinyl alcohol and diketene react, the method of reacting polyvinyl alcohol and acetic acid ester, and transesterifying, vinyl acetate and vinyl acetate And a method of saponifying a copolymer thereof. Among these, since a manufacturing process is simple and the polyvinyl alcohol which has a favorable acetic acid ester group is obtained, it is preferable to manufacture by the method of making polyvinyl alcohol and diketene react.

Examples of the monomer having copolymerizability 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, and ethylene and propylene. Olefin, allylsulfonic acid, metalylsulfonic acid, allylsulfonic acid soda, metalylsulfonic acid soda, sulfonic acid soda, sulfonic acid soda monoalkyl maleate, disulfonic acid soda alkyl maleate, N-methylol acrylamide, acrylamide alkyl sulfonic acid alkali salt, N -Vinylpyrrolidone, N-vinylpyrrolidone derivatives, and the like, and these monomers are preferably 10 mol% or less, particularly 5 mol% of the total structural units. When too much, water solubility may fall, or compatibility with (C) component mentioned later may fall.

The polystyrene reduced weight average molecular weight (Mw) by gel permeation chromatography (GPC) is 10,000 to 200,000, and the saponification degree (hydrolysis rate) of (B) component (85) is that the water resistance is improved and the durability of the membrane is improved. Since the property is improved, the component (B) having a saponification degree of 95 to 100 is more preferable because the water resistance is further improved.

As the component (B), the following general formula (III)

When the compound which has a structural unit represented by is used, since it is especially excellent in the heat resistance, water resistance, and moisture heat resistance of the hardened | cured material obtained from the water-soluble composition of this invention, it is more preferable.

Content of the structural unit represented by General formula (III) is 0.1-20 mol% normally, and also 0.2-15 mol%, especially 0.3-10 mol% of the water resistance of hardened | cured material, crosslinking rate, water solubility, and aqueous solution It is preferable from a stability point of view.

A commercial item can also be used as (B) component, For example, Cosenex Z-100, Z-200, Z-220, Z-300, Z-410 (made by Japan Synthetic Chemical Co., Ltd.), etc. are mentioned.

1-99 mass parts is preferable with respect to the total amount of 100 mass parts of (A) component and (B) component, (B) component, More preferably, it is 5-95 mass parts, and 10-90 mass parts is the most preferable. Do. When content of (B) component is the said range, since the hardened | cured material excellent in heat resistance, water resistance, and moisture heat resistance with a highly precise pattern is obtained, it 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 the component (B) can be crosslinked. As the component (C), for example, conventionally known organic crosslinking agents, metal chelate complexes having chelating agents, zirconium compounds and titanium compounds can be preferably used.

As an organic type crosslinking agent, it can select arbitrarily and can use from what is conventionally used as a crosslinking agent, For example, the amino resin which has a bisdiazide compound, a hydroxyl group, or an alkoxyl group, for example, melamine resin, urea resin, guar Namin resins, glycoluril-formaldehyde resins, succinylamide-formaldehyde resins, ethylene urea-formaldehyde resins, and the like. These can be used by reacting melamine, urea, guanamine, glycoluril, succinylamide, and ethylene urea with formalin in boiling water, to methylolation or to further alkoxylation of lower alcohols.

Examples of the chelating agent include hydroxycarboxylic acid or salts thereof, glyoxylic acid or salts thereof, aminoalcohol, aminocarboxylic acid, alanine, arginine, leucine, isoleucine, dihydroxypropylglycine, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, Examples of the nitrile include triacetic acid, β-diketone, dimethylglyoxime, citric acid, tartaric acid, maleic acid, polyhydrazide, and phosphate esters, and these may be used alone or in combination of two or more thereof.

When a metal chelate complex having a chelating agent capable of coordinating at two or more polydents by covalent bonds, hydrogen bonds or the like with respect to one metal atom is used, the crosslinking reaction rate is suitably controlled. Do. Specifically as a chelate ligand, hydroxycarboxylic acid or its salt, amino alcohol, (beta) -diketone, etc. are mentioned.

Examples of the zirconium compound include zirconium halides such as zirconium oxychloride, zirconium hydroxy chloride, zirconium tetrachloride and zirconium bromide; Zirconium salts of minerals such as zirconium sulfate, basic zirconium sulfate, zirconium oxynitrate, zirconium oxyacetate, and zirconium oxycarbonate; Zirconium salts of organic acids such as zirconium formate, zirconium acetate, zirconium propionate, zirconium caprylic acid, zirconium stearate, zirconium stearate, zirconium lactate, zirconium nitrate, zirconium carbonate, zirconium carbonate, zirconium citrate, and zirconium phosphate; One or two or more chelating agents besides zirconium complex salts such as ammonium zirconium carbonate, sodium zirconium sulfate, zirconium ammonium acetate, zirconium carbonate ammonium, zirconium potassium carbonate, sodium zirconium sodium, zirconium sodium citrate, zirconium ammonium citrate and ammonium zirconium lactate For example, a zirconium chelate complex having a ligand as the ligand may be mentioned. 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 ethyl Acetoacetate, zirconium acetate, and the like.

Among the zirconium compounds, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium oxyhalogenated zirconium, zirconium oxynitrate, zirconium lactate ammonium, zirconium sulfate and zirconium oxyacetate, and the like, are preferred. These can be used as 1 type or in mixture of 2 or more types.

A commercial item can also be used as a zirconium compound, For example, a zirconium-acid salt, a zircosol ZC-2, a zircosol ZN, a zircosol HA, a zircosol AC-7, a zircosol ZK-10, a zircosol ZN, a zircosol ZA -10, zircosol ZA-20, zirconyl octylic acid, zirconyl carbonate, (manufactured by Daiichi Heochemistry Co., Ltd.), orgatics ZA-45, orgatics ZA-65, orgatics ZB-126, orgatics ZC-126 Orgastics ZC-150, orgastics ZC-200, orgastics ZC-300, orgastics ZC-320, orgastics ZC-540, orgastics ZC-580, orgastics ZC-700, ZC-300 (Matsumoto Fine Chemical company).

As a titanium compound, tetramethyl titanate, tetraethyl titanate, tetranormal propyl titanate, tetra isopropyl titanate, tetra normal butyl titanate, tetra isobutyl titanate, tetra-tert- butyl titanate, tetraoctyl titanate Titanium alkoxides such as tetra (2-ethylhexyl) titanate and tetramethyl titanate; Oligomers and polymers obtained by hydrolysis reaction of titanium alkoxides such as titanium butyl dimer and titanium butyl tetramer and derivatives thereof; Titanium chelate complexes such as titanium acetylacetonato, titanium octylene glycolate, titanium tetraacetylacetonato, titanium ethyl acetoacetate, titanium triethanol aluminate and titanium oxalate; Titanium acylates such as polyhydroxy titanium steareto; Titanium tetrachloride, titanium lactate, titanium triethanol aluminate, diisopropoxy citabis bis (triethanol aluminate), etc. are mentioned, These can be used as 1 type, or 2 or more types of mixtures.

A commercial item can also be used as a titanium compound, For example, orthotics TA-8, orgastics TA-10, orgastics TA-12, orgastics TC-100, orgastics TC-120, orgastics TC-300, orgas TIX TC-310, ORGATIX TC-315, ORGATIX TC-335, ORGATIX TC-401, ORGATIX TC-800 (made by Matsumoto Fine Chemical).

In consideration of the good moist heat resistance of the cured product obtained from the water-soluble composition of the present invention, a zirconium compound or a titanium compound is particularly preferable among the components (C).

It is preferable that (C) component is 0.01-5 mass parts with respect to 100 mass parts of (B) components, since there is no change, such as precipitation and thickening, and a water-soluble composition is stable.

Although the metal powder derived from (C) component is contained in the water-soluble composition of this invention, 0.01-3 mass% is preferable in the component except the solvent of a water-soluble composition, and, as for metal content, More preferably, it is 0.01-1 Mass%.

<(D) component>

The water-soluble composition of this invention is a following general formula (IV) as (D) component.

It may contain the compound represented by. 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. , X ² represents an alkylene group having 1 to 6 carbon atoms, 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 is 0 to When the number of 30 is represented, * means a bonding hand, and there are a plurality of groups represented by a plurality of general formulas (IV), a plurality of R ¹ , X ¹ , X ² , and n may be the same or different, respectively. do.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ² in General Formula (IV) is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms And 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. In the case of using as a (B) component, since the sensitivity is favorable, an alkyl group of 1-10 carbon atoms, an alkenyl group of 2-10 carbon atoms, a cycloalkyl group of 3-10 carbon atoms, and a 4-10 carbon atom More preferred are a cycloalkylalkyl group, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and the like.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl and octyl , Isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and isocyl, and the like. As the alkyl group of 10, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2 Ethylhexyl, tert-octyl, nonyl, isononyl, decyl and isodecyl.

As an alkenyl group having 2 to 20 carbon atoms, for example, vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hex Cenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclo Hexenyl, 2,5-cyclohexathienyl-1-methyl, 4,8,12-tetradecattrienyl allyl, and the like. As the alkenyl group having 2 to 10 carbon atoms, for example, 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 and 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 tetradecahydroanthracenyl, and the like, and as the cycloalkyl group having 3 to 10 carbon atoms, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, Adamantyl, decahydronaphthyl, octahydropentalene and bicyclo [1.1.1] pentanyl.

The cycloalkylalkyl group having 4 to 20 carbon atoms means a group in which the hydrogen atom of the alkyl group has 4 to 20 carbon atoms 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-cycloheptyl Propyl, 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, cyclononnirumethyl, 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.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl and the like, the alkyl group, the alkenyl group, carboxyl group, halogen atom and the like. One or more substituted phenyl, biphenylyl, naphthyl, anthryl and the like, for example 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl The aryl group having 6 to 10 carbon atoms includes, for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and the like, and one of the alkyl group, the alkenyl group, carboxyl group, halogen atom, and the like. Or more substituted phenyl, biphenylyl, naphthyl, anthryl and the like, for example, 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, and the like. have.

The arylalkyl group having 7 to 20 carbon atoms means a group in which the hydrogen atom of the alkyl group has 7 to 30 carbon atoms substituted with an aryl group. For example, benzyl, (alpha) -methylbenzyl, (alpha), (alpha)-dimethylbenzyl, phenylethyl, naphthylpropyl, etc., and the said arylalkyl group of 7-20 carbon atoms is a hydrogen atom of an alkyl group substituted with the aryl group. It means group which has a carbon atom of -20. 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 General Formula (IV) include linear alkyl such as methylene group, ethylene group, propylene group, butylene group, pentylene group and hexylene group. And branched chain alkylene groups such as isene groups, isopropylene groups, and isobutylene groups.

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

The said alkylene oxide modified acrylate compound is a compound in which R <^1> is a hydrogen atom, X <^{1> an} oxygen atom, n is 1-30 in general formula (IV), The said alkylene oxide modified methacrylate compound is general In formula (IV), R <^1> is a methyl group, X <^1> is an oxygen atom, n is a compound of 1-30.

As said alkylene oxide modified acrylate compound, For example, diethylene oxide modified neopentyl glycol diacrylate, dipropylene oxide modified neopentyl glycol diacrylate, diethylene oxide modified 1, 6- hexanediol diacrylate, Dipropylene oxide modified 1,6-hexanediol diacrylate, and the like. Examples of the alkylene oxide-modified methacrylate compound include diethylene oxide-modified neopentyl glycol dimethacrylate and dipropylene oxide-modified neopentyl. Glycol dimethacrylate, diethylene oxide modified 1,6-hexanediol dimethacrylate, dipropylene oxide modified 1,6-hexanediol dimethacrylate, and the like.

As said alkylene oxide modified acrylate compound and said alkylene oxide modified methacrylate compound, a commercial item can also be used preferably, For example, NK ester A-600, A-GLY-20E, NK economer A-PG5054E (Manufactured by Shin-Nakamura Chemical Co., Ltd.).

In the alkylene oxide modified acrylate compound and the alkylene oxide modified methacrylate compound, X ² in the general formula (IV) is preferably an ethylene group or a propylene group, because it is excellent in water solubility, and particularly preferably an ethylene group. Since it is excellent in water solubility, it is preferable.

When the said alkylene oxide modified acrylate compound and the said alkylene oxide modified methacrylate compound have one group represented by general formula (IV), since water solubility is excellent, the case where n is 6 or more is especially preferable. When the said alkylene oxide modified acrylate compound and the alkylene oxide modified methacrylate compound have two or more groups represented by General formula (IV), since water solubility is excellent, it is especially preferable that the total of n which exists in multiple numbers is 10 or more. Do.

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

As said acrylamide compound, hydroxy acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, N-butyl acrylamide, diacetone acrylamide, N, N- dimethyl acrylamide, N Examples include N-diethyl acrylamide, N, N-dipropyl acrylamide, acryloyl morpholine, Nn-butoxymethyl acrylamide, N-isobutoxymethyl acrylamide, and N-methoxymethyl acrylamide. As the methacrylamide compound, hydroxy methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-isopropyl methacrylamide, N-butyl methacrylamide, diacetone methacrylamide , N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N, N-dipropylmethacrylamide, methacryloylmorpholine, Nn-butoxymethylmethacrylamide, N-isobutoxy Methyl methacrylamide, N -Methoxymethyl methacrylamide etc. are mentioned.

As said acrylamide compound and said methacrylamide compound, a commercial item can also be used preferably, For example, there exist FFM-2, FFM-3, FFM-4, and FFM-5 (made by Fujifilm). .

When it contains (D) component, content of (D) component is 1-50 mass parts with respect to 100 mass parts of total amounts of (A) component, (B) component, and (D) component, and (D) component When content of is in this range, since the water-soluble composition with favorable sclerosis | hardenability is obtained, and the hardened | cured material excellent in heat resistance, water resistance, and moisture heat resistance with a pattern of a higher precision than this water-soluble composition is obtained, it is preferable.

The water-soluble composition of the present invention may contain water as a solvent and may be used in combination with an organic solvent. However, when one liquid of only water is used as the solvent, it is preferable since the water-soluble composition does not invade the organic material. .

As said organic solvent, by using together with water, the solvent obtained by melt | dissolving or disperse | distributing said component ((A) component, (B) component, (C) component, and (D) component) etc., for example, methyl ethyl Ketones such as ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and 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; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol or amyl alcohol; Ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether (PGM), propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3- Ether ester solvents such as methoxy butyl acetate and ethoxy ethyl propionate; Aromatic solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene hydrocarbon oils such as terepin oil, D-limonene and pinene; Mineral spirit, Swasol # 310 (above, manufactured by Cosmomatsuyama Oil); And Sorbetso # 100 (above, manufactured by Exxon Chemical); Paraffin solvents such as these; 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 and water Since it has good compatibility with water, an alcohol solvent is preferable.

The water-soluble composition of this invention contains water as a solvent. Although it is also possible to use together with the organic solvent, it is preferable that it is one liquid only water as a solvent, since it does not invade an organic material, when apply | coating to environmental low load and an organic material yarn.

Although the usage-amount of the said solvent in the water-soluble composition of this invention is not specifically limited, It is preferable that it is 70-95 mass% with respect to the water-soluble composition whole quantity. When the content of the solvent is in the above-described range, the thickness of the curable composition and the cured product excellent in handling properties (viscosity or wettability of the curable composition) and liquid stability (without precipitation or sedimentation of components contained in the composition) are appropriately controlled. It is preferable because it can be done.

In the water-soluble composition of this invention, the water-soluble polymer which does not belong to (A) component and (B) component, an organic acid, a coupling agent, a sensitizer, surfactant, a basic compound, a coloring agent, a radical initiator, a water-soluble preservative, and an electroconductive substance as needed. Or the like.

As a water-soluble polymer which does not belong to (A) component and (B) component, cellulose derivatives, such as oxidized starch, etherified, esterified, grafted modified starch, gelatin casein, carboxymethylcellulose, polyvinylpyrroli Money, water-soluble polyester resin, water-soluble polyacrylic acid ester resin, such as 2-hydroxypropyl acrylate polymer, 4-hydroxybutyl acrylate polymer, water-soluble polycarbonate resin, water-soluble polyvinyl acetate resin, water-soluble styrene acrylate resin, water-soluble Water-soluble polyamide resin, such as vinyltoluene acrylate resin, water-soluble polyurethane resin, polyvinylamide polyacrylamide, 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 A water-soluble resin and a styrene-butadiene copolymer, an acrylic acid ester copolymer resin such as polyacrylonitrile, ethylene and the like can be mentioned vinyl acetate copolymer as an example.

As said organic acid, if it is a weakly acidic compound which has a carboxyl group, it 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, capric acid, gluconic 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 dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltrimethoxysilane. Alkenyl functional alkoxysilane, 3-methacryloxypropyl triethoxysilane, such as alkyl functional alkoxysilane, vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, allyl trimethoxysilane, such as these, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyl Epoxy functional alkoxysilanes such as trimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and N-β (aminoethyl) -γ- Aminopropyltrimethoxy Column, mercapto-functional alkoxysilanes such as amino-functional alkoxysilanes such as γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane Can be used.

The said sensitizer is a compound which can expand the wavelength range to which light is applicable when hardening by light irradiation, As a sensitizer, benzophenone, 3-hydroxy benzophenone, 4-hydroxy, for example. Benzophenone, 4,4-dihydroxybenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone, 4-meth Benzophenones such as oxybenzophenone, 4,4-dimethoxybenzophenone, 3,3-dimethyl-4-methoxybenzophenone, 4-phenylbenzophenone, acetophenone, 4-methoxyacetophenone, 2,4 Dimethoxyacetophenone, 2,5-dimethoxyacetophenone, 2,6-dimethoxyacetophenone, 4,4-dimethoxyacetophenone, 4-ethoxyacetophenone, diethoxyacetophenone, 2,2-die Acetophenones such as oxyacetophenone, 2-ethoxy-2-phenylacetophenone, 4-phenylacetophenone, anthraquinone, hydroxyanthraquinone, 1-nitroanthraquinone and aminoant Anthraquinones such as quinone, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, anthraquinonesulfonic acid, 1,2-benzanthraquinone and 1,4-hydroxyanthraquinone (quinizarin), Anthracenes such as anthracene, 1,2-benzoanthracene, 9-cyanoanthracene, 9,10-dicyanoanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-bis (phenylethyl) anthracene, 2,3-dichloro-6-dicyano-p-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, methoxybenzoquinone, 2,5-dichloro-p-benzoquinone, Quinones such as 2,6-dimethyl-1,4-benzoquinone, 9,10-phenanthrequinone, camphorquinone, 2,3-dichloro-1,4-naphthoquinone and xanthone, thioxanthone, 2 -Thioxanes, such as methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone and 2,4-isopropyl thioxanthone, dibenzosuberon Cycloheptanes, such as dibenzosuberen, dibenzosuberenol, and dibenzosuberan, 2-methoxy naphthal , Aromatic compounds such as benzoin isopropyl ether, 4-benzoyldiphenyl, o-benzoylbenzoic acid, o-benzoylbenzoic acid methyl, 4-benzoyl-4-methyl-diphenyl sulfide, benzyl, benzoin methyl ether, and pigment Coumarin-based, thiazine-based, azine-based, acridine-based, and xanthene-based compounds that are sensitizers.

Examples of the surfactant include fluorine surfactants such as pafluoroalkyl phosphate esters and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, higher amine halogenates, and quaternary grades. Surfactants such as cationic surfactants such as ammonium salts, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and nonionic surfactants such as fatty acid monoglycerides, amphoteric surfactants and silicone surfactants, It can also be used in combination.

Examples of the basic compound include ammonia, sodium hydroxide, potassium hydroxide, triethylamine, triethanolamine, diethanolamine, monoethanolamine, triisopropanolamine, diisopropanolamine, monoisopropanolamine, and N, N-dimethylethanol. Amine, ethyleneimine, pyrrolidine, piperidine, polyethyleneimine, and the like, and 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 or the like.

As the colorant, pigments and dyes can be used. As a pigment and dye, an inorganic color material or an organic color material can be used, respectively, These can be used individually or in mixture of 2 or more types. Here, a pigment refers to the coloring agent insoluble in the solvent mentioned later, The thing insoluble in a solvent among the inorganic or organic coloring materials, or the thing which rake-ized the inorganic or organic dye are also included.

As said pigment, the carbon black obtained by the furnace method, the channel method, or the thermal method, or carbon black, such as acetylene black, Ketjen black, or lamp black, the carbon black adjusted or coated with an epoxy resin, the said carbon The black is previously dispersed in a solvent and coated with a resin of 20 to 200 mg / g, the acidic or alkaline surface treated carbon black, an average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less Carbon black, carbon black, graphitized carbon black, graphite, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon having a total amount of oxygen calculated from CO and CO ₂ in volatile matter at 950 ° C at 9 mg or more per 100 m ² surface area. Black pigments represented by nanohorns, carbon aerogels, fullerenes, aniline blacks, pigment blacks 7, titanium blacks, chromium oxide green, millory blue, cobalt green, cobalt Blue, Manganese, Ferrocyanide, Phosphate Ultramarine Blue, Royal Blue, Ultramarine, Cerulean Blue, Viridian, Emerald Green, Lead Sulfate, Lead Yellow, Zinc Sulfur, Bengala (Red Iron Oxide (III)), Cadmium Red, Synthetic Iron Organic or inorganic pigments, such as black, an amber, and a lake pigment, are mentioned, Since a light shielding property is high, it is preferable to use a black pigment, and it is more preferable to use carbon black as a black pigment.

As said pigment, a commercial item can also be used, for example, MICROPIGMO WMYW-5, MICROPIGMO WMRD-5, MICROPIGMO WMBN-5, MICROPIGMO WMGN-5, MICROPIGMO WMBK-5, MICROPIGMO WMBE-5, MICROPIGMO WMVT-5, MICROPIGMO WMWE-1, BONJET BLACK CW-1 (above, Orient Chemical 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 Gris- is 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.

As said dye, a nitroso compound, a nitro compound, an azo compound, a diazo compound, a xanthene compound, a quinoline compound, an anthraquinone compound, a coumarin compound, a cyanine compound, a phthalocyanine compound, an isoindolinone compound, isoin, for example Dolin compound, quinacridone compound, anthrone compound, perinone compound, perylene compound, diketopyrrolopyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compound, quinophthalone compound, naphthalenetetracarboxylic acid, azo dye And metal complex compounds of cyanine dyes.

It is possible to use a conventionally known compound as the radical initiator. For example, Japanese Patent Application Laid-Open No. 57-197289, Japanese Patent Application Laid-Open No. 6-228218, Japanese Patent Publication No. 2009-102455, and Japanese Patent Publication In addition to those described in Japanese Patent Application Laid-Open No. 2012-007071, Japanese Patent Application No. 2016-510314, WO2014 / 050551, Japanese Patent Application Laid-Open No. 06-239910, Japanese Patent Application Laid-Open No. 2003-192712, Japanese Patent Application Laid-Open No. 2016-185929, Hydrogen drawing such as phenone and salts thereof, dicarboxybenzophenone and salts thereof, thioxanthone, 1-chloro-4-propoxycyxanthone, isopropyl thioxanthone, diethyl thioxanthone and ethyl anthraquinone Photopolymerization initiator); Phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane (α-hydroxyalkylphenone), benzoin, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4'-morpholinobenzoyl ) Propane, 2-morpholinyl-2- (4'-methylmercapto) benzoylpropane, 4-benzoyl-4'-methyldiphenylsulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2 -Hydroxy-2- (4'-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoyl formate, 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 (trichlorome ) -s-triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1-2'-biimidazole, acylphosphine oxide, bisacylphosphine Photodegradation type photoinitiators, such as an oxide and a triphenylphosphine oxide, can be used, A photodegradation type photoinitiator is preferable at the point of reactivity.

Among the photolysis-type photopolymerization initiators, water-soluble initiators such as Irg2959, Irg819DW (manufactured by BASF Corporation), ESACURE ONE, ESACURE 1001M, ESACURE KIP 150, and ESACURE DP 250 (Lamberti) are preferred because they have high affinity for water. Do.

As said dye, a commercial item can also be used, As a 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, WATER 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, WATER BLUE 117-L, WATER 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 XXX, BONJET CYAN XXX, BONJET BLACK 891-L Orient Chemical Co., Ltd.).

As a oil-soluble dye, VALIFAST YELLOW 1101, VALIFAST YELLOW 3150, VALIFAST RED 1308, VALIFAST RED 2320, VALIFAST PINK 1364, VALIFAST PINK 2310N, VALIFAST VIOLET 1701, VALIFAST BLACK 1815, VALIFAST BLACK 1807, VALIFVAL BLACKASTE Examples include 3810, VALIFAST BLACK 3820, VALIFAST BLACK 3830, VALIFAST BLACK 3840, VALIFAST BLACK 3866, VALIFAST BLACK 3870, VALIFAST ORANGE 2210, VALIFAST BROWN 3402, VALIFAST BLUE 1613, and VALIFAST BLUE 1605 (above, are manufactured by Orient Chemical Industries, Ltd.). have.

Examples of the water-soluble preservative include those having high solubility in water and having a solubility at room temperature of 1% or more, and specifically, methyl paraben, benzoic acid, benzoate, salicylic acid, salicylate, phenoxyethanol, and water-soluble cationic antimicrobial agent. , Organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, parabens, propanediol substances, isothiazolinones, quaternary compounds, benzoates, low molecular weight alcohols, dehydroacetic acid, ACQ Ammonium compound), CUAZ (copper-azole compound), AAQ (quaternary ammonium compound), sodium hydrogen sulfite, sodium hydrogen sulfate, sodium thiosulfate, ascorbate, benzalkonium chloride, chlorobutanol, thimerosal, phenyl mercury acetate , Phenyl mercury borate, phenyl mercury nitrate, paraben, methyl paraben, polyvinyl alcohol, benzyl alcohol, isothiazolone, triazine, bronopol, thia Imidazole, there may be mentioned zinc-rich blood as an example one, kaben compaction, pyridine oxide-thiol sodium salt, and phenyl ethanol.

As said water-soluble preservative, a commercial item can also be used, and mountain eye bag P, the mountain eye bag 300K, the mountain eye bag IT-15SA, the mountain eye bag AS-30, the mountain eye bag T-10, the mountain eye bag M-30, and the acid eye bag sodium ohmic (all Sanai Petroleum Co., Ltd.) is mentioned as an example.

Examples of the conductive material include metals, oxides of metals, conductive carbons, conductive polymers, and the like.

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. And alloys composed of two or more metals such as -lead alloys, tin-copper alloys, tin-silver alloys, and tin-lead-silver alloys. Especially, 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, Graphitized Ketjenblack and mesophoras carbon and the like.

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-ethoxypyrrole), poly (3-octoxypyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), 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-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3 , 4-ethylenethioxythiophene), polyaniline, poly (2-methylaniline), poly (2-octylaniline), poly (2-isobutylaniline), poly (3-isobutylaniline), poly (2-aniline Rinsulfonic acid), poly (3-anilinesulfonic acid) and polythiophene derivatives (PEDOT: poly (3,4) -ethylenedioxythiophene) doped with polystyrenesulfonic acid (PSS).

As long as the effect of the present invention is not impaired, a photopolymerization initiator, a thermal polymerization initiator, a photobase initiator, an acid generator, an inorganic filler, an organic filler, an antifoaming agent, and a thickener (if necessary) I), leveling agents, organometallic coupling agents, thixotropic agents, carbon compounds, metal fine particles, metal oxides, flame retardants, plasticizers, light stabilizers, thermal stabilizers, antioxidants, elastomer particles, chain transfer agents, polymerization inhibitors And various resin additives such as ultraviolet absorbers, antioxidants, antistatic agents, mold release agents, flow regulators, adhesion promoters, unsaturated monomers, cationically polymerizable compounds such as epoxy compounds, oxetane compounds, and vinyl ethers. Can be added.

Next, the pattern former of this invention is demonstrated. The pattern former of this invention consists of the water-soluble composition of this invention. The pattern forming agent of the present invention has photolithographic properties. Specifically, after light irradiation through a mask, the pattern forming agent is developed using a developer (water, an organic solvent, an aqueous alkali solution, or the like), thereby producing a pattern of 1000 µm or less. It can be reproduced and formed satisfactorily with a precision within 10%.

The manufacturing method of the hardened | cured material of this invention is performed using the water-soluble composition or pattern forming agent of this invention. About the manufacturing method of the hardened | cured material using the water-soluble composition or pattern forming agent of this invention, a preferable application | coating method and hardening conditions are shown below.

Preferable application | coating methods are applied on support bodies, such as glass, a metal, paper, and a plastic, by well-known means, such as a spin coater, a bar coater, a roll coater, a curtain coater, various printing, and immersion. Moreover, after performing on support bodies, such as a film, you may also transfer on another support substrate, There is no restriction | limiting in the application method.

As a material of a transparent support body, For example, inorganic materials, such as glass; Cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose and nitrocellulose; Polyamides; Polycarbonate; Polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutyl Polyesters such as lenterephthalate; polystyrene; Polyolefins such as polyethylene, polypropylene and polymethylpentene; Acrylic resins such as polymethyl methacrylate; Polycarbonate; Polysulfones; Polyether sulfone; Polyether ketones; Polyetherimide; Polymer materials such as polyoxyethylene and norbornene resins. It is preferable that it is 80% or more, and, as for the transmittance | permeability of a transparent support body, it is more preferable that it is 86% or more. It is preferable that it is 2% or less, and, as for haze, it is more preferable that it is 1% or less. It is preferable that refractive index is 1.45-1.70.

Preferable curing conditions include irradiation conditions such as wavelength, intensity and irradiation time of light to be irradiated after applying the water-soluble composition or pattern forming agent of the present invention on a transparent support, such as the activity of the photoinitiator and the light used. Although it adjusts suitably according to the activity of a synthetic resin, etc., it is preferable that it is a wavelength peak of 300-500 nm, More preferably, it is a wavelength peak of 350-450 nm, Most preferably, as light wavelength normally, in order to fully enter light inside Is a wavelength peak of 360-380 nm. Moreover, as light intensity, 10-300 mW / cm <^2> is preferable, More preferably, it is 25-100 mW / cm <^2> , As for irradiation time, 5-500 second is preferable, More preferably, it is 10-300 second.

A crosslinking reaction can also be advanced by heating after apply | coating the water-soluble composition or pattern forming agent of this invention on a transparent support body. Heating is performed at 50-200 degreeC, Preferably it is 70 to 150 degreeC for 10 to 1 hour. When it is lower than 50 degreeC, a crosslinking reaction may not advance, and when higher than 200 degreeC, decomposition | disassembly of (A)-(D) component may arise or the transparency of an optical film may be inferior.

When creating the pattern of hardened | cured material by photolithography, 5.0-5.5 in water thickness is carried out by the stylus type | mold measuring device (Dektak150 manufactured by ULVAC) on the glass substrate, the water-soluble composition or pattern forming agent of this invention. After apply | coating using the spin coater which adjusted conditions to become micrometer, it prebaked for 10 minutes on the 90 degreeC hot plate. Thereafter, the mixture was cooled to room temperature and irradiated with 500 mJ / cm ^{2 of} light having a wavelength of 365 nm using a high pressure mercury lamp through a photomask (LINE / SPACE = 50 μm / 50 μm), and ion at 23 ° C. After soaking in the exchange water for 1 minute, the water adhered by the 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 above.

The hardened | cured material of this invention consists of the water-soluble composition or pattern forming agent of this invention. Specific uses of the water-soluble composition and pattern forming agent of the present invention include optical materials, paints, various coating agents, lining agents, inks, resists, liquid resists, adhesives, liquid crystal droppings, and the like represented by glasses and imaging lenses. Sealants for construction methods, image forming materials, pattern forming materials, printing plates, insulating varnishes, insulating sheets, laminates, printed boards, semiconductor devices, LED packages, liquid crystal inlets, organic EL, optical elements, electrical insulation Encapsulant for electronic parts and separators, molding materials, putty, building materials, siding, glass fiber impregnants, sealers, passivation films for semiconductors and solar cells, interlayer insulating films, protective films The lens portion of a lens sheet such as a prism lens sheet used for a backlight of a liquid crystal display device, a Fresnel lens sheet used for a screen such as a projection TV, a lenticular lens sheet, or such a sheet. Protective films or spacers of liquid crystal color filters, such as backlights, DNA separation chips, microreactors, nanobio devices, recording materials for hard disks, solid-state imaging devices, solar panels, light emitting diodes, organic light emitting devices, luminescent films, fluorescent Examples include films, MEMS devices, actuators, holograms, plasmon devices, polarizing plates, polarizing films, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, optical molding agents, and the like. Examples of the substrate that can be applied include metals, wood, rubber, plastics, glass, ceramic products, and the like.

When using the water-soluble composition and pattern forming agent of this invention for an optical film, an optical film does not extend | stretch (or orientation-processes) the obtained film or sheet | seat by the conventional method by film or sheet shaping | molding. You may manufacture without, or 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 cast molding method (flexible film forming method, solution flexible method) may be used.

Although the optical film using the water-soluble composition and pattern forming agent of this invention is not specifically limited about a shape, Usually, it is a film which has an optical film on a transparent support body, and is used for optical use, and is for polarizing plates used for liquid crystal display devices, etc. Various functional films, such as a protective film, a retardation film, a viewing angle expansion film, an antireflection film used for a plasma display, a low reflectivity film, and various functional films used for organic electroluminescent displays, etc. are mentioned.

The optical film using the water-soluble composition and pattern forming agent of this invention is an optical recording layer of the recordable optical disk (CD + R, DVD + R, next generation high density disk, etc.) which applied the optical film to the support body; Various lenses; Optical filters for image display devices; Various filters represented by color filters and color conversion filters; Or it can be used as protective sealing films, such as an organic electroluminescent element, an inorganic electroluminescent element, or an electronic paper display body.

Example

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

[Manufacturing method: (A) component aqueous solution No. 1 and No. 2]

138 parts of the hydroxyl group-containing polymer shown in [Table 1] were slowly added to a reaction flask containing 1000 parts of ion-exchanged water, stirred for 1 hour, and then heated to 90 ° C to completely dissolve. It cooled to 50 degreeC, and it injected | thrown-in 2 mol% N-methylol acrylamide and p-toluenesulfonic acid 0.1 part for hydroxyl groups as a photosensitizer, and stirred at 50 degreeC for 3 hours. After cooling the solution to room temperature, ion-exchange water was added so that solid content might be 15%, and it stirred for further 1 hour at room temperature, filtered with a 5 micrometer filter, and ion-exchange water was added, and solid content was made into 10 mass%. It adjusted and the (A) component aqueous solution No. 1 and No. 2 were obtained. About the obtained (A) component aqueous solution No. 1 and No. 2, the combination of the hydroxyl group containing polymer and the photosensitive agent provision agent which were used were shown collectively in [Table 1], respectively.

[Manufacturing method: (A) component aqueous solution No. 3-6]

138 parts of the hydroxyl group-containing polymer shown in [Table 1] were slowly added to a reaction flask containing 1000 parts of ion-exchanged water, stirred for 1 hour, and then heated to 90 ° C to completely dissolve. It cooled to 40 degreeC, the photosensitizer imparting agent shown in [Table 1] for 2 mol%, and 0.7 parts of phosphoric acid were thrown into the hydroxyl group, and stirring was continued at 40 degreeC for 2 hours. After cooling the solution to room temperature, ion-exchange water was added so that solid content might be 15%, and it stirred for further 1 hour at room temperature, filtered with a 5 micrometer filter, and ion-exchange water was added, and solid content was made into 10 mass%. It adjusted and the (A) component aqueous solution No. 3-No. 6 were obtained. About the obtained (A) component aqueous solution No.3-No.6, the combination of the hydroxyl group containing polymer and the photosensitive agent provision agent which were used were shown collectively in [Table 1], respectively.

TABLE 1

The structure of said (A) component aqueous solution No.1-No.6 was shown collectively in [Table 2].

TABLE 2

Here, in a 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 hydroxyl group-containing polymer was slowly added to 90.0 g of stirred ion-exchanged water, and the mixture was stirred at room temperature as it is for 1 hour. Then, internal temperature was adjusted from 85 degreeC to 90 degreeC, and stirring was continued for 2 hours. After confirming the dissolution, the solution was cooled to room temperature, filtered through a 1 µm filter, and (B) component aqueous solutions No. 1 to No. 3 were obtained. The combination of obtained (B) component aqueous solution No.1-No.3 and the used hydroxyl-containing polymer was put together in [Table 3], and was shown.

TABLE 3

The structure of the (B) component aqueous solution used by the Example was put together in [Table 4], and was shown.

TABLE 4

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

Examples 1-39 and Comparative Examples 1-8 Preparation of water-soluble composition

After stirring each component at room temperature for 1 hour according to the mixing | blending of Table 5-Table 10, it filtered with the 1 micrometer filter and obtained the water-soluble composition (Examples 1-39 and Comparative Examples 1-8). In addition, the numerical value of the compounding in a table | surface shows a mass part. In addition, 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: (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: Component aqueous solution No. 2 (B) Component aqueous solution (B)

B-3: (B) component aqueous solution No. 3 [(B) component aqueous solution]

C-1: Orgastics TC-335

(Titanium lactate ammonium salt aqueous solution: 75% of component concentration, Ti

Content 5%; Matsumoto Fine Chemical Manufacturing)

C-2: Orgastics ZC-126

(Zirconyl chloride solution: 30% component concentration, 11% Zr content);

Matsumoto Fine Chemical Manufacturing)

C-3: Zircosol ZN

(Aqueous zirconyl nitrate solution, component concentration 46%, Zr content 25%;

Daiichi Heteroelement Chemical Industry)

C-4: Orgastics WS-700

(Organic titanium-modified polyethyleneimine, component concentration 10% aqueous solution;

Matsumoto Fine Chemical Manufacturing)

D-1: NK ester A-600

(Alkylene oxide modified acrylate; Shin-Nakamura Chemical Co., Ltd. product)

D-2: NK ester A-GLY-20E

(Alkylene oxide modified acrylate; Shinnakamura Chemical Co., Ltd. product)

D-3: NK Economizer A-PG5054E

(Alkylene oxide modified acrylate; Shinnakamura Chemical Co., Ltd. product)

D-4: FFM-2 (polyfunctional acrylamide compound; manufactured by Fujifilm)

D-5: acryloyl morpholine

D-6: hydroxyacrylamide

E-1: Megapack 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; sun eye oil product)

E-4: DL-Lactic Acid

E-5: N, N-bis (2-hydroxyethyl) butane-1 aluminum = phenyl (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 aluminum-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

(Orient Chemical Co., Ltd., modified carbon black self dispersion, concentration 20%)

F-2: MICROPIGMO WMRD-5

(Orien Chemicals, Pigment Red 17 resin dispersion, concentration 20%)

F-3: MICROPIGMO WMGN-5

(Orien Chemicals, Pigment Green 7 resin dispersion, concentration 21%)

F-4: MICROPIGMO WMBE-5

(Orient Chemical Co., Ltd. Pigment Blue 15: 6 resin 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, coating property, photolithographic property, state change (humidity heat resistance 1) and haze change (humidity heat resistance 2) Was carried out in the following procedure. A result is written together to [Table 5]-[Table 10].

(Compatibility)

The state of each water-soluble composition was confirmed by visual observation, and the following reference | standard evaluated.

○: uniform

(Triangle | delta): Although it is a homogeneous system, it is slightly cloudy as a result of visual observation.

X: It is not compatible and a gelation or insoluble thing is observed.

The thing with evaluation (circle) can be used preferably, and the thing with evaluation x is not suitable for use.

(Applicability)

Each water-soluble composition was applied onto a glass substrate using a spin coater adjusted to a film thickness of 5.0 to 5.5 占 퐉 by means of a tactile shape measuring instrument (Dektak150 manufactured by Earl), followed by a 90 ° C hot plate (hot plate) was prebaked for 10 minutes. The state of the film at this time was confirmed by visual observation and evaluated according to the following criteria.

○: coating film is uniform

(Triangle | delta): Although it is a uniform film | membrane, turbidity is observed by visual observation.

×: non-uniform state or precipitate is confirmed, such as unevenness on the surface

It can be used preferably that evaluation is (circle), and it is not suitable to use that evaluation is x.

(Photolithographic)

Each water-soluble composition was applied onto a glass substrate using a spin coater adjusted to a film thickness of 5.0 to 5.5 占 퐉 by a tactile shape measuring instrument (Dektak150 manufactured by Earl), followed by a hot plate at 90 占 폚. Prebaking was performed for 10 minutes. Thereafter, the mixture was cooled to room temperature and irradiated with 500 mJ / cm ^{2 of} light having a wavelength of 365 nm using a high-pressure mercury lamp through a photomask (LINE / SPACE = 50 μm / 50 μm), and ion at 23 ° C. After soaking in the exchange water for 1 minute, the water adhered by the air gun was removed, and the substrate was dried in an oven at 140 ° C for 30 minutes. The pattern after drying was confirmed with the laser microscope, and the following reference | standard evaluated.

○: pattern within 50 ± 3 μm

Δ: within 50 ± 10 μm

X: exceeds 50 ± 10 μm or the pattern disappears

The thing whose evaluation result is (circle) or (triangle | delta) can be used as a pattern forming agent, Especially, what is (circle) can use especially preferably, and what is x is not suitable as a pattern forming agent.

(Moisture heat resistance 1: state change of hardened | cured material)

Each water-soluble composition was applied onto a glass substrate using a spin coater adjusted to a film thickness of 5.0 to 5.5 占 퐉 by a tactile shape measuring instrument (Dektak150 manufactured by Earl), followed by a hot plate at 90 占 폚. Prebaking was performed for 10 minutes. Then, after cooling to room temperature, using a high pressure mercury lamp, 3000 mJ / cm <^{2> of} light containing the wavelength of 365 nm was irradiated, and the board | substrate was dried in 140 degreeC oven for 30 minutes. After leaving the obtained hardened | cured material for 24 hours on 85 degreeC and 85% RH conditions, the state of hardened | cured material was confirmed by visual observation. The condition of the film after the moisture resistance test was evaluated based on the following criteria.

(Circle): It does not change before a test, and there is no change, such as peeling and discoloration.

×: there is a change

The hardened | cured material whose evaluation result is (circle) can be used for the use which requires moisture heat resistance, and the hardened | cured material whose evaluation result is x cannot be used for the use which requires moisture heat resistance.

(Moisture heat resistance 2: haze change)

Each water-soluble composition was applied onto a glass substrate using a spin coater adjusted to a film thickness of 5.0 to 5.5 占 퐉 by a tactile shape measuring instrument (Dektak150 manufactured by Earl), followed by a hot plate at 90 占 폚. Prebaking was performed for 10 minutes. Thereafter, after cooling to room temperature, a high pressure mercury lamp was used to irradiate 500 mJ / cm ^{2 of} light having a wavelength of 365 nm, and the substrate was dried in an oven at 140 ° C. for 30 minutes. The haze of the obtained hardened | cured material was measured by Japan color HAZEMETER NDH5000. Moreover, after leaving the obtained hardened | cured material for 24 hours on 85 degreeC and 85% RH conditions, the haze of hardened | cured material was measured similarly. Before and after the moisture resistance test, the following criteria evaluated.

◎: change in haze is less than 0.5

○: change in haze 0.5 or more and less than 1

(Triangle | delta): The change amount of haze is 1 or more and less than 3

×: change in haze 3 or more

The hardened | cured material whose evaluation result is (circle), (circle), and (triangle | delta) can be used for the use which requires moisture-heat resistance, and is excellent in moisture-heat resistance in order of (◎), (circle), and (triangle | delta). Especially, hardened | cured material which is (◎) is especially suitable for the use for which moisture-heat resistance is calculated | required. On the other hand, hardened | cured material which is x cannot be used for the use which is required for heat and moisture resistance. And about Examples 32-39 and Comparative Examples 6-8, since the coloring agent was added, the haze was not measured.

TABLE 5

TABLE 6

TABLE 7

TABLE 8

TABLE 9

TABLE 10

From Tables 1 to 10, it was found that the water-soluble composition of the present invention had high compatibility, excellent coating properties, excellent photolithography, and good heat and moisture resistance of the cured product obtained. Therefore, the water-soluble composition of this invention can be used suitably for uses, such as an ink, an image forming material, and a pattern forming agent, and the hardened | cured material of this invention can be used suitably for uses, such as an optical film.

Claims (10)

A water-soluble photosensitive polymer (A) having a photosensitive group and a hydroxyl group,
In addition to the water-soluble photosensitive polymer (A), the following general formula (I)

Compound (B) which has a structural unit represented by (In the said general formula (I), * means a bond.), And
A water-soluble composition containing a crosslinking agent (C). The method of claim 1,
The said water-soluble photosensitive polymer (A) has the following general formula (IIα), general formula (IIβ), and general formula (IIγ)

(In the above general formula (IIα), general formula (IIβ) and general formula (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 Each independently represent a photosensitive group, and * represents a bonding hand), wherein the water-soluble composition has at least one structural unit selected from the group consisting of: The method according to claim 1 or 2,
The water-soluble composition in which the said photosensitive group is a steel barzolium group, a cinnamoyl group, an acryl group, a methacryl group, an acrylamide group, or a methacrylamide group. The method according to any one of claims 1 to 3,
The said water-soluble photosensitive polymer (A) has the following general formula (IIδ) or general formula (IIε)

(In the general formulas (IIδ) and (IIε), An ^{q −} represents a q-valent anion, q represents 1 or 2, p represents a coefficient for maintaining charge neutral, and * represents a bond. Water-soluble composition containing the structural unit represented by the following). The method according to any one of claims 1 to 4,
The compound (B) is represented by the following general formula (III)

The water-soluble composition which is a compound which has a structural unit represented by (In said general formula (III), * means a bond.). The method according to any one of claims 1 to 5,
In addition to the water-soluble photosensitive polymer (A), the following general formula (IV)

(In the general formula (IV), R ¹ is a hydrogen atom or a methyl group, X ¹ is an oxygen atom or -NR ² - represents a, R ² is, represents a hydrogen atom or a hydrocarbon of 1 to 20 carbon atoms , X ² represents an alkylene group having 1 to 6 carbon atoms, the 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, and n is 0 to 30 Represents a number of *, * means a bonding hand, 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 may be the same or different, respectively. The water-soluble composition which further contains the compound (D) which has one or more groups represented by). The method according to any one of claims 1 to 6,
A water-soluble composition, wherein the crosslinking agent (C) is a zirconium compound or a titanium compound. The pattern forming agent which consists of a water-soluble composition in any one of Claims 1-7. The manufacturing method of hardened | cured material using the water-soluble composition of any one of Claims 1-7. Hardened | cured material which consists of water-soluble composition of any one of Claims 1-7.