WO2018117138A1 - 水溶性組成物、パターン形成剤、これらを用いた硬化物の製造方法および硬化物 - Google Patents
水溶性組成物、パターン形成剤、これらを用いた硬化物の製造方法および硬化物 Download PDFInfo
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- WO2018117138A1 WO2018117138A1 PCT/JP2017/045662 JP2017045662W WO2018117138A1 WO 2018117138 A1 WO2018117138 A1 WO 2018117138A1 JP 2017045662 W JP2017045662 W JP 2017045662W WO 2018117138 A1 WO2018117138 A1 WO 2018117138A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/04—Acyclic compounds
- C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/02—Esters of monocarboxylic acids
- C08F18/04—Vinyl esters
- C08F18/08—Vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Definitions
- 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.
- 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.
- 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.
- 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.
- 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.
- 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).
- the water-soluble photosensitive polymer (A) has the following general formulas (II ⁇ ), (II ⁇ ) and (II ⁇ ), (In the general formulas (II ⁇ ), (II ⁇ ) and (II ⁇ ), 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.
- the photosensitive group is preferably 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 (II ⁇ ) or (II ⁇ ), (In general formulas (II ⁇ ) and (II ⁇ ), 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.
- 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.
- 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.
- X 2 represents an alkylene group having 1 to 6 carbon atoms
- a hydrogen atom of the alkylene group having 1 to 6 carbon atoms represented by X 2 may be substituted with a halogen atom or a hydroxyl group
- n represents a number from 0 to 30, * means a bond
- the compound (D) which has 1 or more groups represented by these may be different.
- 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.
- the method for producing a cured product of the present invention is characterized by using the water-soluble composition of the present invention.
- the cured product of the present invention is characterized by comprising the water-soluble composition of the present invention.
- cured material 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.
- 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),
- component (A) a water-soluble photosensitive polymer having a photosensitive group and a hydroxyl group
- component (B) having a structural unit represented by: and a crosslinking agent (C) (hereinafter also referred to as “component (C)”.
- component (B) having a structural unit represented by: and a crosslinking agent (C) (hereinafter also referred to as “component (C)”.
- component (C) hereinafter also referred to as “component (C)”.
- * 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.
- each component will be described in order.
- 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 (II ⁇ ) to (II ⁇ ) as structural units because the cured product has high heat resistance, water resistance, and moist heat resistance.
- (II ⁇ ) and a compound having (II ⁇ ) 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.
- 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
- * represents a bond.
- An q ⁇ represents a q-valent anion
- q represents 1 or 2
- p represents a coefficient for maintaining a neutral charge
- * represents a bond.
- the divalent linking group represented by Y 1 , Y 2 and Y 3 in the general formulas (II ⁇ ), (II ⁇ ) and (II ⁇ ) is not particularly limited, and examples thereof include a methylene group, an ethylene group, and trimethylene.
- 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 (II ⁇ ), (II ⁇ ) and (II ⁇ ) 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, ⁇ -phenylmaleimide group, 2-pyrone group, azide group, thymine group, quinone group, uracil group, pyrimidine group, stilbazolium group, styrylpyridinium group 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
- 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.
- 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). A thing is 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.
- preferable component (A) include water-soluble photosensitive polymers represented by the following general formula (V) and the following general formula (VI).
- Y 1 and Q 1 are the same as the general formula (II ⁇ )
- Y 3 and Q 3 are the same as the general formula (II ⁇ )
- a, b, c, and d is a number from 0 to 5000, a and d are not 0 simultaneously, 100 ⁇ a + b + c + d ⁇ 5000, and * is a bond.
- 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.
- the polymer represented by the general formula (VI) can be obtained by subjecting a butenediol-polyvinyl alcohol copolymer to an acetalization reaction of an aldehyde having a photosensitive group under conditions of pH 1 to 4. It can also be produced by using commercially available products. For example, G polymer (butenediol vinyl alcohol copolymer) OKS-1081, OKS-1083, OKS-1109 manufactured by Nippon Synthetic Chemical Co., Ltd. It can also be obtained by carrying out an acetalization reaction under the conditions of .about.4.
- the component (A) is preferably 1 to 99 parts by mass, more preferably 5 to 95 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 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.
- 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, ⁇ -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 the total structural units. If the amount is too large, the water solubility may decrease, or the compatibil
- 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.
- the component (B) the following general formula (III),
- 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%, more preferably 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.
- component (B) commercially available products may be used, and examples thereof include Gohsenx Z-100, Z-200, Z-220, Z-300 and Z-410 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
- Component (B) is preferably 1 to 99 parts by weight, more preferably 5 to 95 parts by weight, most preferably 10 to 90 parts by weight, based on 100 parts by weight of the sum of components (A) and (B). preferable.
- 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.
- 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).
- 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.
- 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, ⁇ -diketone, dimethylglyoxime, citric acid, tartaric acid, maleic acid, polyhydrazide, phosphoric acid ester and the like can be mentioned, and these can be used alone or in combination of two or more.
- the chelate type ligand include hydroxycarboxylic acid or a salt thereof, amino alcohol, ⁇ -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 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; 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, dicarbonate
- zirconium complex salts such as potassium potassium, sodium zirconium oxalate, sodium zirconium citrate, ammonium zirconium citrate, and zirconium lactate ammonium
- zirconium chelate complexes having one or more chelating agents as ligands can be mentioned. .
- water-soluble zirconium is preferable, and
- zirconium chelate complex examples 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.
- 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.
- 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 Elemental Chemical Co., Ltd.), ORGATIZ ZA-45, ORGATIZ ZA-65, ORGATIZ ZB-126, ORGATIZ ZC-126, ORGATICS 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
- 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 chelates such as titanium ethyl acetoacetate, titanium triethanolaluminate, titanium oxalate Body; titanium acylates such as polyhydroxyt
- 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.
- a zirconium compound or a titanium compound is particularly preferable among the components (C) because the cured product obtained from the water-soluble composition of the present invention has good heat and 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 in 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), and the metal content is preferably 0.01 to 3% by mass in the component excluding the solvent of the water-soluble composition. Preferably, the content is 0.01 to 1% by mass.
- 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.
- 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 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
- N represents a number from 0 to 30, * means a bond
- R 1 , X 1 , X 2 , n May be the same or different.
- the hydrocarbon group having 1 to 20 carbon atoms represented by R 2 in the general formula (IV) is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms, 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.
- an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 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.
- alkyl group having 1 to 20 carbon atoms examples 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.
- alkyl group having 1 to 10 carbon atoms examples 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, etc. It is below.
- alkenyl group having 2 to 20 carbon atoms examples 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.
- alkenyl group having 2 to 10 carbon atoms examples include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, and 3-pentenyl. , 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl 3- octenyl, 3-nonenyl 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.
- 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.
- 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.
- aryl group having 6 to 20 carbon atoms for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, etc., one or more substituted with the above alkyl group, the above alkenyl group, carboxyl group, halogen atom, etc.
- Phenyl, biphenylyl, naphthyl, anthryl, etc. such as 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, etc.
- aryl group of ⁇ 10 for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, etc., phenyl, biphenylyl, naphthyl, substituted with one or more of the above alkyl group, the above alkenyl group, carboxyl group, halogen atom, etc.
- Anthril for example, 4- Rorofeniru, 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.
- Examples include benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and naphthylpropyl.
- the above arylalkyl group having 7 to 20 carbon atoms means that the hydrogen atom of the alkyl group is an aryl group.
- substituted is meant a group having 7 to 20 carbon atoms. Examples include benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl and phenylethyl.
- alkylene group having 1 to 6 carbon atoms represented by X 2 in the general formula (IV) examples include linear chains such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.
- alkylene groups and branched alkylene groups such as isopropylene groups and isobutylene groups.
- an alkylene oxide modified acrylate compound for example, 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).
- the alkylene oxide-modified methacrylate compound is a compound represented by the general formula In (IV), R 1 is a methyl group, X 1 is an oxygen atom, and n is a compound of 1 to 30.
- alkylene oxide-modified acrylate compound examples 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.
- alkylene oxide-modified methacrylate compound examples 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. Examples include propylene oxide modified 1,6-hexanediol dimethacrylate It is.
- alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound commercially available products can also be preferably used.
- NK ester A-600, A-GLY-20E, NK Economer A-PG5054E (hereinafter, Shin-Nakamura Chemical) (Made by industry) etc. are mentioned.
- 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 it is excellent in
- n 6 or more because of excellent water solubility.
- the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound have a plurality of groups represented by the general formula (IV)
- 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 ) Are compounds in which R 1 is a methyl group, X 1 is NR 2 —, and n is 0.
- acrylamide compound examples include hydroxyacrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-butylacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N. -Dipropylacrylamide, acryloylmorpholine, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, etc.
- methacrylamide compound examples 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. Can be mentioned.
- acrylamide compound and the methacrylamide compound 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.).
- the content of the component (D) is 1 to 50 parts by mass with respect to 100 parts by mass of the sum of the components (A), (B) and (D), )
- 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.
- organic solvent examples 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 mono Mechi Cellosolve solvents such as ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propan
- 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.
- 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.
- 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.
- 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.
- water-soluble polymer not belonging to the component (A) and the component (B) examples 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 poly salt Vinyl resins, water-soluble polyacrylate resin, a water-soluble resin and a styrene-
- any weakly acidic compound having a carboxyl group can be used without limitation.
- 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.
- 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, and allyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, ⁇ -glyci Epoxy-functional alkoxysilanes such as xylpropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -amino Use amino-functional alkoxysilane
- 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-dimethoxy Acetophenones such as cetophenone, 4,4-dimethoxyacetophenone, 4-ethoxyacetophenone, diethoxyacetophen
- the surfactant examples 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.
- fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates
- anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates,
- 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.
- pigments and dyes can be used.
- 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.
- 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.
- the pigment examples 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
- 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 examples of the carbon black
- a resin is previously dispersed in a resin and coated with a resin of 20 to 200 mg / g, an acid or alkaline surface treatment of the above carbon black, 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.
- 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, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (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.
- MICROPIGMO WMYW-5 MICROPIGMO WMRD-5, MICROPIGMO WMBN-5, MICROPIGMO WMGN-5, MICROPIGMO WMBK-5, MICROPIGMO WMBE-5, MICROPIGMOWMM, 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, 20 , 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,
- the dye examples 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.
- water-soluble initiators such as Irg2959, Irg819DW (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.
- water-soluble dyes examples include WATER YELLOW 1, WATER YELLOW 2, WATER YELLOW 6C, WATER YELLOW 6CL, WATER ORANGE 18, WATER ORANGE 25, WATERREDER 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 BLUE 105S, WER BLUE 105S VIOLET 7, WATER B ACK 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, BONJETBL ENT Chemical Industry Co., Ltd.).
- water-soluble preservative examples 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, C acid phenylmercuri
- 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 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 ( -Dodecylthiophene), poly (3-methoxythiophene), poly (3-ethoxythi
- 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.
- 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.
- 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 ⁇ m or less can be formed with good accuracy within ⁇ 10%.
- the method for producing a cured product of the present invention is performed using the water-soluble composition or pattern forming agent of the present 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 to a supporting substrate such as glass, metal, paper, plastic, etc. 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
- the transparent support material examples include inorganic materials such as glass; cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; polyamides; polycarbonates; polyethylene terephthalate Polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polyester such as polybutylene terephthalate; polystyrene; polyethylene, Polyolefin such as polypropylene and polymethylpentene; Acrylic resin such as polymethyl methacrylate; Polycarbonate; Polysulfone Polyether sulfone; polyether ketone; polyetherimides; polyoxyethylene, and polymer materials such as norbornene resins.
- the transmittance of the transparent support is preferably 80% or more,
- the irradiation conditions such as the wavelength, intensity, and irradiation time of the irradiated light are light.
- the light wavelength is preferably one having a wavelength peak of 300 to 500 nm in order to allow light to sufficiently enter the inside. More preferred is a wavelength peak of 350 to 450 nm, and most preferred is a wavelength peak of 360 to 380 nm.
- the light intensity is preferably 10 to 300 mW / cm 2 , more preferably 25 to 100 mW / cm 2
- the irradiation time is preferably 5 to 500 seconds, more preferably 10 to 300 seconds.
- the crosslinking reaction can also be advanced by heating after applying the water-soluble composition or pattern forming agent of the present invention on the transparent support. 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 lowered.
- 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 ⁇ m, pre-baking was performed on a hot plate at 90 ° C. for 10 minutes.
- a stylus-type shape measuring instrument (Dektak 150 manufactured by ULVAC) in a film thickness of 5.0 to 5.
- the cured product of the present invention is composed of 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
- the base material that can be applied as a coating agent include metals, wood, rubber, plastics, glass, and ceramic products.
- 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
- a melt molding method such as extrusion molding or blow molding
- a casting method cast film forming method, solution casting method
- 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.
- solid content described in a present Example means the mass% which the component except a solvent occupies.
- ⁇ in the table means that the corresponding structural unit is included, and ⁇ means that the corresponding structural unit is not included.
- composition of the component (B) aqueous solution used in the examples is summarized in [Table 4].
- ⁇ 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 ⁇ m filter. (Examples 1 to 39 and Comparative Examples 1 to 8) were obtained.
- surface represents a mass part.
- surface represents the following component.
- 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 Olga Tix 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
- the pattern is within 50 ⁇ 3 ⁇ m ⁇ : Within 50 ⁇ 10 ⁇ m ⁇ : The evaluation result that exceeds 50 ⁇ 10 ⁇ m or the pattern disappears is ⁇ or ⁇ 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.
- the water-soluble composition of the present invention has high compatibility, excellent coating properties, excellent photolithographic properties, and good wet 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.
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Abstract
Description
(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。
(一般式(IIα)、(IIβ)および(IIγ)中、Y1、Y2およびY3は、それぞれ独立に直接結合または2価の連結基を表し、Q1、Q2およびQ3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、Anq-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、R1は水素原子またはメチル基を表し、X1は酸素原子または-NR2-を表し、R2は、水素原子または炭素原子数1~20の炭化水素基を表し、X2は炭素原子数1~6のアルキレン基を表し、X2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R1、X1、X2、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。
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。
本発明の水溶性組成物に係る(A)成分とは、感光基および水酸基を有していればよく、特に限定されない。(A)成分として好ましいものとして、硬化物の耐熱性、耐水性および耐湿熱性が高いことから、下記一般式(IIα)~(IIε)を構成単位として有する化合物が挙げられ、中でも、(IIδ)および(IIε)を構成単位として有する化合物は、LED光源(365nm)を用いた場合においても硬化性に優れる水溶性組成物並びに耐熱性、耐水性および耐湿熱性に優れる硬化物が得られることからより好ましい。
ここで、一般式(IIδ)、(IIε)中、Anq-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。
本発明の水溶性組成物に係る(B)成分とは、上記感光基を構造中に有さず、かつ、下記一般式(I)で表される構成単位を有していればよく、特に限定されない。
本発明の水溶性組成物に含有される(C)成分は、(B)成分を架橋し得るものであれば、制限なく用いることができる。(C)成分としては、例えば、従来既知の有機系架橋剤、キレート化剤を有している金属キレート錯体、ジルコニウム化合物およびチタン化合物を好ましく用いることができる。
本発明の水溶性組成物は、(D)成分として、下記一般式(IV)、
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、R1は水素原子またはメチル基を表し、X1は酸素原子または-NR2-を表し、R2は、水素原子または炭素原子数1~20の炭化水素基を表し、X2は炭素原子数1~6のアルキレン基を表し、X2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R1、X1、X2、nは、それぞれ同一であっても異なっていてもよい。
1000部のイオン交換水を入れた反応フラスコに[表1]に示す水酸基含有ポリマー138部をゆっくり投入し、1時間攪拌した後、90℃まで加温して完全に溶解させた。50℃まで冷却し、感光性付与剤として水酸基の2mol%分のN-メチロールアクリルアミドとp-トルエンスルホン酸0.1部を投入し、50℃3時間攪拌を継続した。溶液を室温まで冷却後、固形分が15%となるよう、イオン交換水を追加し、室温で更に1時間攪拌を行ない、5μmフィルターでろ過した後、イオン交換水を加えて固形分を10質量%に調整し、(A)成分水溶液No.1およびNo.2を得た。得られた(A)成分水溶液No.1およびNo.2について、それぞれ用いた水酸基含有ポリマーおよび感光基付与剤の組み合わせを[表1]にまとめた。
1000部のイオン交換水を入れた反応フラスコに[表1]に示す水酸基含有ポリマー138部をゆっくり投入し、1時間攪拌した後、90℃まで加温して完全に溶解させた。40℃まで冷却し、水酸基の2mol%分の[表1]に示す感光基付与剤とリン酸0.7部を投入し、40℃で2時間攪拌を継続した。溶液を室温まで冷却後、固形分が15%となるよう、イオン交換水を追加し、室温で更に1時間攪拌を行ない、5μmフィルターでろ過した後、イオン交換水を加えて固形分を10質量%に調整し、(A)成分水溶液No.3~No.6を得た。得られた(A)成分水溶液No.3~No.6について、それぞれ用いた水酸基含有ポリマーおよび感光基付与剤の組み合わせを[表1]にまとめた。
水酸基含有ポリマー10.0gを、攪拌しているイオン交換水90.0gにゆっくり添加し、そのまま室温で1時間攪拌した。その後、内温を85℃から90℃に調整し、2時間攪拌を継続した。溶解を確認した後に、室温まで冷却し、1μmフィルターでろ過し、(B)成分水溶液No.1~No.3を得た。得られた(B)成分水溶液No.1~No.3と用いた水酸基含有ポリマーの組み合わせを[表3]にまとめた。
[表5]~[表10]の配合に従って各成分を室温で1時間撹拌後、1μmフィルターでろ過し、水溶性組成物(実施例1~39および比較例1~8)を得た。なお、表中の配合の数値は質量部を表す。また、表中の各成分の符号は、下記の成分を表す。
A-1:(A)成分水溶液No.1 [(A)成分水溶液]
A-2:(A)成分水溶液No.2 [(A)成分水溶液]
A-3:(A)成分水溶液No.3 [(A)成分水溶液]
A-4:(A)成分水溶液No.4 [(A)成分水溶液]
A-5:(A)成分水溶液No.5 [(A)成分水溶液]
A-6:(A)成分水溶液No.6 [(A)成分水溶液]
B-1:(B)成分水溶液No.1 [(B)成分水溶液]
B-2:(B)成分水溶液No.2 [(B)成分水溶液]
B-3:(B)成分水溶液No.3 [(B)成分水溶液]
C-1:オルガチックスTC-335
(チタンラクテートアンモニウム塩水溶液:成分濃度75%、Ti
含有量5%;マツモトファインケミカル製)
C-2:オルガチックスZC-126
(塩化ジルコニル水溶液:成分濃度30%、Zr含有量11%;
マツモトファインケミカル製)
C-3:ジルコゾールZN
(硝酸ジルコニル水溶液、成分濃度46%、Zr含有量25%;
第一稀元素化学工業製 )
C-4:オルガチックスWS-700
(有機チタン変性ポリエチレンイミン、成分濃度10%水溶液;
マツモトファインケミカル製)
D-1:NKエステル A-600
(アルキレンオキサイド変性アクリレート;新中村化学工業製)
D-2:NKエステル A-GLY-20E
(アルキレンオキサイド変性アクリレート;新中村化学工業製)
D-3:NKエコノマー A-PG5054E
(アルキレンオキサイド変性アクリレート;新中村化学工業製)
D-4:FFM-2(多官能アクリルアミド化合物;富士フィルム製)
D-5:アクリロイルモルフォリン
D-6:ヒドロキシアクリルアミド
E-1:メガファックF-444(フッ素系レベリング剤;DIC製)
E-2:KP-112(シリコン系レベリング剤;信越化学工業製)
E-3:サンアイバックIT-15SA(防腐剤;三愛石油製)
E-4:DL-乳酸
E-5:N,N-ビス(2-ヒドロキシエチル)ブタン-1アミニウム=フ
ェニル(2,4,6-トリメチルベンゾイル)ホスフィネート(ラ
ジカル開始剤)
E-6:3-((4-(2-メチル-2-モルホリノプロパノイル)フェニ
ル)チオ)プロパン酸=ナトリウム塩(ラジカル開始剤)
E-7:N,N-ビス(2-ヒドロキシエチル)ブタン-1アミニウム-2
-カルボキシベンゾフェノン(ラジカル開始剤)
E-8:カリウム-2-カルボキシベンゾフェノン(ラジカル開始剤)
E-9:ジカリウム-4,4’-ジカルボキシベンゾフェノン(ラジカル開
始剤)
F-1:BONJET BLACK CW-1
(オリヱント化学工業社製、改質カーボンブラック自己分散体、濃
度20%)
F-2:MICROPIGMO WMRD-5
(オリヱント化学工業社製、Pigment Red17樹脂分散
体、濃度20%)
F-3:MICROPIGMO WMGN-5
(オリヱント化学工業社製、Pigment Green7樹脂分
散体、濃度21%)
F-4:MICROPIGMO WMBE-5
(オリヱント化学工業社製、Pigment Blue15:6樹
脂分散体、濃度20%)
実施例1~39および比較例1~8の水溶性組成物において、相溶性、塗布性、フォトリソ性、硬化物の状態変化(耐湿熱性1)およびヘイズ変化(耐湿熱性2)の評価を、下記の手順で行った。結果を[表5]~[表10]に併記する。
各水溶性組成物の状態を目視で確認し、以下の基準で評価した。
○:均一である
△:均一系であるが、目視で若干濁っている
×:相溶しない、ゲル化または不溶物が見られる
評価が○であるものは、好ましく使用でき、評価が×のものは使用に適さない。
各水溶性組成物をガラス基板上に触針式形状測定器(アルバック製Dektak150)により膜厚が5.0~5.5μmとなるように条件を調整したスピンコーターを用いて塗布した後、90℃のホットプレートで10分間プリベークを行なった。このときの膜の状態を目視で確認し、以下の基準で評価した。
○:塗布膜が均一である
△:均一な膜であるが、目視で濁りが観測される
×:表面にムラがある等不均一な状態または析出物が確認された
評価が○であるものは、好ましく使用でき、評価が×のものは使用に適さない。
各水溶性組成物をガラス基板上に、触針式形状測定器(アルバック製Dektak150)により膜厚が5.0~5.5μmとなるように条件を調整したスピンコーターを用いて塗布した後、90℃のホットプレートで10分間プリベークを行なった。その後、室温まで冷却し、フォトマスク(LINE/SPACE=50μm/50μm)を介し、高圧水銀ランプを用い、365nmの波長を含む光を500mJ/cm2照射し、23℃のイオン交換水に1分間浸漬した後、エアーガンで付着した水を除去し、基板を140℃のオーブン内で30分乾燥させた。乾燥後のパターンをレーザー顕微鏡で確認し、以下の基準で評価した。
○:パターンが50±3μm以内
△:50±10μm以内
×:50±10μmを超えるあるいはパターンが無くなる
評価結果が、○または△のものは、パターン形成剤として使用でき、その中でも○のものは特に好ましく使用でき、×のものはパターン形成剤として適さない。
各水溶性組成物をガラス基板上に、触針式形状測定器(アルバック製Dektak150)により膜厚が5.0~5.5μmとなるように条件を調整したスピンコーターを用いて塗布した後、90℃のホットプレートで10分間プリベークを行なった。その後、室温まで冷却した後、高圧水銀ランプを用い、365nmの波長を含む光を3000mJ/cm2照射し、基板を140℃のオーブン内で30分乾燥させた。得られた硬化物を85℃、85%RHの条件で24時間放置した後、硬化物の状態を目視で確認した。耐湿性試験後の膜の状態を、以下の基準で評価した。
○:試験前と変わらず、剥がれ、色抜け等の変化の無い
×:変化がある
評価結果が、○の硬化物は耐湿熱性が要求される用途に使用でき、評価結果が×の硬化物は、耐湿熱性が要求される用途に使用することができない。
各水溶性組成物をガラス基板上に、触針式形状測定器(アルバック製Dektak150)により膜厚が5.0~5.5μmとなるように条件を調整したスピンコーターを用いて塗布した後、90℃のホットプレートで10分間プリベークを行なった。その後、室温まで冷却した後、高圧水銀ランプを用い、365nmの波長を含む光を500mJ/cm2照射し、基板を140℃のオーブン内で30分乾燥させた。得られた硬化物のヘイズを日本電色HAZEMETER NDH5000で測定した。更に得られた硬化物を85℃、85%RHの条件で24時間放置した後、硬化物のヘイズを同様に測定した。耐湿性試験前後において、以下の基準で評価した。
◎:ヘイズの変化量が0.5未満
○:ヘイズの変化量が0.5以上1未満
△:ヘイズの変化量が1以上3未満
×:ヘイズの変化量が3以上
評価結果が◎、○および△の硬化物は耐湿熱性が要求される用途に使用でき、◎、○、△の順に耐湿熱性に優れる。中でも◎である硬化物は、特に、耐湿熱性が要求される用途に好適である。一方、×である硬化物は、耐湿熱性が要求される用途には使用することができない。なお、実施例32~39および比較例6~8については、着色剤を添加しているため、ヘイズの測定は行っていない。
Claims (10)
- 前記感光基が、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請求項1または2記載の水溶性組成物。
- 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、R1は水素原子またはメチル基を表し、X1は酸素原子または-NR2-を表し、R2は、水素原子または炭素原子数1~20の炭化水素基を表し、X2は炭素原子数1~6のアルキレン基を表し、X2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R1、X1、X2、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)を含有する請求項1~5のうちいずれか一項記載の水溶性組成物。 - 前記架橋剤(C)が、ジルコニウム化合物またはチタン化合物である請求項1~6のうちいずれか一項記載の水溶性組成物。
- 請求項1~7のうちいずれか一項記載の水溶性組成物からなるパターン形成剤。
- 請求項1~7のうちいずれか一項記載の水溶性組成物を用いたことを特徴とする硬化物の製造方法。
- 請求項1~7のうちいずれか一項記載の水溶性組成物からなることを特徴とする硬化物。
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KR102478397B1 (ko) | 2022-12-15 |
JP7096772B2 (ja) | 2022-07-06 |
JPWO2018117138A1 (ja) | 2019-10-31 |
TWI753072B (zh) | 2022-01-21 |
CN110036343B (zh) | 2023-06-13 |
TW201831584A (zh) | 2018-09-01 |
CN110036343A (zh) | 2019-07-19 |
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