CN112384538A

CN112384538A - Polymer, composition containing same, method for curing same, cured product thereof, and method for producing polymer

Info

Publication number: CN112384538A
Application number: CN201980043255.7A
Authority: CN
Inventors: 原宪司; 宫田涉
Original assignee: Adeka Corp
Current assignee: Adeka Corp
Priority date: 2018-08-21
Filing date: 2019-08-19
Publication date: 2021-02-19
Also published as: WO2020040094A1; JPWO2020040094A1

Abstract

Providing: a polymer used in a composition having excellent chemical resistance, particularly excellent water resistance, capable of obtaining a cured product having a high-definition pattern and excellent transparency, a composition containing the same, a curing method thereof, a cured product thereof, and a method for producing the polymer. A polymer having a structure represented by the following general formula (I) wherein R is¹、R²、R³And R⁴Each independently represents a hydrogen atom or the like, X represents a group represented by the following formula (I alpha) or (I beta), and n represents 0 to 2In the general formulae (I α) and (I β), R represents an atomic bond¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶And R¹⁷Each independently represents a hydrogen atom or the like, and represents an atomic bond.

Description

Polymer, composition containing same, method for curing same, cured product thereof, and method for producing polymer

Technical Field

The present invention relates to a polymer, a composition containing the same, a method for curing the same, a cured product thereof, and a method for producing the polymer, and more particularly to: a polymer used in a composition having excellent chemical resistance, particularly excellent water resistance, capable of obtaining a cured product having a high-definition pattern and excellent transparency, a composition containing the same, a curing method thereof, a cured product thereof, and a method for producing the polymer.

Background

Polyvinyl alcohol is used for various applications such as paints, inks, adhesives, and optical films. For example, patent document 1 proposes a resin composition containing a resin such as polyvinyl alcohol and a metal-organic compound such as a titanium organic compound or a zirconium organic compound, and having excellent gas barrier properties and water resistance. Patent document 2 proposes a heat-sensitive recording material containing an acetoacetyl-modified polyvinyl alcohol and a silane coupling agent having an amino group as a crosslinking agent, and having excellent chemical resistance and viscosity. Further, patent document 3 proposes a method for producing a crosslinked polyvinyl alcohol resin which is obtained by crosslinking an acetoacetate group-containing polyvinyl alcohol resin with glyoxylate, is less discolored with time by ultraviolet rays, and has excellent weather resistance.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 11-310712

Patent document 2: japanese laid-open patent publication No. 2009-039874

Patent document 3: japanese patent laid-open publication No. 2013-028697

Disclosure of Invention

Problems to be solved by the invention

Currently, for applications such as patterning agents, inks, various resists, optical films for flat panel displays, coating materials for optical films, and adhesives, compositions capable of obtaining cured products having high-definition patterns and excellent moist heat resistance are increasingly required. In such a case, the compositions proposed in patent documents 1 to 3 are not always compatible with the compositions at a high level required by the market, and further improvements are currently required for the compositions.

Accordingly, an object of the present invention is to provide: a polymer used in a composition having excellent chemical resistance, particularly excellent water resistance, capable of obtaining a cured product having a high-definition pattern and excellent transparency, a composition containing the same, a curing method thereof, a cured product thereof, and a method for producing the polymer.

Means for solving the problems

The present inventors have made extensive studies to solve the above problems, and as a result, have found that: the present invention has been completed by the fact that the above-mentioned problems can be solved by using a polymer having a specific structure.

That is, the polymer of the present invention is characterized by having a structure represented by the following general formula (I),

here, in the general formula (I), R¹、R²、R³And R⁴Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,

R¹、R²、R³and R⁴1 or 2 or more methylene groups in the group are optionally replaced by-O-, -CO-, -COO-, -OCO-, -NR-under the condition that oxygen is not adjacent⁵-、-NR⁵CO-、-S-、-CS-、-SO₂-, -SCO-, -COS-, -OCS-or-CSO-,

R⁵represents hydrogenA hydrocarbon group having 1 to 20 atoms or carbon atoms,

R¹、R²、R³、R⁴and R⁵The hydrogen atom in the group is optionally substituted by a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic group having 2 to 20 carbon atoms,

x represents a group represented by the following formula (I alpha) or (I beta),

n represents an integer of 0 to 2,

when n is 2, a plurality of R's present in the molecule³And R⁴Optionally identical or different, represent an atomic bond.

Here, in the general formulae (I α), (I β), R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶And R¹⁷Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,

R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶and R¹⁷1 or 2 or more methylene groups in the group are optionally replaced by-O-, -CO-, -COO-, -OCO-, -NR-under the condition that oxygen is not adjacent¹⁸-、-NR¹⁸CO-、-S-、-CS-、-SO₂-, -SCO-, -COS-, -OCS-or-CSO-,

R¹⁸represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷and R¹⁸The hydrogen atom in the group is optionally substituted by halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl ether group, mercapto group, isocyanate group or the likeThe heterocycle is substituted with a group having 2 to 20 carbon atoms and represents an atomic bond.

In the polymer of the present invention, R in the general formula (I) is preferable¹、R²、R³And R⁴One or more of them is a hydrogen atom. In the polymer of the present invention, R in the general formula (I) is preferably R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶And R¹⁷One or more of them is a hydrogen atom.

Another polymer of the invention is characterized by having the structure: a structure obtained by reacting a polymer having a structure represented by the following general formula (II) with a compound represented by the following general formula (III).

Here, in the general formula (II), R²¹、R²²、R²³And R²⁴Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,

R²¹、R²²、R²³and R²⁴1 or 2 or more methylene groups in the group are optionally replaced by-O-, -CO-, -COO-, -OCO-, -NR-under the condition that oxygen is not adjacent²⁵-、-NR²⁵CO-、-S-、-CS-、-SO₂-, -SCO-, -COS-, -OCS-or-CSO-,

R²⁵represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

R²¹、R²²、R²³、R²⁴and R²⁵Wherein 1 or 2 or more hydrogen atoms in the group are optionally substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic ring-containing group having 2 to 20 carbon atoms,

m represents an integer of 0 to 2, and when m is 2, a plurality of R's present in the molecule²³And R²⁴Optionally identical or different, represent an atomic bond.

In the general formula (III), R³¹、R³²And R³³Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,

R³¹、R³²and R³³1 or 2 or more methylene groups in the group are optionally replaced by-O-, -CO-, -COO-, -OCO-, -NR-under the condition that oxygen is not adjacent³⁴-、-NR³⁴CO-、-S-、-CS-、-SO₂-, -SCO-, -COS-, -OCS-or-CSO-,

R³⁴represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

R³¹、R³²、R³³and R³⁴The hydrogen atom in the group is optionally substituted by a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic group having 2 to 20 carbon atoms.

The composition of the present invention is characterized by containing the polymer of the present invention.

The method for producing a cured product of the present invention is characterized by comprising a step of curing the composition of the present invention.

The cured product of the present invention is characterized by being obtained from the composition of the present invention.

The method for producing a polymer of the present invention is characterized by comprising a step of reacting a polymer having a structure represented by general formula (II) with a compound represented by general formula (III).

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: a polymer used in a composition having excellent chemical resistance, particularly excellent water resistance, capable of obtaining a cured product having a high-definition pattern and excellent transparency, a composition containing the same, a curing method thereof, a cured product thereof, and a method for producing the polymer. The composition of the present invention can be suitably used for applications such as an ink material or an adhesive, for example, a pattern forming agent, an optical film for a flat panel display, a coating material for an optical film, and a binder for ink.

Detailed Description

The polymer of the present invention, a composition containing the same, a method for curing the same, a cured product thereof, and a method for producing the polymer will be described in detail below.

The composition of the present invention is a composition containing the polymer of the present invention having a structure represented by the following general formula (I) (hereinafter, also referred to as polymer (a1)) or another polymer of the present invention having a structure obtained by reacting a polymer having a structure represented by the following general formula (II) with a compound represented by the following general formula (III) (hereinafter, also referred to as polymer (a2)), and the composition of the present invention is excellent in storage stability and can exist in a single component, and therefore a cured product can be easily produced. First, the polymer (a1) will be described.

R⁵represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

R¹、R²、R³、R⁴and R⁵The hydrogen atoms in the groups are optionally replaced by halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl ether groups, mercapto groups, isocyanate groups or hetero groupsA ring substituted with a group having 2 to 20 carbon atoms,

n represents an integer of 0 to 2,

R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷and R¹⁸The hydrogen atom in the group is optionally substituted by a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic group having 2 to 20 carbon atoms, and represents an atomic bond.

In the polymer (A1), R in the general formula (I)¹～R⁴In the case where at least one of them is a hydrogen atom, R is particularly preferred because it is excellent in storage stability and chemical resistance¹～R⁴All are hydrogen atoms.

R in the general formula (I)¹¹～R¹⁷Among them, more than one hydrogen atom is excellent in storage stability and reactivity, and the cured product has excellent chemical resistance, so that R is particularly preferable¹¹～R¹⁷All are hydrogen atoms.

The polymer having n of 1 in the general formula (I) is preferable because it has excellent storage stability and good productivity.

When the ratio of the structure represented by the general formula (I) to the polymer (a1) is 1 to 20% by mass, the water solubility is excellent and the moist heat resistance of the resulting cured product is excellent, and therefore 1 to 10% by mass is particularly preferable.

The polymer (A1) having a pullulan-equivalent weight average molecular weight (Mw) of 1000 to 200000 by Gel Permeation Chromatography (GPC) is excellent in water solubility and the resulting cured product is excellent in moist heat resistance, and is preferably 30000 to 120000.

When the hydroxyl value of the polymer (A1) is 100 to 2000mgKOH/g, the water solubility is excellent and the moist heat resistance of the resulting cured product is excellent, and therefore 500 to 1500mgKOH/g is particularly preferable. In the present invention, the hydroxyl value is measured in accordance with JIS K0070-1992.

The polymer (A1) preferably has a degree of saponification of 70 to 99 from the viewpoint of excellent water solubility, and particularly preferably 85 to 99 from the viewpoint of water resistance. The polymer (a1) having a saponification degree within the above range is preferable because it has excellent water solubility and excellent storage stability of an aqueous solution.

The polymer (A1) preferably has a 4% aqueous solution viscosity of 3 to 60 mPaS, particularly preferably 4 to 50 mPaS, from the viewpoint of excellent handling. Here, the 4% aqueous solution viscosity means, unless particularly limited: the value obtained by measuring a 4% aqueous solution adjusted to 20 ℃ with an E-type viscometer.

In the general formula (I), R¹～R⁵And R¹¹～R¹⁸The hydrocarbon group having 1 to 20 carbon atoms is not particularly limited, but is preferably an alkyl group having 1 to 20 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 or a carbon atomAnd arylalkyl groups having 7 to 20 carbon atoms, more preferably C1-10 alkyl groups, C2-10 alkenyl groups, C3-10 cycloalkyl groups, C4-10 cycloalkylalkyl groups, C6-10 aryl groups, and C7-10 arylalkyl groups, from the viewpoint of good chemical resistance when added to the composition.

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a tert-octyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, and. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a tert-octyl group, a nonyl group, an isononyl group, a decyl group, and an isodecyl group.

Examples of the alkenyl group having 2 to 20 carbon atoms include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 2-butenyl group, a 4-pentenyl group, a 3-pentenyl group, a 2-hexenyl group, a 3-hexenyl group, a 5-hexenyl group, a 2-heptenyl group, a 3-heptenyl group, a 4-heptenyl group, a 3-octenyl group, a 3-nonenyl group, a 4-decenyl group, a 3-undecenyl group, a 4-dodecenyl group, a 3-cyclohexenyl group, a2, 5-cyclohexadienyl-1-methyl group, and a4, 8, 12-tetradecatrienylallyl group. Examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 2-butenyl group, a 4-pentenyl group, a 3-pentenyl group, a 2-hexenyl group, a 3-hexenyl group, a 5-hexenyl group, a 2-heptenyl group, a 3-heptenyl group, a 4-heptenyl group, a 3-octenyl group, a 3-nonenyl group, and a 4-decenyl group.

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 thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalenyl, bicyclo [1.1.1] pentyl and tetradecahydroanthracenyl. 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] pentyl groups.

The cycloalkyl alkyl group having 4 to 20 carbon atoms is: a group having 4 to 20 carbon atoms, wherein a hydrogen atom of the alkyl group is substituted with a cycloalkyl group. Examples thereof include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl, 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl, 4-cyclononylbutyl, 4-cyclodecylbutyl, cycloheptylbutyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclononylethyl, cycloethylmethyl, cyclodecylethyl, 2-cyclononylethyl, 2-cyclonon, 3-3-adamantylpropyl, decahydronaphthylpropyl, and the like. Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl group, 2-cyclobutylethyl group, 2-cyclopentylethyl group, 2-cyclohexylethyl group, 2-cycloheptylethyl group, 2-cyclooctylethyl group, 3-cyclobutylpropyl group, 3-cyclopentylpropyl group, 3-cyclohexylpropyl group, 3-cycloheptylpropyl group, 4-cyclobutylbutyl group, 4-cyclopentylbutyl group, and 4-cyclohexylbutyl group.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and the like; phenyl, biphenyl, naphthyl, anthryl and the like obtained by substituting 1 or more with the above alkyl group, the above alkenyl group, carboxyl group, halogen atom and the like, for example, 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4, 6-trimethylphenyl and the like. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, and the like; phenyl, biphenyl, naphthyl, anthryl and the like obtained by substituting 1 or more with the above alkyl group, the above alkenyl group, carboxyl group, halogen atom and the like, for example, 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4, 6-trimethylphenyl and the like.

The arylalkyl group having 7 to 20 carbon atoms is: a group having 7 to 20 carbon atoms, wherein hydrogen atoms of the alkyl group are substituted with an aryl group. Examples thereof include benzyl, α -methylbenzyl, α -dimethylbenzyl, phenylethyl, and naphthylpropyl. The arylalkyl group having 7 to 10 carbon atoms is: examples of the group having 7 to 10 carbon atoms, which is obtained by substituting a hydrogen atom of an alkyl group with an aryl group, include benzyl, α -methylbenzyl, α -dimethylbenzyl, phenylethyl, and the like.

R in the general formula (I)¹～R⁴And R¹¹～R¹⁷A C2-20 group containing a heterocycle and R¹～R⁵And R¹¹～R¹⁷Among the groups shown, the group having 2 to 20 carbon atoms which contains a heterocyclic ring when a hydrogen atom is substituted is not particularly limited, and examples of the heterocyclic ring include an aliphatic heterocyclic group and an aromatic heterocyclic group.

Examples of the aliphatic heterocyclic group include tetrahydrofuryl, dioxolanyl, pyranyl, tetrahydropyranyl, pyrrolidinyl, pyrazolyl, piperidinyl, piperazinyl, pyrrolidinyl, 2-pyrrolidin-1-yl, 2-piperidon-1-yl, 2, 4-dioxoimidazolidin-3-yl, morpholinyl, and 2, 4-dioxooxazolidin-3-yl, and examples of the aromatic heterocyclic group include pyrrolyl, pyridyl, pyridylethyl, pyrimidinyl, furyl, thienyl, benzoxazol-2-yl, imidazolyl, thiazolyl, isothiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isoxazolyl, triazolyl, triazolylmethyl, quinolyl, isoquinolyl, benzimidazolyl, 2, 4-dioxoimidazolidin-3-yl, tetrazolyl, pyridyl, etc, Triazolyl, furyl, benzofuryl, thiophenyl, benzothiophenyl, indolyl and the like, and these heterocyclic groups may be substituted with the above-mentioned aliphatic hydrocarbon, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, mercapto group, -COOR⁴¹or-SO₂H is substituted at 1 or more positions. R⁴¹Is a hydrogen atom or does not have the above-mentioned substitutionA hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the substituent include groups having the following structures.

In the formula, R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z represents a direct bond or an alkylene group having 1 to 6 carbon atoms. In the above formula, an x represents an atomic bond.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R in the above formula include alkyl groups having 1 to 6 carbon atoms as exemplified above for the alkyl group having 1 to 20 carbon atoms.

Examples of the alkylene group having 1 to 6 carbon atoms represented by Z in the above formula include groups obtained by removing one hydrogen atom from the alkyl group having 1 to 6 carbon atoms.

In the polymer (a1), structural units other than those of the general formula (I) are described below.

The structural units other than the general formula (I) are not particularly limited, and the structural units of the polymers exemplified below can be preferably used. For example, in addition to polyvinyl alcohol obtained by polymerizing vinyl alcohol, partially saponified polyvinyl alcohol, and completely saponified polyvinyl alcohol, which is generally called "POVAL", carboxyl group-modified polyvinyl alcohol, acetoacetate group-modified polyvinyl alcohol, hydroxymethyl group-modified polyvinyl alcohol, amino group-modified polyvinyl alcohol, ester group-modified polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, amide group-modified polyvinyl alcohol, 1- [ 2-styryl ] pyridinium group-modified polyvinyl alcohol, quaternary ammonium group-modified polyvinyl alcohol, allyl group-modified polyvinyl alcohol, oxypropylene group-modified polyvinyl alcohol, urethane group-modified polyvinyl alcohol, ether group-modified polyvinyl alcohol, phosphate group-modified polyvinyl alcohol, acetal group-modified polyvinyl alcohol, butyral group-modified polyvinyl alcohol, silanol group-modified polyvinyl alcohol, photosensitive group-modified polyvinyl alcohol, and polyvinyl alcohol having 1 in a side chain, modified polyvinyl alcohols such as polyvinyl alcohol having a 2-diol structure; and saponified products of copolymers of vinyl acetate and monomers copolymerizable with vinyl acetate. Examples of such monomers include unsaturated carboxylic acids and esters thereof such as maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, acrylic acid, and methacrylic acid, α -olefins such as ethylene and propylene, allylsulfonic acid, methallylsulfonic acid (methallylsulfonic acid), sodium allylsulfonate, sodium methallyl sulfonate, sodium sulfonate monoalkyl malate, sodium disulfonate alkyl malate, N-methylolacrylamide, N-methylolmethacrylamide, N-alkanolalkylacrylamide, N-alkanolmethacrylamide, acrylamide, methacrylamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylalkylamide, and acrylamide alkylsulfonate salts.

Among these, the structural unit represented by the following general formula (I-1) is preferable in that the structure represented by the general formula (I) can be easily introduced.

Here, in the general formula (I-1), R¹～R⁴And n are each the same as in the general formula (I).

Next, the polymer (a2) will be described. Polymer (a2) has the following structure: a structure obtained by reacting a polymer having a structure represented by general formula (II) with a compound represented by general formula (III). The composition using the polymer (a2) had good storage stability, and a cured product obtained from the composition had a highly fine pattern and was excellent in chemical resistance (water resistance) and transparency.

Among the structural units of the polymer having a structure represented by the general formula (II), examples of the structural units other than those represented by the general formula (II) include carboxyl group-modified polyvinyl alcohol, acetoacetate group-modified polyvinyl alcohol, methylol group-modified polyvinyl alcohol, amino group-modified polyvinyl alcohol, ester group-modified polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, amide group-modified polyvinyl alcohol, 1- [ 2-styryl ] pyridinium group-modified polyvinyl alcohol, quaternary ammonium group-modified polyvinyl alcohol, allyl group-modified polyvinyl alcohol, oxypropylene group-modified polyvinyl alcohol, urethane group-modified polyvinyl alcohol, ether group-modified polyvinyl alcohol, phosphate group-modified polyvinyl alcohol, acetal group-modified polyvinyl alcohol, butyral group-modified polyvinyl alcohol, silanol group-modified polyvinyl alcohol, photosensitive group-modified polyvinyl alcohol, and polyvinyl alcohol having a1, 2-diol structure in a side chain, Modified polyvinyl alcohol; and saponified products of copolymers of vinyl acetate and monomers copolymerizable with vinyl acetate. Examples of such monomers include unsaturated carboxylic acids and esters thereof such as maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, acrylic acid, and methacrylic acid, α -olefins such as ethylene and propylene, allylsulfonic acid, methallylsulfonic acid, sodium allylsulfonate, sodium methallylsulfonate, sodium sulfonate monoalkyl malate, sodium disulfonate alkyl malate, N-methylolacrylamide, N-methylolmethacrylamide, N-alkanolacrylamides, N-alkanolmethacrylamide, acrylamide, methacrylamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylalkylamide, acrylamide alkylsulfonate salts, and the like.

Examples of the compound represented by the general formula (III) include N-vinylformamide, N- (1-propenyl) formamide, N- (1-methylvinyl) formamide, N- (2-methyl-1-propenyl) formamide, N- (2-methyl-1-phenyl-1-propenyl) formamide, N- (2-methyl-1-butyl) formaldehyde, N- (1, 3-butadienyl) formamide, N- (2-ethyl-1-hexyl) formaldehyde, and acetals of these compounds.

R in the general formula (II)²¹～R²⁵R of the hydrocarbon group having 1 to 20 carbon atoms and the polymer (A1)¹Etc. to carbon atomsThe same applies to the hydrocarbon groups having a number of 1 to 20.

R in the general formula (II)²¹～R²⁴A group containing 2-20 carbon atoms of a heterocyclic ring and R²¹～R²⁵A C2-20 heterocyclic ring-containing group in which a hydrogen atom is substituted in the group and R of the polymer (A1)¹The same applies to the group containing 2 to 20 carbon atoms of the heterocycle.

R in the general formula (II)²¹～R²⁴Among them, one or more of the hydrogen atoms in the polymer is preferably R, particularly preferably R, because of excellent storage stability and chemical resistance²¹～R²⁴All are hydrogen atoms.

The polymer (a2) having m of 1 in the general formula (II) is preferable because it has excellent storage stability and can be easily produced.

R in the general formula (III)³¹～R³⁴R of the hydrocarbon group having 1 to 20 carbon atoms and the polymer (A1)¹¹The same applies to the hydrocarbon group having 1 to 20 carbon atoms.

R in the general formula (III)³¹～R³³A group containing 2-20 carbon atoms of a heterocyclic ring and R³¹～R³⁴A C2-20 heterocyclic ring-containing group in which a hydrogen atom is substituted in the group and R of the polymer (A1)¹¹The same applies to the group containing 2 to 20 carbon atoms of the heterocycle.

R in the general formula (III)³¹～R³³Among them, one or more of the hydrogen atoms are preferable because of excellent storage stability and reactivity, and excellent chemical resistance of the cured product, and R is particularly preferable³¹～R³³All are hydrogen atoms.

The polymer (A2) having a reaction rate of the compound represented by the general formula (III) with respect to the amount of hydroxyl groups in the polymer represented by the general formula (II) of 1 to 20 mol% is preferable because it is excellent in water solubility and the resulting cured product is excellent in moist heat resistance, and 1 to 10 mol% is particularly preferable.

When the weight average molecular weight of the polymer (a2) in terms of pullulan by Gel Permeation Chromatography (GPC) is 1000 to 200000, the water solubility is excellent and the moist heat resistance of the obtained cured product is excellent, and therefore 30000 to 120000 is particularly preferable.

When the hydroxyl value of the polymer (A2) is 100 to 2000mgKOH/g, the water solubility is excellent and the moist heat resistance of the resulting cured product is excellent, and therefore 500 to 1500mgKOH/g is particularly preferable.

The polymer (A2) preferably has a saponification degree of 70 to 99 from the viewpoint of excellent water solubility, and particularly preferably 85 to 99 from the viewpoint of water resistance. The polymer (a2) having a saponification degree within the above range is preferable because it has excellent water solubility and excellent storage stability of an aqueous solution.

The polymer (A2) preferably has a 4% aqueous solution viscosity of 3 to 60 mPaS, particularly preferably 4 to 50 mPaS, from the viewpoint of excellent handling. Here, the 4% aqueous solution viscosity means, unless particularly limited: the value obtained by measuring a 4% aqueous solution adjusted to 20 ℃ with an E-type viscometer.

The content of the polymer (a1) and the polymer (a2) (hereinafter, the polymer (a1) and the polymer (a2) are collectively referred to as the (a) component) in the composition of the present invention is preferably 5 to 100 mass%, more preferably 10 to 90 mass%, particularly preferably 20 to 50 mass%, based on 100 mass% of the components other than the solvent described later in the composition, from the viewpoint that the obtained cured product is excellent in water resistance and transparency.

(A) The component (b) can be produced by the following polymer production method. That is, the aqueous solution of the component (a) can be obtained by adding an aqueous solution of N-vinylformamide and an aqueous solution of phosphoric acid to a polyvinyl alcohol copolymer dissolved in ion-exchanged water and reacting them.

The composition of the present invention may be prepared by using water and an organic solvent in combination at an arbitrary ratio as a solvent, and when the ratio of water in the solvent is 80% by mass or more, the environment is low and the organic material is not corroded when applied to the organic material, and therefore, it is preferable that the ratio of water is 90% by mass or more.

Examples of the organic solvent include: a solvent capable of dissolving or dispersing the component (a) or the like by using in combination with water, for example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether solvents such as diethyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane and dipropylene glycol dimethyl ether; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and ester alcohols; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol and pentanol; ether ester solvents such as 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-methoxybutyl acetate, and ethoxyethyl propionate; aromatic solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene-based hydrocarbon oils such as turpentine, D-limonene and pinene; mineral essential Oil, Swasol #310 (supra, Cosmo Matsuyama Oil co., ltd.); paraffin solvents such as SOLVESSO #100 (manufactured by Exon Chemical co., ltd.); 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-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and water are preferred because these solvents are compatible with water.

In the composition of the present invention, the amount of the solvent used is not particularly limited, but is preferably 70 to 95% by mass based on the total amount of the composition. When the content of the solvent is in the above range, the thickness of the curable composition and the thickness of the cured product, which are excellent in handling properties (viscosity and wettability of the curable composition) and liquid stability (which are not accompanied by precipitation and sedimentation of components contained in the composition), can be appropriately controlled, and therefore, the content is preferable.

The composition of the present invention may contain, if necessary, a water-soluble polymer (B), a water-soluble polymer crosslinking agent (C), a water-soluble monomer (D), another water-soluble polymer, an organic acid, a coupling agent, a sensitizer, a surfactant, an alkaline compound, a colorant, a radical initiator, a water-soluble preservative, a conductive substance, and the like.

< Water-soluble Polymer (B) >

The water-soluble polymer (B) (hereinafter, also referred to as component (B)) means: the polymer containing the component (A) of the present invention is not dissolved in 100g of water at 25 ℃ by 10g or more, and may be used in combination with the component (A) in order to adjust the physical properties of a cured product.

Among the water-soluble polymers, a water-soluble polymer having a structural unit represented by the general formula (IV) [ hereinafter, also referred to as a water-soluble polymer (B) ] is preferable because it has good compatibility with the component (A).

Here, in the general formula (IV), denotes an atomic bond.

When a polymer having a structural unit represented by the following general formula (V) in addition to a structural unit represented by the general formula (IV) is used as the component (B), the cured product obtained from the composition of the present invention is particularly excellent in heat resistance, water resistance and moist heat resistance, and is more preferable.

The content of the structural unit represented by the general formula (V) is usually 0.1 to 20 mol%, and from the viewpoint of water resistance, crosslinking rate, water solubility of a cured product, and stability of an aqueous solution, 0.2 to 15 mol% is more preferable, and 0.3 to 10 mol% is particularly preferable.

(B) The component may have a photosensitive group. The photosensitive group means: the reactive group is activated by itself with light such as ultraviolet light, or the reactive group is activated by an active material generated by light such as ultraviolet light.

Examples of the photosensitive group include a cinnamyl group, a cinnamoyl group, a cinnamylidene acetyl group, a chalcone group, a coumarin group, an isocoumarin group, a2, 5-dimethoxystilbene group, a maleimide group, an α -phenylmaleimide group, a 2-pyrone group, an azide group, a thymine group, a quinone group, a uracil group, a pyrimidine group, a 1-methyl-4- [ (E) -2-styryl ] pyridinium group (stilbazolium group), a 1- [ 2-styryl ] pyridinium group, a styrylquinolinium group (Japanese: チリルキノリウム group), an epoxy group, an oxetanyl group, a vinyl ether group, an allyl group, an acryloyl group, a methacryloyl group, an acrylamide group, a methacrylamide group, a vinyl group, an allyl group, a styryl group and the like, among them, 1-methyl-4- [ (E) -2-styryl ] pyridinium group, cinnamoyl group, acryloyl group, methacryloyl group, acrylamide group, or methacrylamide group can be preferably used from the viewpoint that a water-soluble composition having high photosensitivity and high liquid stability (without thickening, gelation, precipitation, or the like) can be obtained.

Among these photosensitive groups, 1-methyl-4- [ (E) -2-styryl ] pyridinium group has high solubility in water and has an absorption band in the vicinity of 365nm, and therefore, a water-soluble composition exhibiting photosensitivity can be obtained even with a light source having a relatively long wavelength such as an LED light source (365 nm). The water-soluble composition is particularly preferably used because it can give a cured product of a pattern having high heat resistance, water resistance, and moist heat resistance and high definition.

(B) Examples of the components include: polyvinyl alcohol obtained by polymerizing vinyl alcohol, partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, or a saponified product of a copolymer of vinyl acetate and a copolymerizable monomer, which is the same as conventionally known polyvinyl alcohol and is generally referred to as "POVAL", as a main chain. The polyvinyl alcohol constituting the component (B) may be a homopolymer having vinyl alcohol as an essential monomer or a copolymer.

The method for producing the component (B) is not particularly limited, and examples thereof include the following methods: a method of reacting polyvinyl alcohol with diketene; a method of reacting polyvinyl alcohol with acetoacetate ester and performing transesterification; a method of saponifying a copolymer of vinyl acetate and vinyl acetoacetate; and the like. Among them, the polyvinyl alcohol is preferably produced by a method of reacting polyvinyl alcohol with diketene, from the viewpoint that the production process is simple and polyvinyl alcohol having an acetoacetate group with good quality can be obtained.

Examples of the monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids and esters thereof such as maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, acrylic acid, and methacrylic acid, α -olefins such as ethylene and propylene, allylsulfonic acid, methacrylsulfonic acid, sodium allylsulfonate, sodium methallylsulfonate, sodium sulfonate monoalkylmalate, sodium disulfonate alkyl malate, N-methylolacrylamide, acrylamide alkyl sulfonate base salt, N-vinylpyrrolidone, and N-vinylpyrrolidone derivatives, and these monomers are preferably 10 mol% or less, and particularly preferably 5 mol% of all the structural units, from the viewpoint of excellent compatibility with the component (a).

The pullulan-based weight average molecular weight (Mw) by Gel Permeation Chromatography (GPC) of 10000 to 200000 and the saponification degree (hydrolysis rate) of 85 to 100 improves the water resistance of the component (B), and the durability of the film is improved, and therefore, the component (B) having a saponification degree of 95 to 100 is more preferably improved in water resistance.

The component (B) preferably has a saponification degree of 70 to 98, particularly preferably 85 to 95, from the viewpoint of excellent water solubility. Component (B) having a saponification degree within the above range is preferable because it is excellent in 70% water solubility and excellent in storage stability of an aqueous solution.

As the 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 industries, Ltd.).

The content of the component (B) in the composition of the present invention is preferably 0 to 85 mass%, particularly preferably 5 to 40 mass%, based on 100 mass% of the components other than the solvent in the composition, from the viewpoint of excellent water resistance and transparency of the resulting cured product.

< Water-soluble Polymer crosslinking agent (C) >)

The water-soluble polymer crosslinking agent (C) (hereinafter also referred to as component (C)) can be used without limitation as long as it can crosslink the water-soluble polymer (B). As the component (C), for example, a conventionally known organic crosslinking agent, a metal chelate compound having a chelating agent, a zirconium compound and a titanium compound can be preferably used.

The component (C) can be used by being arbitrarily selected from those generally used as a crosslinking agent, and examples thereof include a diazide compound, an amino resin having a hydroxyl group or an alkoxy group, and melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinamide-formaldehyde resin, and ethylene urea-formaldehyde resin. Melamine, urea, guanamine, glycoluril, succinamide, and ethylene urea are methylolated by reacting them with formalin in boiling water, or alkoxylated by further reacting them with a lower alcohol.

Examples of the chelating agent include hydroxycarboxylic acids or salts thereof, glyoxylic acid or salts thereof, ammonia alcohol, aminocarboxylic acids, alanine, arginine, leucine, isoleucine, dihydroxypropylglycine, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, β -diketone, dimethylglyoxime, citric acid, tartaric acid, maleic acid, polyhydrazide, and phosphate esters, and one or a combination of two or more thereof may be used.

When a metal chelate compound having a chelating agent capable of 2 or more teeth coordination to 1 metal atom by a covalent bond, a hydrogen bond or the like is used, the crosslinking reaction rate is preferably adjusted to a moderate level. Specific examples of the chelating ligand include hydroxycarboxylic acids and salts thereof, alcohols, and β -diketones.

As the zirconium compound, a halogenated zirconium such as zirconium oxychloride, zirconium hydroxychloride, zirconium tetrachloride, zirconium bromide, etc.; zirconium salts of inorganic acids such as zirconium sulfate, basic zirconium sulfate, zirconyl nitrate, zirconyl acetate, and zirconyl carbonate; zirconium salts of organic acids such as zirconium formate, zirconium acetate, zirconium propionate, zirconium octylate, zirconium stearate, zirconium lactate, zirconium nitrate, zirconium carbonate, zirconium octylate, zirconium citrate, and zirconium phosphate; zirconium complex salts such as ammonium zirconium carbonate, sodium zirconium sulfate, ammonium zirconium acetate, ammonium zirconium carbonate, potassium zirconium carbonate, sodium zirconium oxalate, sodium zirconium citrate, ammonium zirconium citrate, and ammonium zirconium lactate, and also zirconium chelate complexes in which one or two or more chelating agents are used as ligands. Among them, water-soluble zirconium is preferable, and zirconium oxyhalide, zirconyl acetate, zirconium sulfate, and zirconyl nitrate are more preferable.

Examples of the zirconium chelate compound include zirconium tetraacetoacetate, zirconium monoacetoacetate, zirconium oxyhalide, zirconium oxynitrate, zirconium ammonium lactate, zirconium sulfate, zirconium oxyacetate, zirconium bisacetoacetate, zirconium monoethylacetoacetate, and zirconium acetate.

Among the zirconium compounds, zirconium tetraacetoacetate, zirconium monoacetoacetate, zirconium oxyhalide, zirconyl nitrate, zirconium ammonium lactate, zirconium sulfate, zirconyl acetate and the like are preferable because they are high in stability, water solubility and reactivity. They may be used in one kind or in the form of a mixture of two or more kinds.

As the zirconium compound, commercially available products may be used, for example, zirconium chloride, ZIRCOSOL ZC2, ZIRCOSOL ZN, ZIRCOSOL HA, ZIRCOSOL AC7, ZIRCOSOL ZK-10, ZIRCOSOL ZN, ZIRCOSOL ZA-10, ZIRCOSOL ZA-20, zirconium octylate, zirconium carbonate, (DAIICHI KIGENSO KAGAKU KOGYO Co., manufactured by Ltd.), ORGATIX ZA-45, ORGATIX ZA-65, ORGATIX ZB126, ORGATIX ZC150, ORGATIX ZC200, ORGATIX ZC300, ORGATIX ZC320, ORGATIX ZC540, ORGATIX ZC580, ORGATIX ZC700, ORGATIX ZC300(Mats Co., Ltd., manufactured by chemical Co., etc.).

Examples of the titanium compound include titanium alkoxides such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-t-butyl titanate, tetraoctyl titanate, tetra (2-ethylhexyl) titanate, and tetramethyl titanate; oligomers, polymers and derivatives thereof obtained by hydrolytic decomposition reaction of titanium alkoxide such as butyl titanium dimer and butyl titanium tetramer; titanium chelates such as titanium acetylacetonate, titanium octanedioxide, titanium tetraacetylacetonate, titanium ethylacetoacetate, titanium triethanolate, titanium oxalate, etc.; titanium acylates such as polyhydroxytitanium acetate; titanium tetrachloride, titanium lactate, titanium triethanolate, titanium diisopropoxybis (triethanolaluminate), and the like, and they may be used alone or in a mixture of two or more.

As the titanium compound, commercially available products can be used, and examples thereof include ORGATIX TA-8, ORGATIX TA-10, ORGATIX TA-12, ORGATIX TC-100, ORGATIX TC-120, ORGATIX TC-300, ORGATIX TC-310, ORGATIX TC-315, ORGATIX TC-335, ORGATIX TC-401, and ORGATIX TC-800(Matsumoto Fine Chemicals Co., Ltd.).

Among the component (C), a zirconium compound or a titanium compound is particularly preferable from the viewpoint of improving the moist heat resistance of a cured product obtained from the composition of the present invention.

When the amount of the component (C) is 0.01 to 5 parts by mass based on 100 parts by mass of the total of the components (A) and (B), the composition is stable without causing any change such as precipitation or thickening.

The composition of the present invention contains a metal component derived from the component (C), but the metal content is preferably 0.01 to 3% by mass, more preferably 0.01 to 1% by mass, of the components of the composition other than the solvent.

< Water-soluble monomer (D) >)

The composition of the present invention may contain a compound represented by the general formula (VI) as the water-soluble monomer (D) (hereinafter, also referred to as component (D)).

Here, in the formula (VI), R⁵¹Represents a hydrogen atom or a methyl group, X¹Represents an oxygen atom or-NR⁵²-，R⁵²X represents a hydrogen atom or a hydrocarbon group of 1 to 20 carbon atoms²X represents an alkylene group having 1 to 6 carbon atoms²The hydrogen atom of the alkylene group having 1 to 6 carbon atoms is optionally substituted by a halogen atom or a hydroxyl group, k represents a number of 0 to 30, represents an atomic bond, and when a plurality of groups represented by the general formula (VI) have a plurality, a plurality of R's are present⁵¹、X¹、X²And k are optionally the same or different.

R in the formula (VI)⁵²The hydrocarbon group having 1 to 20 carbon atoms and R in the polymer (A1)¹The same applies to the hydrocarbon group having 1 to 20 carbon atoms.

As X in the formula (VI)²The alkylene group having 1 to 6 carbon atoms is the same as the alkylene group having 1 to 6 carbon atoms represented by Z.

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

The alkylene oxide-modified acrylate compound means: in the general formula (VI) R⁵¹Is a hydrogen atom, X¹The alkylene oxide-modified methacrylate compound is a compound having an oxygen atom and k of 1 to 30, and the alkylene oxide-modified methacrylate compound is: in the general formula (VI) R⁵¹Is methyl, X¹Is a compound having 1 to 30 of k and an oxygen atom.

Examples of the alkylene oxide-modified acrylate compound include ethylene oxide-modified neopentyl glycol diacrylate, propylene oxide-modified neopentyl glycol diacrylate, ethylene oxide-modified 1, 6-hexanediol diacrylate, propylene oxide-modified 1, 6-hexanediol diacrylate and the like, and examples of the alkylene oxide-modified methacrylate compound include ethylene oxide-modified neopentyl glycol dimethacrylate, propylene oxide-modified neopentyl glycol dimethacrylate, ethylene oxide-modified 1, 6-hexanediol dimethacrylate, propylene oxide-modified 1, 6-hexanediol dimethacrylate and the like.

As the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound, commercially available ones can also be preferably used, and examples thereof include NK Ester A-600 and A-GLY-20eNK EKONOMA A-PG5054E (manufactured by shinkamura chemical industries, Ltd.).

X in the general formula (VI) in the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound²In the case of an ethylene group or a propylene group, the water solubility is preferable because it is excellent, and the water solubility of the ethylene group is particularly excellent, so that it is preferable.

When the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound have one group represented by the general formula (VI), a case where k is 6 or more is particularly preferable in view of excellent water solubility. When the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound have a plurality of groups represented by the general formula (VI), it is particularly preferable that the sum of k in the presence of a plurality of alkylene oxide-modified acrylate compounds and alkylene oxide-modified methacrylate compounds is 10 or more, from the viewpoint of excellent water solubility.

The acrylamide compound refers to: in the general formula (VI) R⁵¹Is a hydrogen atom, X¹Is NR⁵²-k is 1 to 0, and the methacrylamide compound is: in the general formula (VI) R⁵¹Is methyl, X¹Is NR⁵²-, k is 0.

Examples of the acrylamide compound include hydroxyacrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-butylacrylamide, diacetoneacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-dipropylacrylamide, acryloylmorpholine, N-N-butoxymethacrylamide, N-isobutoxymethacrylamide, N-methoxymmethacrylamide and the like, and examples of the methacrylamide compound include hydroxymethacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N-butylmethacrylamide, diacetoneacrylamide and N, n-dimethylmethacrylamide, N-diethylmethacrylamide, N-dipropylmethacrylamide, methacryloylmorpholine, N-N-butoxymethylmethacrylamide, N-isobutoxymethylmethacrylamide, N-methoxymethylmethacrylamide, and the like.

As the acrylamide compound and the methacrylamide compound, commercially available ones can be preferably used, and examples thereof include FAM-401, FAM-301, FFM-402 and FFM-201 (manufactured by FUJIFILM Corporation).

When the component (D) is contained, the content of the component (D) is preferably 1 to 1000 parts by mass based on 100 parts by mass of the total of the components (a) and (B), and when the content of the component (D) is in this range, a composition having good curability can be obtained, and a cured product having a high-definition pattern and excellent heat resistance, water resistance and moist heat resistance can be obtained from the composition. From the viewpoint of film-forming properties, it is more preferably 1 to 500 parts by mass relative to 100 parts by mass of the total of the components (a) and (B).

< other polymers, etc. >

Other water-soluble polymers, organic acids, coupling agents, sensitizers, surfactants, basic compounds, colorants, radical initiators, water-soluble preservatives, conductive substances, and the like may also be added to the composition of the present invention.

The other water-soluble polymer is a water-soluble polymer which does not belong to the components (A) and (B). Examples of the other water-soluble polymer include oxidized starch, etherified/esterified/grafted modified starch, cellulose derivatives such as gelatin/casein/carboxymethylcellulose, water-soluble polyacrylate resins such as polyvinylpyrrolidone, water-soluble polyester resins, 2-hydroxypropyl acrylate polymers/4-hydroxybutyl acrylate polymers, water-soluble polycarbonate resins, water-soluble polyvinyl acetate resins, water-soluble styrene acrylate resins, water-soluble vinyl toluene acrylate resins, water-soluble polyurethane resins, water-soluble polyamide resins such as polyvinyl amide/polyacrylamide and modified acrylamide, water-soluble urea resins, water-soluble polycaprolactone resins, water-soluble polystyrene resins, water-soluble polyvinyl chloride resins, water-soluble polyacrylate resins, water-soluble cellulose derivatives, water-soluble polyvinyl pyrrolidone, water-soluble styrene acrylate resins, water-soluble 2-hydroxypropyl acrylate polymers, water-soluble polyvinyl chloride resins, water-soluble urea resins, water-soluble resins such as water-soluble polyacrylonitrile resins, and styrene/butadiene copolymers, acrylate copolymers, ethylene/vinyl acetate copolymers, and the like.

The organic acid is not limited as long as it is a weakly acidic compound having a carboxyl group, and examples thereof include acetic acid, citric acid, malic acid, glycolic acid, lactic acid, carbonic acid, formic acid, oxalic acid, propionic acid, octanoic acid, decanoic acid, glucuronic acid, stearic acid, benzoic acid, mandelic acid, and the like. Among them, lactic acid, acetic acid, citric acid, glycolic acid, or malic acid is preferable.

Examples of the coupling agent include alkyl-functional alkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane, alkenyl-functional alkoxysilanes such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ -glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and the like, Epoxy-functional alkoxysilanes such as gamma-glycidoxypropylmethyldiethoxysilane and beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, amino-functional alkoxysilanes such as N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane and N-phenyl-gamma-aminopropyltrimethoxysilane, and mercapto-functional alkoxysilanes such as gamma-mercaptopropyltrimethoxysilane.

The sensitizer is a compound which can expand the wavelength range of light to be accommodated when curing by light irradiation, and examples of the sensitizer include benzophenones such as benzophenone, 3-hydroxybenzophenone, 4-dihydroxybenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2, 5-dimethylbenzophenone, 3, 4-dimethylbenzophenone, 4-methoxybenzophenone, 4-dimethoxybenzophenone, 3-dimethyl-4-methoxybenzophenone, 4-phenylbenzophenone, acetophenone, 4-methoxyacetophenone, 2, 4-dimethoxyacetophenone, 2, 5-dimethoxyacetophenone, and mixtures thereof, Acetophenones such as 2, 6-dimethoxyacetophenone, 4-dimethoxyacetophenone, 4-ethoxyacetophenone, diethoxyacetophenone, 2-diethoxyacetophenone, 2-ethoxy-2-phenylacetophenone and 4-phenylacetophenone, anthraquinones such as anthraquinone, hydroxyanthraquinone, 1-nitroanthraquinone, aminoanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, anthraquinone sulfonic acid, 1, 2-benzoanthraquinone and 1, 4-hydroxyanthraquinone (quinizarine), anthraquinones, 1, 2-benzanthracene, 9-cyanoanthracene, 9, 10-dicyanoanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-bis (phenylethyl) anthracene, anthraquinones such as 2, 3-dichloro-6-dicyano-p-benzoquinone, Quinones such as 2, 3-dimethoxy-5-methyl-1, 4-benzoquinone, methoxybenzoquinone, 2, 5-dichloro-p-benzoquinone, 2, 6-dimethyl-1, 4-benzoquinone, 9, 10-phenanthroquinone, camphorquinone, 2, 3-dichloro-1, 4-naphthoquinone, xanthone, thioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-isopropylthioxanthone, thioxanthone, dibenzosuberone, 5-dibenzocycloheptenone, cycloheptatrien-5-ol, cycloheptenone, and other cycloheptanes, 2-methoxynaphthalene, benzoin isopropyl ether, 4-benzoyldiphenyl ester, Aromatic compounds such as o-benzoylbenzoic acid, o-benzoylmethyl benzoate, 4-benzoyl-4-methyl-diphenylsulfide, benzil, and benzoin methyl ether, and coumarin-, thiazine-, azine-, acridine-, and xanthene-based compounds as dye-based sensitizing substances.

As the surfactant, a fluorinated surfactant such as a perfluoroalkyl phosphate ester or a perfluoroalkyl carboxylate, an anionic surfactant such as a higher fatty acid base salt, an alkylsulfonate, or an alkylsulfate, a cationic surfactant such as a higher amine halide salt or a quaternary ammonium salt, a nonionic surfactant such as a polyethylene glycol alkyl ether, a polyethylene glycol fatty acid ester, a sorbitan fatty acid ester, or a fatty acid monoglyceride, an amphoteric surfactant, or a silicone surfactant may be used, or a combination thereof may be used.

Examples of the basic compound include ammonia, sodium hydroxide, potassium hydroxide, triethylamine, triethanolamine, diethanolamine, monoethanolamine, triisopropanolamine, diisopropanolamine, monoisopropanolamine, N-dimethylethanolamine, ethyleneimine, pyrrolidine, piperidine, and polyethyleneimine, and one or more of these compounds may be used in combination, and the basic compound may be added for the purpose of adjusting pH or the like.

As the colorant, pigments and dyes can be used. The pigment and the dye may be an inorganic coloring material or an organic coloring material, and they may be used alone or in combination of two or more. Here, the pigment means: the colorant insoluble in a solvent described later includes those insoluble in an inorganic or organic coloring material and also insoluble in a solvent, and those formed by chelating an inorganic or organic dye.

Examples of the pigment include: carbon black obtained by a furnace method, a tank method or a pyrolysis method; or carbon black such as acetylene black, ketjen black or lamp black; those carbon blacks are adjusted or covered with epoxy resin; the carbon black is dispersed in a resin in a solvent in advance and covered with 20 to 200mg/g of the resin; those obtained by subjecting these carbon blacks to an acidic or alkaline surface treatment; carbon black having an average particle diameter of 8nm or more and a DBP oil absorption of 90ml/100g or less; from CO and CO in volatile components at 950 DEG C₂Calculated total oxygen amount per unit surface area of 100m²Organic or inorganic pigments such as black pigment represented by carbon black, graphitized carbon black, graphite, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, titanium black, etc., chromium oxide green, chromium blue, cobalt green, cobalt cyan, manganese series, ferrocyanide, ultramarine, sky blue, chromium green, bright green, lead sulfate, yellow lead, zinc yellow, indian red (red iron oxide (III)), cadmium red, synthetic iron black, amber, lake pigment, etc., of 9mg or more, and from the viewpoint of high light-shielding property, black pigment is preferably used, and carbon black is more preferably used as the black pigment.

As the pigment, commercially available products may be used, and examples thereof include MICROPIGMO WMYW-5, MICROPIGMO WMRD-5, MICROPIGMO WMBN-5, MICROPIGMO WMGN-5, MICROPIGMO WMBK-5, MICROPIGMO WMBE5, MICROPIGMO WMVT5, MICROPIGMO WMWE1, BONJET BLACK CW-1 (manufactured by Orient Chemical Industries Co., Ltd.) pigment Red1, 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, 202, 209, 215, 216, 217, 220, 223, 224, 226, 228, 227, 254, 184, 226, 228, and 240; 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 green7, 10, 36, and 58; pigment blue15, 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, 50, and the like.

Examples of the dye include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthanthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinoline yellow compounds, naphthalene tetracarboxylic acids, azo dyes, cyanine dye metal complex compounds, and the like.

As the dye, commercially available ones can be used, and examples of the water-soluble dye include WATERYELLOW 1, WATERYELLOW 2, WATERYELLOW 6C, WATERYELLOW 6CL, WATERORANGE 18, WATERORANGE 25, WATERRED 1, WATERRED 2S, WATERRED 3, WATERRED 9, WATERRED 27, WATERPINK 2S, WATERBROWN 16, WATERGREEN 8, WATERBLUE 3, WATERBLUE 9, WATERBLUE 105S, WATERBLUE 106, WATERBLUE 117-L, WATERVIOLET 7, WATERBLACK 31, WATERBLACK 191-L, WATERBLACK 256-L, WATERBLACK 455, WATERBLACK R510, BONJET YELLOW 161-L, BONJET MAGETDA XXX, BONT CYAN, BONJET BLACK XXX 1-L (manufactured by Orient Industries, Co., Ltd.).

Examples of the oil-soluble dye include 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, VALIFAST BLACK 3804, VALIFAST BLACK 3810, VALIFAST BLACK 3820, VALIFAST BLACK 3830, VALIFAST BLACK 3840, VALIFAST BLACK 3866, VALIFAST BLACK 3870, VALIT FASANGE, VALIFAST BROWN 3402, VALIFAST BLAUE 1613, and VALIFAST BLACE 1605 (available from original Chemical Industries Co., Ltd.).

As the radical initiator, conventionally known compounds can be used, and for example, in addition to those described in Japanese Kokai publication Sho-57-197289, Japanese Kokai publication Hei-6-228218, Japanese Kokai publication 2009-102455, Japanese Kokai publication 2012-007071, Japanese Kokai publication 2016-510314, WO2014/050551, Japanese Kokai publication Hei-06-239910, Japanese Kokai publication 2003-192712, and Japanese Kokai publication 2016-185929, it is possible to use: hydrogen abstraction type photopolymerization initiators such as benzophenone, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone and ethylanthraquinone; phenylbiphenone, 1-hydroxy-1-benzoylcyclohexane (. alpha. -hydroxyalkylphenone), benzoin, benzildimethylketal, 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-phenoxybenzoyl dichloromethane, methyl benzoylformate, 1-hydroxy-cyclohexyl-phenyl-ketone, methyl benzoylformate, methyl-benzyl-2-hydroxy-2- (4 ' -isopropyl) benzoylpropane, methyl-4-benzoylchloride, methyl-4-phenoxybenzoyl chloride, methyl-benzoate, methyl-hydroxy-cyclohexyl-, 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' -morpholinoisobutyryl) carbazole, 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4, 6-bis (trichloromethyl) -s-triazine, 2-bis (2-chlorophenyl) -4, a photodegradable photopolymerization initiator such as 5,4 ', 5 ' -tetraphenyl-1-2 ' -biimidazole, acylphosphine oxide, bisacylphosphine oxide, and triphenylphosphine oxide, and a photodegradable photopolymerization initiator is preferable from the viewpoint of reactivity.

Among the photo-degradable photopolymerization initiators, water-soluble initiators such as Irg2959 and Irg819DW (manufactured by BASF corporation), ESACURE ONE ESACURE 1001M, ESACURE KIP 150, and ESACURE DP 250(Lamberti Co.) are preferable because of their high affinity for water.

Examples of the water-soluble preservative include those having high solubility in water and solubility at room temperature of 1% or more, specifically, methyl paraben, benzoic acid, benzoate, salicylic acid, salicylate, phenoxyethanol, water-soluble cationic antibacterial agents, organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, parabens, propanediol materials, isothiazolinone, quaternary compounds, benzoate esters, low molecular weight alcohols, dehydroacetic acid, ACQ (copper/quaternary ammonium compound), CUAZ (copper/oxazole compound), AAQ (quaternary ammonium compound), sodium bisulfite, sodium bisulfate, sodium thiosulfate, ascorbate, benzalkonium chloride, chlorobutanol, thimerosal, phenylmercuric acetate, phenylmercuric borate, phenylmercuric nitrate, parabens, methylparaben, Polyvinyl alcohol, benzyl alcohol, isothiazolone, triazine, bronopol, thiabendazole, zinc pyrithione, carbendazim, sodium salt of pyridine oxidized thiol, phenyl ethanol, and the like.

As the water-soluble preservative, commercially available ones can be used, and examples thereof include San-AI Back P, San-AI Back 300K, San-AI Back IT15SA, San-AI Back AS-30, San-AI Back T10, San-AI Back M-30, and San-AI Back Sodium Omadine (all manufactured by SAN-AI OIL Co., Ltd.).

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

Examples of the metal include metals such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, and cadmium, and alloys composed of two or more metals such as tin-lead alloy, tin-copper alloy, tin-silver alloy, and tin-lead-silver alloy. Among them, 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 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), poly (3, 4-dimethylpyrrole), poly (3, 4-dibutylpyrrole), poly (3-hydroxypyrrole), poly (3-methyl-4-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-octyloxypyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (N-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-octyloxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3, 4-ethylenedioxythiophene), polyaniline, poly (2-methylaniline), poly (2-octylaniline), poly (2-isobutylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), poly (3-anilinesulfonic acid), and polythiophene derivatives (PEDOT poly (3,4) -ethylenedioxythiophene) doped with polystyrenesulfonic acid (PSS).

In addition, as long as the effects of the present invention are not impaired, in addition to these, as necessary: and various resin additives such as photopolymerization initiators, thermal polymerization initiators, photobase generators, acid generators, inorganic fillers, organic fillers, antifoaming agents, thickeners, leveling agents, organometallic coupling agents, thixotropic agents, carbon compounds, fine metal particles, metal oxides, flame retardants, plasticizers, light stabilizers, heat stabilizers, antioxidants, elastomer particles, chain transfer agents, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, mold release agents, flow control agents, adhesion promoters, preservatives, antifungal agents, unsaturated monomers, epoxy compounds, oxetane compounds, vinyl ethers, and other cationically polymerizable compounds.

The composition of the present invention can be preferably used as a pattern forming agent. The pattern forming agent means: specifically, a substance having a lithographic property is irradiated with light through a mask and then developed with a developing solution (water, an organic solvent, an aqueous alkali solution, or the like), whereby a pattern having a thickness of 1000 μm or less can be formed with accuracy within ± 10% and with good reproducibility.

Next, a method for producing a cured product of the present invention will be described.

The method for producing a cured product of the present invention includes a step of curing the composition of the present invention. Preferred coating methods and curing conditions for the method for producing a cured product of the present invention are shown below.

Preferred coating methods are known means such as spin coater, bar coater, roll coater, curtain coater, various printing, dipping, etc., and are used for a support substrate such as glass, metal, paper, cloth, plastic, etc. Further, after being temporarily applied to a supporting substrate such as a film, the film may be transferred to another supporting substrate, and the application method is not limited.

Examples of the material of the transparent support include inorganic materials such as glass; cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, and nitrocellulose; a polyamide; a polycarbonate; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, 1, 4-cyclohexanedimethylene terephthalate, polyethylene-1, 2-diphenoxyethane-4, 4' -dicarboxylate, and polybutylene terephthalate; polystyrene; polyolefins such as polyethylene, polypropylene, polymethylpentene and the like; acrylic resins such as polymethyl methacrylate; a polycarbonate; polysulfones; polyether sulfone; a polyether ketone; a polyetherimide; high polymer materials such as polyoxyethylene and norbornene resins. The transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze is preferably 2% or less, and more preferably 1% or less. The refractive index is preferably 1.45-1.70.

Preferred curing conditions are as follows: in the case of light irradiation, the irradiation conditions such as the wavelength, intensity and irradiation time of the light to be irradiated can be appropriately adjusted depending on the activity of the photoinitiator, the activity of the photopolymerizable resin to be used and the like, and the wavelength of the light is usually preferably 300 to 500nm in wavelength, more preferably 350 to 450nm in wavelength, and most preferably 360 to 380nm in wavelength in order to allow the light to sufficiently enter the inside. The light intensity is preferably 10 to 300mW/cm²More preferably 25-100 mW/cm²The irradiation time is preferably 5 to 500 seconds, more preferably 10 to 300 seconds.

The composition of the present invention may be heated to cause the crosslinking reaction to proceed. The heating is carried out at 50 to 230 ℃, preferably 70 to 150 ℃ for 10 minutes to 1 hour. If the temperature is lower than 50 ℃, the crosslinking reaction may not proceed, and if the temperature is higher than 200 ℃, the decomposition of the components (a) to (D) or the decrease in the transparency of the optical film may occur.

When a cured product is patterned by photolithography, the pattern can be formed as follows: the composition or the pattern forming agent of the present invention was applied to a glass substrate by a spin coater adjusted so that the film thickness after exposure was 5.0 to 5.5 μm using a stylus type shape measuring device (Dektak 150 manufactured by ULVAC), and then prebaked on a hot plate at 90 ℃ for 10 minutes, and then cooled to room temperature, and 500mJ/cm of light having a wavelength of 365nm was irradiated with a high-pressure mercury lamp through a photomask (LINESPACE: 50 μm/50 μm)²The substrate was exposed to light and immersed in ion-exchanged water at 23 ℃ for 1 minute, and then the adhered water was removed with an air gun, and the substrate was dried in an oven at 140 ℃ for 30 minutes. The preferred curing conditions are the same as described above.

Next, the cured product of the present invention will be described.

The cured product of the present invention is formed from the composition of the present invention. Specific applications of the composition of the present invention include: optical materials including glasses and imaging lenses, paints, nail-care materials, cosmetics, various coating agents, lining agents, inks, resists, liquid resists, adhesives, sealants for liquid crystal dropping processes, image-forming materials, pattern-forming materials, printing plates, insulating varnishes, insulating sheets, laminate plates, printing substrates, sealing agents for semiconductor devices/LED packages/liquid crystal injection ports/organic EL/optical elements/electrical insulation/electronic components/separation films, molding materials, putties, building materials, wall plates, glass fiber impregnants, caulking agents, passivation films for semiconductors/solar cells, interlayer insulation films, protective films, prism lenses for backlights of liquid crystal display devices, fresnel lenses for screens of projection televisions, and the like, Examples of the substrate that can be used as a coating agent include metals, woods, rubbers, plastics, glasses, ceramics, papers, and cloths, and the like, and the substrate can be used as a substrate for a coating agent.

When the composition of the present invention is used for an optical film, the optical film may be formed into a film or a sheet by a conventional method, may be produced without stretching (or orienting treatment) the obtained film or sheet, or may be produced by stretching (or orienting treatment). In film formation, a melt molding method (melt film forming method) such as extrusion molding or blow molding may be used, and a casting method (casting film forming method or solution casting method) may be used.

The shape of the optical film using the composition of the present invention is not particularly limited, and is usually a film for optical use having an optical film on a transparent support, and examples thereof include: examples of the functional films include various functional films such as a protective film for a polarizing plate, a retardation film, a viewing angle expanding film, an antireflection film, and a low reflectance film used for a plasma display, which are used for a liquid crystal display device, and various functional films used for an organic EL display.

Optical films using the compositions of the present invention can be used as: an optical recording layer of a write-in type magneto-optical disk (CD + -R, DVD + -R, next generation type high-density disk, etc.) using an optical film as a support; various lenses; a filter for an image display device; various filters typified by color filters and color conversion filters; or a protective sealing film for an organic EL light-emitting device, an inorganic EL light-emitting device, an electronic paper display, or the like.

Examples

The present invention will be described in further detail below with reference to examples and the like, but the present invention is not limited to these examples. The solid components described in the present example mean: the mass% of the components other than the solvent.

[ (A) component aqueous solution No. 1-5 ]

Into a reaction flask containing 1000 parts of ion-exchanged water was slowly charged [ Table 1]]198 parts of the hydroxyl group-containing polymer shown was stirred for 1 hour, and then heated to 90 ℃ to completely dissolve the hydroxyl group-containing polymer. The mixture was cooled to 40 ℃ and 9.9 parts of N-vinylformamide and phosphoric acid each in an amount of 9 mol% of the hydroxyl group were added thereto, followed by stirring at 40 ℃ for 5 hours. After neutralizing the acid, the reaction solution was cooled to room temperature, ion-exchanged water was added so that the solid content became 15 mass%, and the mixture was further stirred at room temperature for 1 hour, filtered through a 5 μm filter, and then ion-exchanged water was added to adjust the solid content to 10 mass%. The hydroxyl group-containing polymers used for the aqueous solutions of Components (A) Nos. 1 to 5 obtained are summarized in [ Table 1]]. Measurement of¹H-NMR、¹³C-NMR, IR and weight-average molecular weight Mw confirmed that the obtained component (A) had a structural unit represented by the general formula (I).

The conditions for measuring the weight average molecular weight Mw are as follows.

High performance liquid chromatograph Chromaster (manufactured by Hitachi High-Tech Science Corporation)

Eluting solvent water: MeOH ═ 7: 3 (buffer 0.02MNaH₂PO₄)

Measuring column SB806M HQ (manufactured by SHODEX Co., Ltd.)

The measurement temperature was 40 deg.C

Flow rate 1.0 mL/min

The weight average molecular weight Mw was measured in terms of a pullulan standard sample.

[ Table 1]

[ (B) component aqueous solution Nos. 1 to 4]

100 parts of a hydroxyl group-containing polymer was slowly charged into a reaction flask containing 500 parts of ion-exchanged water, stirred for 1 hour, and then heated to 90 ℃ to be completely dissolved. After cooling to 40 ℃ and charging a photosensitive group-imparting agent shown in Table 2 in an amount of 2 mol% based on the hydroxyl group and 0.1 part of p-toluenesulfonic acid, the mixture was stirred at 50 ℃ for 3 hours. After cooling the solution to room temperature, ion-exchanged water was added so that the solid content became 15 mass%, stirring was further carried out at room temperature for 1 hour, and after filtering was carried out with a 5 μm filter, ion-exchanged water was added to adjust the solid content to 10 mass%, thereby obtaining aqueous solutions nos. 1 to 4 of component (B). The combinations of the hydroxyl group-containing polymers and the photosensitive group-imparting agents used for the aqueous solutions of components (B) obtained in the above-mentioned manner are shown in Table 2.

[ Table 2]

[ (B) component aqueous solution Nos. 5 to 8]

10.0g of a hydroxyl group-containing polymer was slowly added to 90.0g of stirring ion-exchanged water, and the mixture was directly stirred at room temperature for 1 hour. Thereafter, the internal temperature was adjusted from 85 ℃ to 90 ℃ and stirring was continued for 2 hours. After confirming the dissolution, the mixture was cooled to room temperature and filtered through a1 μm filter to obtain aqueous solutions Nos. 5 to 8 of component (B). The combinations of the aqueous solutions of Components (B) Nos. 5 to 8 and the hydroxyl group-containing polymers used are summarized in [ Table 3 ].

[ Table 3]

[ examples 1 to 35 and comparative examples 1 to 13] preparation of compositions

The respective components were stirred at room temperature for 1 hour according to the formulations of [ Table 4] to [ Table 13], and then filtered through a1 μm filter to obtain compositions of examples Nos. 1 to 35 and comparative examples Nos. 1 to 13. The numerical values of the formulations in the tables represent parts by mass. In addition, symbols of each component in the table represent the following components.

A-1: (A) component aqueous solution No.1[ (component aqueous solution A ]

A-2: (A) component aqueous solution No.2[ (component aqueous solution A ]

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

A-4: (A) component aqueous solution No.4[ (component aqueous solution A ]

A-5: (A) component aqueous solution No.5[ (component aqueous solution A ]

B-1: (B) component aqueous solution No.1[ photosensitive group-containing (B) component aqueous solution ]

B-2: (B) component aqueous solution No.2[ photosensitive group-containing (B) component aqueous solution ]

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

B-4: (B) component aqueous solution No.4[ photosensitive group-containing (B) component aqueous solution ]

B-5: (B) component aqueous solution No.5[ photosensitive group-free (B) component aqueous solution ]

B-6: (B) component aqueous solution No.6[ photosensitive group-free (B) component aqueous solution ]

B-7: (B) component aqueous solution No.7[ photosensitive group-free (B) component aqueous solution ]

B-8: (B) component aqueous solution No.8[ photosensitive group-free (B) component aqueous solution ]

C-1：ORGATIX TC335

(titanium ammonium lactate salt aqueous solution: component concentration 75%),

The Ti content is 5 percent; matsumoto Fine Chemicals Co., Ltd.)

C-2：ORGATIX ZC126

(aqueous zirconium chloride solution: 30% in terms of component concentration, 11% in terms of Zr content;

matsumoto Fine Chemicals Co., Ltd.)

C-3：ZIRCOSOL ZN

(zirconium nitrate aqueous solution, component concentration 46%, Zr content 25%;

first rare element chemical industry system)

C-4：ORGATIX WS-700

(organic titanium-modified polyethyleneimine, aqueous solution containing 10% of component concentration;

matsumoto Fine Chemicals Co., Ltd.)

D-1：NK Ester A-600

(alkylene oxide-modified acrylic acid ester manufactured by Mizhongcun chemical industry Co., Ltd.)

D-2：NK Ester A-GLY-20E

D-3：NK EKONOMA A-PG5054E

D-4: FAM-301 (polyfunctional acrylamide compound; Fuji film production)

D-5: acryloyl morpholine

D-6: hydroxy acrylamide

E-1: megaface F-444 (fluorine series leveling agent; manufactured by DIC)

E-2: KP-112 (silicon leveling agent; manufactured by Xinyue chemical industry)

E-3: San-AI Back It15SA (antiseptic; SAN-AI OIL Co., Ltd.)

E-4: DL-lactic acid

E-5: n, N-bis (2-hydroxyethyl) butane-1 aluminum ═ phenyl (2,4, 6-trimethylbenzoyl) phosphinic acid (free radical initiator)

E-6: 3- ((4- (2-methyl-2-morpholinopropionyl) phenyl) thio) propanalkanoic acid ═ sodium salt (free radical initiator)

E-7: 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone

E-8: n, N-bis (2-hydroxyethyl) butane-1 aluminum ═ 9-oxo-thioxanthene-4-carboxylic acid

E-9：BONJET BLACK CW-1

(obtained from Orient Chemical Industry Co., Ltd., modified carbon Black self-Dispersion, concentration 20%)

E-10：MICROPIGMO WMRD-5

(origin Chemical Industry Co., Ltd., Pigment Red17 resin dispersion, concentration 20%)

E-11：MICROPIGMO WMGN-5

(original Chemical Industry Co., Ltd., manufactured by Ltd., Pigment Green7 resin dispersion, concentration 21%)

E-12：MICROPIGMO WMBE-5

(origin Chemical Industry Co., Ltd., manufactured by Ltd., Pigment Blue 15: 6 resin dispersion, concentration 20%)

E-13: nigrosine (manufactured by Tokyo chemical industry, Acid Black 2)

E-14: ion exchange water

[ evaluation of composition and cured product ]

The compositions of examples 1 to 35 and comparative examples 1 to 13 were evaluated for compatibility, coatability, photo-etching properties, residual film ratio, moist heat resistance, PET flexibility and PET adhesion according to the following procedures. The results are also shown in tables 4 to 13. In the table, "-" indicates no evaluation.

(1. compatibility)

The compositions were visually observed and evaluated according to the following criteria.

O: uniformity

And (delta): is a homogeneous system but has white turbidity

X: insoluble, visibly gelled or insoluble material

The evaluation results were good for use when evaluated as "o" and "Δ", good for use when evaluated as "o", and not good for use when evaluated as "x".

(2. coatability)

Each composition was applied onto a glass substrate by a spin coater adjusted to have a film thickness of 5.0 to 5.5 μm after prebaking by using a stylus type shape measuring instrument (Dektak 150 manufactured by ULVAC), and then prebaked on a hot plate at 90 ℃ for 10 minutes. The state of the film at this time was visually confirmed. Evaluation was performed according to the following criteria.

O: uniformity of coating film

And (delta): is uniform but has rough surface

X: uneven state on the surface or precipitates were observed

(3. photoetching property)

Adjusting the conditions by a stylus type shape measuring instrument (Dektak 150 manufactured by ULVAC) so that the film thickness is 5.0 to 5.5 μmThe coating machine coated each composition on a glass substrate, and then prebaked on a hot plate at 90 ℃ for 10 minutes. Then, the mixture was cooled to room temperature, and 500mJ/cm of light having a wavelength of 365nm was irradiated with a high-pressure mercury lamp through a photomask (LINE/SPACE: 50 μm/50 μm)²After immersing the substrate in ion-exchanged water at 23 ℃ for 1 minute, the adhered water was removed by an air gun, and the substrate was dried in an oven at 140 ℃ for 30 minutes. The pattern after drying was confirmed by a laser microscope and evaluated according to the following criteria.

O: the pattern is within 50 +/-3 mu m

And (delta): within 50 +/-10 mu m

X: more than 50 + -10 μm or pattern disappearance

The evaluation result is O or Δ, which is particularly preferable, and the evaluation result is X, which is not suitable as a pattern forming agent.

(4. residual film ratio)

In the light irradiation unit, changes in film thickness after exposure, development, and drying were measured by a stylus type shape measuring instrument (Dektak 150 manufactured by ULVAC), and the changes were measured as a residual film ratio (%) (film thickness after development and drying/film thickness after exposure × 100). The closer the value is to 100, the higher the water resistance can be said to be.

(5. Wet Heat resistance: haze Change)

Each composition was applied onto a glass substrate by a spin coater adjusted to a film thickness of 5.0 to 5.5 μm after exposure by using a stylus profilometer (Dektak 150 manufactured by ULVAC), and then prebaked on a hot plate at 90 ℃ for 10 minutes. Then, after cooling to room temperature, 500mJ/cm of light having a wavelength of 365nm was emitted from a high-pressure mercury lamp²The substrate was dried in an oven at 140 ℃ for 30 minutes by exposure. The haze of the resulting cured product was measured by using Japanese color haze 5000. The obtained cured product was left at 85 ℃ and 85% RH for 24 hours, and then the haze of the cured product was measured in the same manner. Before and after the moisture resistance test, evaluation was performed according to the following criteria.

Very good: haze variation of less than 0.5

O: the haze change amount is 0.5 or more and less than 1

And (delta): the haze value of the glass composition is 1 or more and less than 3

X: the haze value of the glass is 3 or more

As a result, the cured products of ∈ o, · Δ and Δ were used for applications requiring moist heat resistance, and were excellent in the order of ∈ o, · Δ and Δ in moist heat resistance. Among them, the cured product of x is particularly suitable for applications requiring moist heat resistance. On the other hand, a cured product having an x value cannot be used for applications requiring moist heat resistance. In examples 29 to 35 and comparative examples 10 to 13, the haze was not measured because the colorant was added.

(6.PET flexibility and 7.PET adhesion)

The material was coated on a PET film (A4300, Toyo Boseki Co., Ltd., film thickness 38 μm), a line was drawn with a pen so that the film thickness of the cured product became 1.0 to 2.0 μm, and then prebaked on a hot plate at 90 ℃ for 1 minute. Then, after cooling to room temperature, 500mJ/cm of light having a wavelength of 365nm was irradiated with a high-pressure mercury lamp². After the light irradiation, the PET was folded by 180 degrees, and the bendability and the adhesion were measured. The evaluation criteria for the flexibility and the adhesion are as follows.

The PET flexural properties were as follows: when the folding-over is carried out,

o: no crease remained and no damage

And (delta): the condition of not being broken but having creases

X: breakage may occur.

The cured products of PET with bending properties of "o" and "Δ" can be preferably used for coating and printing of packages, and the case of "o" is particularly preferable. When the flex fatigue of PET is evaluated as x, it cannot be used as a coating or a printing of a package.

The PET adhesion was as follows: when the folding-over is carried out,

o: the condition of being unable to be peeled from the substrate

And (delta): peeling in case of scraping from side

X: and peeling off at the time of folding.

The cured products having PET adhesion evaluated as "o" and "Δ" can be preferably used for coating and printing of packages, and particularly preferably "o". When the PET adhesion is evaluated as x, it cannot be used as a coating or a printing of a package.

[ Table 4]

[ Table 5]

[ Table 6]

[ Table 7]

[ Table 8]

[ Table 9]

[ Table 10]

[ Table 11]

[ Table 12]

[ Table 13]

As shown in [ Table 4] to [ Table 13], the compositions of the present invention have high compatibility, excellent coatability and photo-etching properties, and the resulting cured products have excellent film residue ratio, moist heat resistance, PET flexibility and PET adhesion. Therefore, the composition of the present invention can be suitably used for applications such as ink, image forming material, and pattern forming agent, and the cured product of the present invention can be suitably used for applications such as coating for a package, printed matter for a package, and optical film.

Claims

1. A polymer characterized by having a structure represented by the following general formula (I),

in the general formula (I), R¹、R²、R³And R⁴Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,

R¹、R²、R³、R⁴and R⁵The hydrogen atom in the group is optionally substituted by a halogen atom, nitro group, cyano group, hydroxyl group, amino group,A carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic ring-containing group having 2 to 20 carbon atoms,

n represents an integer of 0 to 2,

when n is 2, a plurality of R's present in the molecule³And R⁴Optionally identical or different, represent an atomic bond,

in the general formulas (I alpha) and (I beta), R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶And R¹⁷Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,

2. The polymer according to claim 1, wherein R in the general formula (I)¹、R²、R³And R⁴One or more of them is a hydrogen atom.

3. The polymer according to claim 1 or 2, wherein R in the general formula (I)¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶And R¹⁷One or more of them is a hydrogen atom.

4. A polymer characterized by the structure: a structure obtained by reacting a polymer having a structure represented by the following general formula (II) with a compound represented by the following general formula (III),

in the general formula (II), R²¹、R²²、R²³And R²⁴Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,

m represents an integer of 0 to 2, and when m is 2, a plurality of R's present in the molecule²³And R²⁴Optionally identical or differentRepresents a bond of an atom(s),

5. A composition comprising the polymer according to any one of claims 1 to 4.

6. A method for producing a cured product, comprising a step of curing the composition according to claim 5.

7. A cured product obtained from the composition according to claim 5.

8. A method for producing a polymer, characterized by comprising a step of reacting a polymer having a structure represented by the general formula (II) with a compound represented by the general formula (III),

m represents an integer of 0 to 2, and when m is 2, a plurality of R's present in the molecule²³And R²⁴Optionally identical or different, represent an atomic bond,