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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/96—Esters of carbonic or haloformic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/07—Aldehydes; Ketones
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3432—Six-membered rings
  • C08K5/3435—Piperidines
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

• the present invention relates to a composition, a cured product, and a method for producing the cured product.
• Patent Document 1 When producing films, molded articles, etc. using a curable composition, in order to improve durability such as light resistance and heat resistance of the cured product, the curable composition is stabilized by adding an ultraviolet absorber. A method is known (Patent Document 1).
• UV absorber even when the above-described UV absorber is added, it may not be possible to obtain a cured product with sufficient durability.
• the ultraviolet absorber absorbs the light irradiated for photocuring, and the decomposition of the photopolymerization initiator may be inhibited, resulting in poor curing. be.
• the action as an ultraviolet absorber is inactivated in the composition before curing, and a latent additive such as a latent ultraviolet absorber that can be activated after curing is added. known to use.
• the present invention has been made in view of the above problems, and provides a curable composition capable of producing a cured product having sufficient durability, and having good sensitivity and easy production of a cured product.
• the main purpose is to
• the present inventors have found that a compound in which a phenolic hydroxyl group is protected by a protective group and acts as an ultraviolet absorber after elimination of the protective group, and a hindered amine as a light stabilizer. By using both compounds together, it is found that a cured product having sufficient durability can be obtained, and a curable composition with good sensitivity and easy production of a cured product can be obtained, and the present invention has been completed. reached.
• the present invention is a composition comprising compound A represented by the following general formula (A1), (A2) or (A3), and compound B, which is a hindered amine compound having 3 or less hindered amine structures.
• R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, a group, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic ring-containing group having 2 to 20 carbon atoms or -O-R 9 , wherein at least one of R 1 and R 2 is -O-R 9 , R 3 and R 4 each independently represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 4 carbon atoms.
• R 9 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or 2 to 2 carbon atoms.
• the methylene group in the alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group and trialkylsilyl group is a carbon-carbon double bond, -O-, -S-, -CO-, -O -CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO—S—, —CO—NH—, —NH—CO—, —NH—CO—O—, —NR′—, >P ⁇ O, —S—S— or —SO 2 — or combinations thereof 2 optionally substituted with a valent group, R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, The alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group
• R 1 ' and R 2 ' are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkyl group having 1 to 40 carbon atoms, an alkyl group having 1 to 40 carbon atoms, , an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic ring-containing group having 2 to 20 carbon atoms or —OR 9 , wherein at least one of R 1 ' and R 2 ' is —OR is 9 ; R 5 and R 6 each independently represent a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to represents a 20 arylalkyl group or a heterocyclic ring-containing group having 2 to 20 carbon atoms, R
• the methylene group in the alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group and trialkylsilyl group is a carbon-carbon double bond, -O-, -S-, -CO-, -O -CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO—S—, —CO—NH—, —NH—CO—, —NH—CO—O—, —NR′—, >P ⁇ O, —S—S— or —SO 2 — or combinations thereof 2 optionally substituted with a valent group, R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, The alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group
• R 1 ′′ and R 2 ′′ are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkyl group having 1 to 40 carbon atoms, an alkyl group having 6 to 20 carbon atoms, aryl group, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic ring-containing group having 2 to 20 carbon atoms or —OR 9 , wherein at least one of R 1 ′′ and R 2 ′′ is —OR is 9 ; R 7 and R 8 each independently represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to represents a 20 arylalkyl group or a heterocyclic ring-containing group having 2 to 20 carbon atom atom
• the methylene group in the alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group and trialkylsilyl group is a carbon-carbon double bond, -O-, -S-, -CO-, -O -CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO—S—, —CO—NH—, —NH—CO—, —NH—CO—O—, —NR′—, >P ⁇ O, —S—S— or —SO 2 — or a combination of these 2 optionally substituted with a valent group
• R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, The alkyl group, aryl group, aryl group, heterocyclic ring-containing group, alkenyl
• the present invention relates to a composition, a cured product thereof, and a method for producing the cured product.
• the composition, cured product, and method for producing the cured product of the present invention are described in detail below.
• composition of the present invention is characterized by comprising a compound A represented by the following general formula (A1), (A2) or (A3), and a compound B which is a hindered amine compound having 3 or less hindered amine structures. and
• Compound A is a compound represented by the following general formula (A1), (A2) or (A3).
• the methylene group in the alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group and trialkylsilyl group is a carbon-carbon double bond, -O-, -S-, -CO-, -O -CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO—S—, —CO—NH—, —NH—CO—, —NH—CO—O—, —NR′—, >P ⁇ O, —S—S— or —SO 2 — or combinations thereof 2 optionally substituted with a valent group, R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, The alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group
• the halogen atom represented by ) includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
• the alkyl group having 1 to 40 carbon atoms represented by R 1 etc. includes methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert - octyl, adamantyl and the like.
• Examples of the aryl group having 6 to 20 carbon atoms represented by R 1 etc. include phenyl, naphthyl, anthracenyl and the like.
• Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R 1 etc. include benzyl, fluorenyl, indenyl and 9-fluorenylmethyl groups.
• the heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R 1 etc. includes pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidon-1-yl, 2,4 -dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidin-3-yl and the like.
• the alkyl group having 1 to 20 carbon atoms represented by R 9 satisfies the predetermined number of carbon atoms among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R 1 etc. things are mentioned.
• alkenyl groups having 2 to 20 carbon atoms represented by R 9 include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl and 2-octenyl. be done.
• the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R 9 are represented by R 1 and the like. It is the same as an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and a heterocyclic ring-containing group having 2 to 20 carbon atoms.
• Examples of the trialkylsilyl group represented by R 9 include trimethylsilyl, triethylsilyl, ethyldimethylsilyl and the like.
• Examples of the alkyl group having 1 to 8 carbon atoms represented by R′ include those satisfying a predetermined number of carbon atoms among the groups exemplified as the alkyl group represented by R 1 and the like.
• the methylene group in the alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group and trialkylsilyl group is a carbon-carbon double bond, -O-, -S-, -CO-, -O -CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO—S—, —CO—NH—, —NH—CO—, —NH—CO—O—, —NR′—, >P ⁇ O, —S—S— or —SO 2 — or a combination of these 2 may be substituted with a valent group.
• the alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group and trialkylsilyl group have a structure in which the methylene group in these groups is substituted with the divalent group.
• the group of is also included. However, the number of carbon atoms in each group after replacement is 1 or more.
• the group in which the methylene group at the end of the alkyl group is substituted with -O- includes methyloxy, ethyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, amyloxy, iso -amyloxy, tert-amyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert-heptyl oxy, 1-octyloxy, iso-octyloxy, tert-octyloxy and the like.
• the number of carbon atoms defines the number of carbon atoms in the group before the substitution.
• the 1 to 40 carbon atoms means that the methylene group in the alkyl group is the above divalent group. It refers to the number of carbon atoms before being substituted with and does not refer to the number of carbon atoms after being substituted.
• a methyloxy group corresponds to a group in which a methylene group in an ethyl group is replaced with -O-.
• the alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group and trialkylsilyl group may have a substituent. Having a substituent means that a hydrogen atom in the group is replaced with a substituent. That is, in the present invention, the alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group and trialkylsilyl group have a structure in which a hydrogen atom in these groups is substituted with a substituent described below. A group is also included.
• substituents examples include ethylenically unsaturated groups such as vinyl, allyl, acryl, and methacryl; halogen atoms such as fluorine, chlorine, bromine, and iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, and phenylcarbonyl.
• Acyl groups such as (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl; acetyloxy, benzoyloxy, etc.
• the number of carbon atoms in a group defines the number of carbon atoms in the group after the substitution when the hydrogen atoms in the group are substituted.
• the 1 to 40 carbon atoms refers to the number of carbon atoms after the hydrogen atom is substituted, and the hydrogen atom is substituted. It does not refer to the number of carbon atoms before
• Compound A represented by the general formula (A1) when m1 is 2, has a structure in which two specific groups are bonded via a divalent atom or a linking group represented by X b1 or a direct bond. and when m1 is 3 to 10, it has a structure in which m1 specific groups are linked via an m1-valent atom or a linking group represented by Xb1 . The m1 specific groups are the same or different from each other. Further, the compound A represented by the general formula (A2), when m2 is 2, has a structure in which two specific groups are bonded by a divalent atom or a linking group represented by X b2 or a direct bond.
• m2 When m2 is 3 to 10, it has a structure in which m2 specific groups are linked by an m2-valent atom or a linking group represented by X b2 .
• the m2 specific groups may be the same or different.
• X b1 and X b2 may be collectively referred to as X
• m1 and m2 may be collectively referred to as m.
• the atom or linking group represented by X includes a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a group represented by (II-a) or (II-b) below, —CO—, —NR 10 - and m-valent aliphatic hydrocarbon groups having 1 to 120 carbon atoms, aromatic ring-containing hydrocarbon groups having 6 to 35 carbon atoms and heterocyclic ring-containing groups having 2 to 35 carbon atoms.
• R 10 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or a heterocyclic ring-containing group having 2 to 35 carbon atoms;
• the methylene group in the group hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic ring-containing group is -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO -O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO -, -NH-CO-O-, -NH-CO-O-, -NR 11 -, -S-S-, -SO 2 - or a nitrogen atom or a combination thereof, the aromatic The aromatic ring in the ring-containing hydrocarbon
• the m-valent aliphatic hydrocarbon group having 1 to 120 carbon atoms represented by X includes an alkyl group having 1 to 120 carbon atoms, a cycloalkyl group having 3 to 120 carbon atoms and a cycloalkyl group having 4 to 120 carbon atoms.
• a group obtained by removing m ⁇ 1 hydrogen atoms from the cycloalkylalkyl group of 120 and the like can be mentioned.
• the alkyl group having 1 to 120 carbon atoms may be linear or branched.
• Straight chain alkyl groups include methyl, ethyl, propyl, butyl, iso-amyl, tert-amyl, hexyl, heptyl and octyl.
• Branched alkyl groups include iso-propyl, sec-butyl, tert-butyl, iso-butyl, iso-pentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl and iso-heptyl.
• tert-heptyl iso-octyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebrotadecyl, octadecyl and the like.
• Cycloalkyl groups having 3 to 120 carbon atoms include saturated monocyclic alkyl groups having 3 to 120 carbon atoms, saturated polycyclic alkyl groups having 3 to 120 carbon atoms, and hydrogen atoms in the rings of these groups. Examples include groups having 4 to 120 carbon atoms in which one or more atoms are substituted with an alkyl group.
• the saturated monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.
• Examples of the saturated polycyclic alkyl groups include adamantyl, decahydronaphthyl, octahydropentalene and bicyclo[1.1.1]pentanyl.
• Examples of the alkyl group substituting the hydrogen atom in the ring of the saturated monocyclic or saturated polycyclic alkyl group include the groups exemplified as the alkyl group having 1 to 120 carbon atoms. Bornyl etc. are mentioned as a group by which 1 or more of the hydrogen atoms in the ring of the saturated polycyclic alkyl group were substituted by the alkyl group.
• a cycloalkylalkyl group having 4 to 120 carbon atoms means a group having 4 to 120 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group.
• a cycloalkyl group in a cycloalkylalkyl group may be monocyclic or polycyclic.
• Cycloalkylalkyl groups having 4 to 120 carbon atoms in which the cycloalkyl group is monocyclic include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, 2-cyclodecylethyl and the like.
• the polycyclic cycloalkylalkyl groups having 4 to 20 carbon atoms include 3-3-adamantylpropyl and decahydronaphthylpropyl.
• the m-valent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms represented by X is a hydrocarbon group containing an aromatic hydrocarbon ring and not containing a heterocyclic ring, and an aliphatic hydrocarbon group. may have.
• aromatic hydrocarbon ring-containing groups include groups obtained by removing m ⁇ 1 hydrogen atoms from aryl groups having 6 to 35 carbon atoms and arylalkyl groups having 7 to 35 carbon atoms.
• the aryl group having 6 to 35 carbon atoms may have a monocyclic structure, a condensed ring structure, or two aromatic hydrocarbon rings linked together.
• Examples of the aryl group having a condensed ring structure having 6 to 35 carbon atoms include hydrocarbon-type aromatic condensed ring groups having a structure in which two or more aromatic hydrocarbon rings are condensed and having 7 to 35 carbon atoms. .
• Examples of monocyclic aryl groups having 6 to 35 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, 2,4,6-trimethylphenyl and the like.
• Hydrocarbon type aromatic condensed ring groups having 7 to 20 carbon atoms include naphthyl, anthracenyl, phenanthryl, pyrenyl, fluorenyl and indenofluorenyl.
• the aryl group in which two aromatic hydrocarbon rings are linked may be one in which two monocyclic aromatic hydrocarbon rings are linked. It may be one in which an aromatic hydrocarbon ring having a condensed ring structure is linked to an aromatic hydrocarbon ring having a condensed ring structure.
• a linking group that links two aromatic hydrocarbon rings includes a single bond, a sulfide group (--S--), a carbonyl group, and the like.
• the aryl group in which two monocyclic aromatic hydrocarbon rings are linked includes biphenyl, diphenylsulfide, benzoylphenyl and the like.
• An arylalkyl group having 7 to 35 carbon atoms is a group in which one or more hydrogen atoms in an alkyl group are substituted with an aryl group.
• Arylalkyl groups having 7 to 35 carbon atoms include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and naphthylpropyl groups.
• the m-valent heterocyclic ring-containing group having 2 to 35 carbon atoms represented by X includes a heterocyclic group having 2 to 10 carbon atoms and one or more hydrogen atoms in the m-valent hydrocarbon group. Examples thereof include groups having 3 to 35 carbon atoms substituted with the heterocyclic group having 2 to 10 carbon atoms.
• a heterocyclic group having 2 to 10 carbon atoms is a group obtained by removing one hydrogen atom from a heterocyclic compound.
• the heterocyclic group may have a monocyclic structure or a condensed ring structure.
• Examples of the heterocyclic group having a condensed ring structure having 2 to 10 carbon atoms include a heterocyclic ring-containing condensed ring group having a structure in which a heterocyclic ring and a heterocyclic ring or a hydrocarbon ring are condensed and having 3 to 10 carbon atoms. be done.
• heterocyclic groups include pyridyl, quinolyl, thiazolyl, tetrahydrofuranyl, dioxolanyl, tetrahydropyranyl, methylthiophenyl, hexylthiophenyl, benzothiophenyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolidinyl, piperidinyl.
• the heterocyclic group may have a substituent, and examples of the substituent include a halogen atom, a cyano group, a nitro group, a hydroxyl group, an amino group, a carboxy group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, and a vinyl ether. groups, mercapto groups and isocyanate groups.
• heterocyclic group in the group having 3 to 35 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group are substituted with the above heterocyclic group having 2 to 10 carbon atoms The groups exemplified as the heterocyclic group can be mentioned.
• m-valent hydrocarbon group among the groups exemplified as the aliphatic hydrocarbon group having 1 to 120 carbon atoms and the aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, the number of carbon atoms is from 1 to A group obtained by removing m ⁇ 1 hydrogen atoms from 25 can be mentioned.
• the aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by R 10 and R 11 the aliphatic hydrocarbon group having 1 to 120 carbon atoms was exemplified in the explanation of the group represented by X. Among the groups, those having a predetermined number of carbon atoms are included.
• the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms represented by R 10 and R 11 the carbon atom
• the same groups as exemplified as aromatic ring-containing hydrocarbon groups of 6 to 35 carbon atoms and heterocyclic ring-containing groups of 2 to 35 carbon atoms can be mentioned.
• the atom represented by X includes an oxygen atom and a sulfur atom
• the linking group includes an alkylene group such as methylene, ethylene, propylene, butylene, and butyldiyl; methylene in the alkylene group; groups substituted with -O-, -S-, -CO-O-, -O-CO-; diol residues such as ethanediol, propanediol, butanediol, pentanediol, hexanediol; ethanedithiol, Dithiol residues such as propanedithiol, butanedithiol, pentanedithiol, hexanedithiol; phenylene, arylene groups such as naphthylene; catechol, bifunctional phenol residues such as bisphenol; 2,4,8,10-tetraoxaspiro [5, 5] undecane; pyridine
• the atom represented by X includes a nitrogen atom and a phosphorus atom, and the linking group includes alkylidine such as propylidine and 1,1,3-butylidine; phenyl-1,3, 5-trimethylene; isocyanuric ring, triazine ring, etc.;
• examples of the linking group represented by X include groups represented by the following general formula (1).
• examples of the linking group represented by X include groups represented by the following general formula (2).
• the linking group represented by X includes groups represented by the following general formula (3).
• the linking group represented by X includes a group represented by the following general formula (4).
• the linking group represented by X includes groups represented by the following general formula (5).
• Y 1 is a single bond, —CR 55 R 56 —, —NR 57 —, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, 6 to 35 carbon atoms, An aromatic ring-containing hydrocarbon group or a heterocyclic ring-containing group having 2 to 35 carbon atoms, or a divalent group represented by the following general formulas (1-1) to (1-3), wherein the carbon atom
• the methylene group in the aliphatic hydrocarbon group of 1 to 35, the aromatic ring-containing hydrocarbon group of 6 to 35 carbon atoms and the heterocyclic ring-containing group of 2 to 35 carbon atoms is -O-, -S-, -CO-, -CO-O-, -O-CO- or -NH- or a combination thereof
• R 55 and R 56 represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylal
• R 59 represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms
• R 60 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkyl group, alkoxy group and alkenyl group are substituents; may have c1 is an integer from 0 to 5, * means that the * portion is attached to the adjacent group.
• R 61 and R 62 each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an oxy group, an arylthio group having 6 to 20 carbon atoms, an arylalkenyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic ring-containing group having 2 to 20 carbon atoms, or a halogen atom; and the methylene group in the alkyl group and arylalkyl group may be substituted with an unsaturated bond, -O- or -S-, adjacent R 61 may form a ring, c2 represents a number from 0 to 4, c3 represents a number from 0 to 8, c4 represents a number from 0 to 4, c5 represents a number from 0 to 4, The sum of the numbers of c4 and c
• Y 11 is a trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a represents a heterocycle-containing group
• Z 1 , Z 2 and Z 3 are each independently a direct bond, -O-, -S-, >CO, -CO-O-, -O-CO-, -SO 2 -, -SS-, - SO—, >NR 62 , >PR 62 , an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms; represent, R 62 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or a heterocyclic ring-containing group having 2 to 35 carbon atoms;
• Y 12 is a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or 2 carbon atoms represents a heterocyclic ring-containing group of up to 35, and among the aliphatic hydrocarbon group having 1 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms
• the methylene group of -CO-O-, -O-, -O-CO-, -NH-CO-, -NH- or -CO-NH- may be substituted
• Z 1 to Z 4 are each independently a group in the same range as the groups represented by Z 1 to Z 3 in the general formula (2), * is a * moiety and means to bond with the adjacent group.
• Y 13 is a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a represents a heterocyclic ring-containing group, and a methylene group in the aliphatic hydrocarbon group having 2 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms is optionally substituted with -CO-O-, -O-, -O-CO-, -NH-CO-, -NH- or -CO-NH-, Z 1 to Z 5 are each independently a group in the same range as the groups represented by Z 1 to Z 3 in the general formula (2), * is a * moiety and means to bond with the adjacent group. )
• Y 14 is a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a represents a heterocyclic ring-containing group, and is a methylene group in the aliphatic hydrocarbon group having 2 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the heterocyclic ring-containing group having 2 to 35 carbon atoms is optionally substituted with -CO-O-, -O-, -O-CO-, -NH-CO-, -NH- or -CO-NH-, Z 1 to Z 6 are each independently a group in the same range as the groups represented by Z 1 to Z 3 in the general formula (2), * is a * moiety and means to bond with the adjacent group. )
• the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 1 in the general formula (1) includes an aliphatic hydrocarbon group having 1 to 120 carbon atoms in the description of the group represented by X.
• group hydrocarbon groups those having a predetermined number of carbon atoms can be mentioned.
• the group represented by the above X Examples include the same groups as those exemplified as the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms in the description.
• the alkyl group having 1 to 8 carbon atoms represented by R 55 and R 56 in the general formula (1) is exemplified as an alkyl group having 1 to 120 carbon atoms in the description of the group represented by X. Among the groups described above, those having a predetermined number of carbon atoms can be mentioned.
• the aryl group having 6 to 20 carbon atoms and the arylalkyl group having 7 to 20 carbon atoms represented by R 55 and R 56 in the general formula (1) Among the groups exemplified as the aryl group having 6 to 35 carbon atoms and the arylalkyl group having 7 to 35 carbon atoms, those satisfying the predetermined number of carbon atoms can be mentioned.
• the aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by R 57 and R 58 in the general formula (1) includes an aliphatic hydrocarbon group having 1 to 120 carbon atoms in the description of the group represented by X.
• group hydrocarbon groups those having a predetermined number of carbon atoms can be mentioned.
• the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms represented by R 57 and R 58 in the general formula (1) are represented by the above X and the same groups as those exemplified as the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms in the description of the group.
• the cycloalkyl group having 3 to 10 carbon atoms represented by R 59 in the general formula (1-1) the cycloalkyl group having 3 to 120 carbon atoms in the description of the group represented by X Among the exemplified groups, those having a predetermined number of carbon atoms are included.
• the alkyl group having 1 to 10 carbon atoms represented by R 60 in the general formula (1-1) is exemplified as the alkyl group having 1 to 120 carbon atoms in the description of the group represented by X. Among the groups, those having a predetermined number of carbon atoms are included.
• the alkoxy group having 1 to 10 carbon atoms represented by R 60 in the general formula (1-1) includes methyloxy, ethyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso- butyloxy, amyloxy, iso-amyloxy, tert-amyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyl oxy, tert-heptyloxy, 1-octyloxy, iso-octyloxy, tert-octyloxy and the like.
• the alkenyl group having 2 to 10 carbon atoms represented by R 60 in the general formula (1-1) includes vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2 -pentenyl, 2-octenyl and the like.
• Examples of the halogen atom represented by R 60 in the general formula (1-1) include fluorine atom, chlorine atom, bromine atom and iodine atom.
• the heterocyclic ring-containing group having 2 to 20 carbon atoms includes an alkyl group having 1 to 120 carbon atoms, an aryl group having 6 to 35 carbon atoms, and an aryl group having 7 to 35 carbon atoms in the description of the group represented by X.
• the groups exemplified as the arylalkyl group and the heterocyclic ring-containing group having 2 to 35 carbon atoms those satisfying a predetermined number of carbon atoms can be mentioned.
• Examples of the aryloxy group having 6 to 20 carbon atoms represented by R 61 and R 62 in the general formula (1-3) include phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, 4-vinylphenyldioxy, 3-iso-propylphenyloxy, 4-iso-propylphenyloxy, 4-butylphenyloxy, 4-tert-butylphenyloxy, 4-hexylphenyloxy, 4-cyclohexylphenyloxy, 4-octylphenyloxy, 4-(2-ethylhexyl)phenyloxy, 2,3-dimethylphenyloxy, 2,4-dimethylphenyloxy, 2,5-dimethylphenyloxy, 2,6- dimethylphenyloxy, 3,4-dimethylphenyloxy, 3,5-dimethylphenyloxy, 2,4-di-tert-butylphenyloxy,
• the oxygen atom of the aryloxy group having 6 to 20 carbon atoms is substituted with a sulfur atom. and the like.
• the oxygen atom of the aryloxy group having 6 to 20 carbon atoms is vinyl or allyl.
• halogen atoms represented by R 61 and R 62 in the general formula (1-3) include the same halogen atoms as those represented by R 60 in the general formula (1-1).
• Examples of the ring that may be formed by adjacent R 61 groups in the general formula (1-3) include a cyclopentene ring, a cyclohexene ring and a benzene ring.
• the trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 11 in the general formula (2) includes an aliphatic hydrocarbon group having 1 to 120 carbon atoms in the description of the group represented by X.
• trivalent groups obtained by removing two hydrogen atoms from the groups exemplified as group hydrocarbon groups trivalent groups having a predetermined number of carbon atoms can be mentioned.
• the trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms represented by Y 11 in the general formula (2) are represented by the above X trivalent groups obtained by removing two hydrogen atoms from the groups exemplified as aromatic ring-containing hydrocarbon groups having 6 to 35 carbon atoms and heterocyclic ring-containing groups having 2 to 35 carbon atoms in the description of the groups.
• the aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Z 1 , Z 2 and Z 3 in the general formula (2) includes Among divalent groups obtained by removing one hydrogen atom from the groups exemplified as the 120 aliphatic hydrocarbon groups, divalent groups having a predetermined number of carbon atoms can be mentioned.
• the above X A divalent group obtained by removing one hydrogen atom from the groups exemplified as aromatic ring-containing hydrocarbon groups having 6 to 35 carbon atoms and heterocyclic ring-containing groups having 2 to 35 carbon atoms in the description of the group represented by mentioned.
• the aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by R 62 in the general formula (2) is an aliphatic hydrocarbon group having 1 to 120 carbon atoms in the description of the group represented by X.
• the groups exemplified as the groups those having a predetermined number of carbon atoms can be mentioned.
• the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms represented by R 62 in the general formula (2) the group represented by the above X Examples include the same groups as those exemplified as the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms in the description.
• the tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 12 includes an aliphatic hydrocarbon group having 1 to 120 carbon atoms in the description of the group represented by X.
• tetravalent groups obtained by removing three hydrogen atoms from the groups exemplified as group hydrocarbon groups those satisfying a predetermined number of carbon atoms can be mentioned.
• the tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms represented by Y 12 are represented by the above X tetravalent groups obtained by removing three hydrogen atoms from the groups exemplified as the aromatic ring-containing hydrocarbon groups having 6 to 35 carbon atoms and the heterocyclic ring-containing groups having 2 to 35 carbon atoms in the description of the groups.
• the pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 13 includes an aliphatic hydrocarbon group having 1 to 120 carbon atoms in the description of the group represented by X.
• pentavalent groups obtained by removing four hydrogen atoms from the groups exemplified as group hydrocarbon groups those satisfying a predetermined number of carbon atoms can be mentioned.
• the pentavalent C 6-35 aromatic ring-containing hydrocarbon group and the C 2-35 heterocyclic ring-containing group represented by Y 13 are represented by the above X and a pentavalent group obtained by removing four hydrogen atoms from the groups exemplified as the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms in the description of the group.
• the hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 14 includes an aliphatic hydrocarbon group having 1 to 120 carbon atoms in the description of the group represented by X.
• hexavalent groups obtained by removing five hydrogen atoms from the groups exemplified as group hydrocarbon groups those satisfying a predetermined number of carbon atoms can be mentioned.
• the hexavalent C 6-35 aromatic ring-containing hydrocarbon group and the C 2-35 heterocyclic ring-containing group represented by Y 14 are represented by the above X hexavalent groups obtained by removing five hydrogen atoms from the groups exemplified as aromatic ring-containing hydrocarbon groups having 6 to 35 carbon atoms and heterocyclic ring-containing groups having 2 to 35 carbon atoms in the description of the groups.
• the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, heterocyclic ring-containing group, alkoxy group, alkenyl group, aryloxy group, arylthio group and arylalkenyl group may have a substituent. Having a substituent means that a hydrogen atom in the group is replaced with a substituent. That is, in the present invention, the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, heterocyclic ring-containing group, alkoxy group, alkenyl group, aryloxy group, arylthio group and arylalkenyl group include hydrogen A group having a structure in which an atom is substituted with a substituent described below is also included.
• substituents examples include the substituents exemplified in the description of the group represented by R 1 and the like.
• Compound A used in the present invention is a compound represented by the general formula (A1), (A2) or (A3).
• the compound A can show ultraviolet absorption ability by removing R 9 protecting the phenolic hydroxyl group by heating. Therefore, the composition of the present invention containing the compound A can produce a cured product excellent in durability, ie, light resistance.
• the amount added In order to further increase the durability of the cured product using compound A, the amount added must be increased, but the increased amount may reduce the development speed of the photocurable composition.
• durability can be imparted without increasing the amount of compound A, and the development speed of the photocurable composition can be maintained.
• Conventional ultraviolet absorbers when added to the polymerization system, absorb the light irradiated for photocuring, thereby inhibiting the decomposition of the photopolymerization initiator, thereby inhibiting the curing of the photocurable composition, Decrease sensitivity.
• compound A has a low absorbability of light irradiated for photocuring during polymerization, so inhibition of decomposition of the photopolymerization initiator is suppressed, and curing of the photocurable composition is inhibited. Because it does not, the decrease in sensitivity can be suppressed. Furthermore, compound A can maintain good sensitivity even when used in combination with compound B as a photostabilizer.
• a UV absorber having a phenolic hydroxyl group tends to aggregate in the composition due to the influence of the phenolic hydroxyl group, and it is difficult to increase the amount added to the composition.
• Compound A has a structure in which the phenolic hydroxyl group is protected by R9 , and is therefore excellent in dispersion stability in the composition. As a result, the compound A can be easily added to the composition and easily dispersed in the cured product, compared with conventional UV absorbers having a phenolic hydroxyl group, and its function can be fully realized. can be demonstrated in
• the amount of light transmitted along the thickness direction of the composition is greatly reduced, for example, the adhesion between the cured product and the substrate is reduced, and curing It causes a problem that the object is easily peeled off from the base material.
• the absorption of light irradiated during curing can be suppressed by using compound A as described above, and as a result, a cured product in which peeling from the substrate is suppressed can be obtained.
• the composition of the present invention contains, as a resin component, a component such as a photosensitive resin whose solubility in an alkaline developer changes upon irradiation with light, the ability to absorb irradiated light is low for developing photosensitivity. , it becomes possible to stably express the photosensitivity. Accordingly, the composition of the present invention can be a photosensitive composition that provides a cured product with excellent photosensitivity and excellent durability.
• the compound A has a structure in which a phenolic hydroxyl group is protected by a protecting group R9 , and can be rendered to have ultraviolet absorbing ability by elimination of the protecting group R9 .
• Having ultraviolet absorption ability means being able to absorb light in the wavelength range of 250 nm or more and 450 nm or less.
• the maximum absorption wavelength after elimination of the protecting group R 9 is in the wavelength range of 250 nm or more and 600 nm or less, preferably 250 nm or more and 400 nm or less, more preferably 260 nm or more and 390 nm or less, particularly It is preferably 280 nm or more and 380 nm or less. This is because the composition of the present invention facilitates production of a durable cured product.
• a compound dissolved in a solvent such as chloroform at a concentration of 0.01 g/L is used as an evaluation sample, and this is placed in a quartz cell (optical path length 10 mm, thickness 1 .25 mm) and measure the absorbance using an absorptiometer (for example, U-3900 (manufactured by Hitachi High-Tech Science)).
• a quartz cell optical path length 10 mm, thickness 1 .25 mm
• an absorptiometer for example, U-3900 (manufactured by Hitachi High-Tech Science)
• the compound A can have a maximum absorption wavelength in the wavelength range of 250 nm or more and 600 nm or less on the shorter wavelength side than the compound after elimination of the protecting group R9 .
• the difference between the maximum absorption wavelength of the compound A and the maximum absorption wavelength of the compound after elimination of the protective group R9 can be 1 nm or more, preferably 1 nm or more and 100 nm or less, and particularly 1 nm or more and 50 nm. The following are preferred. This is because when the difference in the maximum absorption wavelength is within the above range, the compound A is excellent in the effect of suppressing curing inhibition.
• the protecting group R9 of the compound A can be released by heating.
• the temperature at which the protecting group R 9 contained in the compound A is eliminated may be 100° C. or higher and 300° C. or lower, preferably 120° C. or higher and 250° C. or lower, particularly 150° C. or higher and 230° C. or lower. Preferably. This is because the above temperature facilitates the production of a durable cured product of the composition.
• the detachment temperature of the protective group can be measured, for example, as the temperature at which the first weight loss begins in the weight change measured using a STA (simultaneous differential thermogravimetric analyzer).
• STA semiconductor differential thermogravimetric analyzer
• 10 mg of compound A is filled in a measurement container, the measurement temperature range is 30° C. to 350° C., and the temperature increase rate is 10° C./min.
• STA7000 manufactured by Hitachi High-Tech Science Co., Ltd.
• STA7000 manufactured by Hitachi High-Tech Science Co., Ltd.
• At least one of R 1 and R 2 in the general formula (A1) is —OR 9 .
• one of R 1 and R 2 is - OR 9 is preferred.
• both R 1 and R 2 are preferably —OR 9 .
• the other is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
• an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms more preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms, particularly a hydrogen atom or carbon
• An alkyl group having 1 to 5 atoms is preferable, and a hydrogen atom and an unsubstituted alkyl group having 1 to 5 carbon atoms are particularly preferable. This is because the compound A has a large change in ultraviolet absorption ability and can suppress the occurrence of curing inhibition.
• R 1 and R 2 described above also apply to R 1 ′ and R 2 ′ in the general formula (A2) and R 1 ′′ and R 2 ′′ in the general formula (A3).
• R 9 is preferably an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, particularly carbon An alkyl group having 1 to 8 atoms is preferred. This is because the compound A has a large change in ultraviolet absorption ability. Moreover, the composition of the present invention facilitates the production of a durable cured product.
• R 9 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or 2 carbon atoms.
• -20 heterocyclic ring-containing groups in which the methylene group at the end on the oxygen atom side is substituted with -CO-O-, i.e., -CO-O- is bonded to the end on the oxygen atom side It is preferable that there is
• an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms in which the methylene group at the terminal on the oxygen atom side is substituted with —CO—O—.
• the alkyl group having 1 to 20 carbon atoms or the alkenyl group having 2 to 20 carbon atoms in which the methylene group at the end on the oxygen atom side is substituted with —CO—O— means “*—CO—O—R 300 " is a group.
• * represents a bond with an oxygen atom
• R 300 represents an alkyl group having 1 to 19 carbon atoms or an alkenyl group having 2 to 19 carbon atoms.
• R 9 is preferably an alkyl group having 1 to 20 carbon atoms in which the terminal methylene group on the oxygen atom side is substituted with —CO—O—, particularly the terminal methylene group on the oxygen atom side is — It is preferably an alkyl group having 1 to 8 carbon atoms substituted with CO-O-, and among these, particularly the terminal methylene group on the oxygen atom side is substituted with -CO-O-. It is preferably an alkyl group having 1 to 8 carbon atoms that is not Preferably. This is because R9 can be easily eliminated from the compound A by heating, for example, to form a phenolic hydroxyl group. As a result, the composition of the present invention can be easily produced into a durable cured product. Examples of those having an alkyl group in which the methylene group at the end on the oxygen atom side is substituted with --CO--O-- include compounds represented by formula (A1-1) described later.
• R 3 , R 4 , R 5 , R 6 , R 7 and R 8 in the general formulas (A1), (A2) and (A3) are each independently a halogen atom or an alkyl having 1 to 40 carbon atoms is preferably an unsubstituted alkyl group having 1 to 40 carbon atoms, an alkyl group having 1 to 40 carbon atoms having an ethylenically unsaturated group as a substituent, and a methylene group at the end an alkyl group having 1 to 40 carbon atoms (alkoxy group having 1 to 40 carbon atoms) substituted with -O-, and a methylene group having 1 to 40 carbon atoms substituted with -O-CO-
• alkyl groups unsubstituted alkoxy groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms with ethylenically unsaturated groups as substituents, and methylene groups in the groups are - an unsubstituted alkyl group having 1 to 10 carbon atoms substituted with O-CO-, or an unsubstituted carbon atom in which a methylene group in the group is substituted with -O-CO- An alkoxy group of number 1 to 10 is preferred.
• R 4 in the general formula (A1) is preferably an unsubstituted alkyl group having 1 to 20 carbon atoms, and an unsubstituted alkyl group having 3 to 15 carbon atoms. and preferably an unsubstituted alkyl group having 5 to 12 carbon atoms. R 4 is also preferably an unsubstituted alkoxy group having 1 to 10 carbon atoms.
• R 5 and R 6 in the general formula (A2) are preferably unsubstituted alkoxy groups having 1 to 10 carbon atoms.
• R 5 and R 6 are also preferably unsubstituted alkyl groups having 1 to 10 carbon atoms, and are preferably unsubstituted alkyl groups having 1 to 5 carbon atoms. more preferred.
• R 7 in the general formula (A3) is preferably an unsubstituted alkyl group having 1 to 10 carbon atoms.
• R 7 is preferably an unsubstituted alkoxy group having 1 to 15 carbon atoms, more preferably an unsubstituted alkoxy group having 2 to 10 carbon atoms.
• composition of the present invention facilitates production of a durable cured product.
• the bonding position of R 4 may be any bondable position, but is preferably ortho or para to the bonding position of —OR 9 .
• the bonding position of R 5 may be any bondable position, but is preferably the meta position with respect to the bonding position of —OR 9 .
• the binding position of R 6 may be any binding position, but is preferably the meta position with respect to the binding position of --OR 9 .
• the bonding position of R 7 may be any bondable position, but is preferably ortho or meta with respect to the bonding position of —OR 9 .
• a1 in the general formula (A1) is an integer of 0 to 4, but a curable composition having good sensitivity and easy production of a cured product having excellent durability is obtained, and further synthesis is possible. From the viewpoint of easiness, it is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 to 1.
• a2 in the general formula (A1) is an integer of 0 to 2, preferably 1 to 2 from the viewpoint of solubility. This is because the composition facilitates production of a cured product having durability and good sensitivity.
• m1 in the general formula (A1) is an integer of 1 to 10, but from the viewpoint of obtaining a curable composition having good sensitivity and easy production of a cured product having excellent durability, 1 An integer of up to 5 is preferred, and an integer of 1-2 is particularly preferred.
• a3 in the general formula (A2) is an integer of 0 to 4, and a curable composition having good sensitivity and easy production of a cured product having excellent durability is obtained, and further synthesis is possible. From the viewpoint of easiness, it is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 to 1.
• a4 in the general formula (A2) is an integer of 0 to 3, but a curable composition having good sensitivity and easy production of a cured product having excellent durability is obtained, and further synthesis is possible. From the viewpoint of easiness, it is preferably an integer of 0 to 2, particularly preferably 1 to 2.
• m2 in the general formula (A2) is an integer of 1 to 10, but from the viewpoint of obtaining a curable composition having good sensitivity and easy production of a cured product having excellent durability, 1 An integer of up to 5 is preferred, and an integer of 1-2 is particularly preferred.
• a5 in the general formula (A3) is an integer of 0 to 3, but a curable composition having good sensitivity and easy production of a cured product having excellent durability is obtained, and further synthesis is possible. From the viewpoint of easiness, it is preferably an integer of 0 to 2, particularly preferably an integer of 1 to 2.
• a6 in the general formula (A3) is an integer of 0 to 3-m3, but a curable composition having good sensitivity and easy production of a cured product having excellent durability is obtained; It is preferably 0 or 2 from the viewpoint of ease of synthesis.
• m3 in the general formula (A3) is an integer of 1 to 3, from the viewpoint that a curable composition having good sensitivity and easy production of a cured product having excellent durability can be obtained. , 1 or 3.
• the linking group represented by X b1 in the general formula (A1) and X b2 in the general formula (A2) is m1 in the general formula (A1) and m1 in the general formula (A2)
• m2(m) is 2, it is preferably an aliphatic hydrocarbon group having 1 to 120 carbon atoms, more preferably an alkylene group or diol residue having 1 to 10 carbon atoms. It is more preferably an alkylene group having 1 to 5 carbon atoms such as methylene group of number 1, and particularly preferably an alkylene group having 1 to 3 carbon atoms. This is because a curable composition that facilitates production of a cured product having excellent durability can be obtained, and synthesis is easy.
• the linking group represented by X is also preferably a substituent represented by the following general formula (101) or (102) or a group selected from Group 1 below.
• the linking group represented by X is preferably a group selected from the following group 2 when (2) m is 3, and (3) a group selected from the following group 3 when m is 4.
• Y 111 and Y 115 each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms
• Y 112 and Y 114 are each independently -O-, -CO-, -CO-O-, -O-CO-, -NR 13 -, -CO-NR 13 - or -NR 13 -CO- represents the group represented
• R 13 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent
• Y 113 is —CR 14 R 15 —, —NR 16 —, an optionally substituted divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, optionally having a substituent represents an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or a substituent represented by the following general formula (103)
• R 14 and R 15 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6
• Y 111 , Y 115 , R 13 , Y 113 and R 16 are —COO; -, -O-, -OCO-, -NHCO-, -NH- or -CONH- may be substituted, * represents a binding site.
• Y 119 and Y 120 each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, * represents a binding site.
• Y 116 and Y 118 each independently represent —NR 17 — or an aliphatic hydrocarbon group having 1 to 8 carbon atoms
• the methylene group in the aliphatic hydrocarbon group may be substituted with an oxygen atom
• Y 117 is a direct bond, —O—, —S—, —SO 2 —, —CR 18 R 19 — or represented by general formula (1-1), (1-2) or (1-3) above.
• R 17 represents a hydrogen atom or an optionally substituted aliphatic hydrocarbon group having 1 to 35 carbon atoms
• R 18 and R 19 each independently represent a hydrogen atom or an optionally substituted halogen atom alkyl group having 1 to 8 carbon atoms
• * represents a binding site.
• R 31 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 35 carbon atoms, an optionally substituted aromatic group having 6 to 35 carbon atoms, represents a ring-containing hydrocarbon group or an optionally substituted heterocyclic ring-containing group having 2 to 35 carbon atoms, * represents a binding site.
• R 32 is the same group as R 57 in the general formula (1), and when there are two or more in the group, they may be the same or different, and Z 11 is the ) represents a group in the same range as the group represented by Z 1 to Z 3 in * represents a binding site.
• R 32 is the same group as R 57 in the general formula (1), and when there are two or more in the group, they may be the same or different, and Z 11 is the same as R 57 in the general formula (2 ) represents a group in the same range as the group represented by Z 1 to Z 3 in * represents a binding site.
• Z 10 , Z 11 , Z 12 , Z 13 and Z 14 represent groups in the same range as the groups represented by Z 1 to Z 3 in the general formula (2), * represents a binding site.
• Z 10 , Z 11 , Z 12 , Z 13 , Z 14 and Z 15 represent groups in the same range as the groups represented by Z 1 to Z 3 in the general formula (2), * represents a binding site.
• aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by Y 111 , Y 115 , Y 116 , Y 118 , Y 119 and Y 120 , Y 1 etc.
• the aliphatic hydrocarbon groups having 1 to 35 carbon atoms which may have a divalent substituent represented by those satisfying a predetermined number of carbon atoms can be mentioned.
• Y 111 and Y 115 may be the same or different.
• Y 116 and Y 118 in the above formula (102) and Y 119 and Y 120 in the above formula (103) may be the same or different.
• an optionally substituted divalent C 1-35 aliphatic hydrocarbon group represented by Y 113 an optionally substituted divalent C 6-35
• a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent represented by Y 1 etc., optionally having a substituent
• the groups exemplified as the bivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms can be mentioned.
• an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent and a number of carbon atoms which may have a substituent
• the groups exemplified as heterocyclic ring-containing groups of 2 to 35 can be mentioned.
• the alkyl group having 1 to 8 carbon atoms, the aryl group having 6 to 20 carbon atoms and the arylalkyl group having 7 to 20 carbon atoms represented by R 14 , R 15 , R 18 and R 19 are R 1 Among the groups exemplified as alkyl groups having 1 to 40 carbon atoms, aryl groups having 6 to 20 carbon atoms and arylalkyl groups having 7 to 20 carbon atoms represented by etc., those satisfying a predetermined number of carbon atoms mentioned.
• a plurality of Z 11 in each formula of Groups 2 and 3, Z 10 to Z 14 in each formula of Group 4, and Z 10 to Z 15 in each formula of Group 5 may be the same, can be different.
• the bonding position of the linking group represented by X to the benzene ring may be any bondable position within the benzene ring .
• a meta position is preferred. This is because the composition of the present invention facilitates production of a durable cured product.
• compound A examples include compounds described in International Publication No. 2014/021023, such as the compounds represented below.
• the compound A may contain a phenolic hydroxyl group that is not protected by a protecting group R9 , but the number of phenolic hydroxyl groups contained in the compound A is preferably 2 or less, and is 0. is preferred. This is because the compound A can suppress the occurrence of curing inhibition.
• the molecular weight of the compound A can be set according to the use of the compound A and the like.
• the molecular weight can be 250 or more and 5000 or less, can be 300 or more and 2500 or less, or can be 350 or more and 1500 or less.
• the molecular weight can be represented by a weight average molecular weight (Mw).
• the weight average molecular weight (Mw) can be obtained as a standard polystyrene conversion value by gel permeation chromatography (GPC).
• the method for producing compound A is not particularly limited as long as it is a method for obtaining a compound having a desired structure, and examples thereof include the method described in International Publication No. 2014/021023.
• Compound B used in the present invention is a hindered amine compound having 3 or less hindered amine structures.
• a hindered amine compound is a compound having at least one 2,2,6,6-tetraalkylpiperidyl group having a secondary amine or tertiary amine at the 4-position in the molecule.
• the compound B is preferably a compound represented by the following general formula (B1) or (B2). This is because the composition of the present invention provides a cured product having good sensitivity and excellent durability.
• R 95 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms
• R 96 represents a residue or a carbonate group obtained by removing a hydrogen atom from the carboxy group of a monovalent to trivalent organic carboxylic acid
• n1 represents an integer of 1-3. However, n1 is 2 when R96 is a carbonate group.
• R 97 represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms
• R 98 represents an alkenylcarbonyl group.
• the alkyl group having 1 to 30 carbon atoms represented by R 95 and R 97 the alkyl group having 1 to 40 carbon atoms represented by R 1 etc. in the general formulas (A1) to (A3) Among the groups exemplified as , those having a predetermined number of carbon atoms can be mentioned.
• Examples of the alkoxy group having 1 to 30 carbon atoms represented by R 95 include groups in which an oxygen atom is bonded to the terminal of the alkyl group having 1 to 30 carbon atoms.
• the "mono- to trivalent organic carboxylic acid" in the "residue obtained by removing a hydrogen atom from the carboxy group of a mono- to trivalent organic carboxylic acid” represented by R 96 is 1 having 2 to 20 carbon atoms. to trivalent organic carboxylic acids.
• monovalent organic carboxylic acids include acetic acid, propionic acid, acrylic acid, butyric acid, isobutyric acid, methacrylic acid, valeric acid, caproic acid, caprylic acid, neodecanoic acid, 2-ethylhexyl acid, pelargonic acid, Undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, nitrilotriacetic acid, thioglycolic acid, octylmethylcaptopropionate acid, benzoic acid, toluic acid, tert-butylbenzoic acid, salicylic acid, 3,5-di-tert-butyl-hydroxyphenylbenzoic acid and 3,5-di-tert-butyl
• Divalent organic carboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, thiodipropionic acid, phthalic acid, isophthalic acid and terephthalic acid. mentioned.
• Trivalent organic carboxylic acids include tricarballylic acid, butanetricarboxylic acid, butenetricarboxylic acid and 1,3,5-pentanetricarboxylic acid.
• R 95 in the general formula (B1) is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. This is because the composition provides a cured product having good sensitivity and excellent durability.
• R 96 is a residue obtained by removing a hydrogen atom from the carboxy group of a monovalent to trivalent organic carboxylic acid
• R 95 is preferably an alkyl group having 1 to 6 carbon atoms, and 1 carbon atom.
• An alkyl group having 1 to 3 carbon atoms is more preferable, an alkyl group having 1 to 2 carbon atoms is more preferable, a methyl group or an ethyl group is still more preferable, and a methyl group is most preferable.
• R 95 is preferably an alkoxy group having 5 to 12 carbon atoms, more preferably an alkoxy group having 10 to 12 carbon atoms, such as decyloxy, undecyloxy or dodecyloxy, most preferably undecyloxy.
• R 96 in the general formula (B1) is a residue obtained by removing a hydrogen atom from the carboxy group of adipic acid, azelaic acid, or sebacic acid, or a carbonate group, from the viewpoint of cost, ease of production, and effect of improving light resistance. More preferably, it is a residue obtained by removing a hydrogen atom from the carboxy group of sebacic acid, or a carbonate group.
• n1 in the general formula (B1) is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of a composition capable of producing a cured product having good sensitivity and excellent durability.
• n1 is 2 when R 96 is a carbonate group.
• Specific examples of the compound represented by the general formula (B1) include the following compounds.
• R 97 in the general formula (B2) is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. This is because the composition provides a cured product having good sensitivity and excellent durability.
• the alkenylcarbonyl group represented by R 98 in the general formula (B2) includes acryloyl, methacryloyl, 3-butenecarbonyl, 2-methyl-3-butenecarbonyl and the like.
• R 98 is preferably acryloyl or methacryloyl, more preferably methacryloyl, from the viewpoints of cost, ease of production, and effect of improving light resistance.
• Specific examples of the compound represented by the general formula (B2) include the following compounds.
• the method for synthesizing the compound represented by the general formula (B1) or (B2) is not particularly limited, and it can be synthesized by a method in ordinary organic synthesis.
• a purification method distillation, recrystallization, reprecipitation, a method using a filtering agent/adsorbent, or the like can be appropriately used.
• most of the commercially available products at low cost are mixtures, which may be used singly or as a mixture, and can be used regardless of the production method, composition, melting point, acid value, and the like.
• composition (I) Contents of Compound A and Compound B The composition of the present invention contains the compound A and the compound B described above. As the content of the compound A, the composition is excellent in sensitivity, as long as it is possible to produce a cured product having the desired durability, 0.01 per 100 parts by mass of the solid content of the composition It can be from 0.05 parts by mass to 20 parts by mass, more preferably from 0.1 parts by mass to 15 parts by mass, and particularly 0.5 parts by mass. It is preferably at least 10 parts by mass. This is because the composition containing the compound A in such an amount can produce a cured product having excellent durability, and has good sensitivity to facilitate production of the cured product.
• solid content means the sum total of all the components other than a solvent.
• the content is based on mass unless otherwise specified.
• the lower limit of the content of the compound A is 100 mass of the solid content of the composition, from the viewpoint of exhibiting sufficient ultraviolet absorption ability. It is preferably 0.6 parts by mass or more, more preferably 0.8 parts by mass or more, and particularly preferably 2 parts by mass or more. This is because by setting the lower limit of the content in this way, it is possible to provide a sufficient ultraviolet absorbing ability even in the case of a thin film member.
• the content of the compound A varies depending on the content of the solvent and the like, but it can be 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition. This is because the above content allows the compound A to be stably dispersed in the composition.
• the composition containing the compound A in such an amount makes it possible to produce a cured product having excellent durability, and has good sensitivity, which facilitates the production of the cured product.
• the content of the compound A is sufficient as long as the composition is excellent in sensitivity and capable of producing a cured product having the desired durability. It can be from 15 parts by mass to 85 parts by mass, and more preferably from 40 parts by mass to 90 parts by mass. This is because the composition containing the compound A in such an amount can produce a cured product having excellent durability, and has good sensitivity to facilitate production of the cured product.
• the content of the compound B is not particularly limited as long as the composition can produce a cured product having excellent sensitivity and desired durability. It can be from 0.005 parts by mass to 10 parts by mass, more preferably from 0.1 parts by mass to 8 parts by mass, and particularly 0.5 parts by mass. It is preferably at least 6 parts by mass and no more than 6 parts by mass. This is because the composition containing the compound B in such an amount can produce a cured product having excellent durability, and has good sensitivity to facilitate production of the cured product.
• the content of the compound B varies depending on the content of the solvent and the like, but it can be 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition. This is because the above content allows the compound B to be stably dispersed in the composition.
• the composition containing compound B in such an amount can produce a cured product having excellent durability, and has good sensitivity, which facilitates the production of the cured product.
• the total content of the compound A and the compound B is sufficient as long as the composition is excellent in sensitivity and can produce a cured product having the desired durability.
• it can be 0.01 to 25 parts by mass, preferably 0.05 to 20 parts by mass, and more preferably 0.1 to 15 parts by mass. In particular, it is preferably 1 part by mass or more and 10 parts by mass or less. This is because the composition containing the compound A and the compound B in such amounts can produce a cured product having excellent durability, and has good sensitivity to facilitate production of the cured product.
• the lower limit of the content of the compound A and the compound B is the lower limit of the content of the composition from the viewpoint that the compound A can exhibit sufficient ultraviolet absorption ability. It is preferably 1.5 parts by mass or more, more preferably 1.8 parts by mass or more, and particularly preferably 3 parts by mass or more based on 100 parts by mass of the solid content.
• the total content of the compound A and the compound B varies depending on the content of the solvent, etc., but can be 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition. This is because the compound A and the compound B can be stably dispersed in the composition when the content is as described above. Moreover, the composition containing the compound A and the compound B in such amounts can produce a cured product having excellent durability, and has good sensitivity, which facilitates the production of the cured product.
• the composition of the present invention may contain a resin component.
• the resin component can be one that can hold the compound A and the compound B, and is appropriately set according to the use of the composition, etc., but a polymerizable compound having a polymerizable group, Examples thereof include polymers having no polymerizable group.
• a polymerizable compound is included. This is because the composition can more effectively exhibit the effect of facilitating the production of a cured product. Specifically, by containing the compound A which absorbs little irradiated light, the composition can more effectively exhibit the effect of facilitating the production of a cured product.
• the said composition can be used as a photocurable composition, a thermosetting composition, etc. by including a polymerizable compound as said resin component.
• the polymerizable compound should be capable of forming a polymer, and is usually a compound having a polymerizable group.
• Such polymerizable compounds can be classified according to the type of polymerizable group, that is, the type of polymerization reaction, and include radically polymerizable compounds, cationically polymerizable compounds and anionically polymerizable compounds.
• the composition of the invention preferably contains a radically polymerizable compound. This is because the composition can more effectively exhibit the effect of facilitating the production of a cured product. Specifically, since the composition contains the compound B in which the scavenging action of radicals is suppressed, the effect of facilitating the production of a cured product can be more effectively exhibited.
• the radically polymerizable compound may have one or more radically polymerizable polymerizable groups, and may have two or more radically polymerizable groups.
• the radically polymerizable polymerizable group include ethylenically unsaturated bond-containing groups such as (meth)acryloyl groups and vinyl groups.
• (Meth)acryloyl is used to include acryloyl and methacryloyl, and (meth)acrylate is used to include acrylate and methacrylate.
• the radical polymerizable compound is usually used together with a radical polymerization initiator.
• the radically polymerizable compound may be a compound having an acid value or a compound having no acid value.
• Compounds having an acid value include compounds having a carboxyl group. Since the composition contains a compound having an acid value as the radically polymerizable compound, the solubility of the light-irradiated portion in an alkaline developer decreases. Therefore, the composition can be used as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation. More specifically, the composition can be used as a negative photosensitive composition by containing a compound having an acid value.
• the alkaline developer those commonly used as alkaline developers such as tetramethylammonium hydroxide (TMAH) aqueous solution and potassium hydroxide aqueous solution can be used.
• compounds having an ethylenically unsaturated bond and an acid value include (meth)acrylic acid, ⁇ -chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic Acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxy phthalate ethyl], ⁇ -carboxypolycaprolactone mono(meth)acrylate, polymer mono(meth)acrylate, hydroxyethyl(meth)acrylate/malate, hydroxypropyl(meth)acrylate/malate having carboxy group and hydroxyl group at both ends such as mono(meth)acrylate , dicyclopentadiene maleate or unsaturated
• R 41 is a direct bond, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, —O—, —S—, —SO 2 —, —SS— , -SO-, -CO-, -OCO- or a substituent represented by the general formulas (1-1) to (1-3),
• R 41 , R 42 , R 43 and R 44 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or represents a halogen atom, d represents an integer of 0 to 10;
• alkyl group having 1 to 5 carbon atoms examples include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl and tert-amyl. .
• alkoxy group having 1 to 8 carbon atoms examples include methyloxy, ethyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, amyloxy, iso-amyloxy, tert-amyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert-heptyloxy, 1-octyloxy, iso-octyl oxy, tert-octyloxy and the like.
• alkenyl group having 2 to 5 carbon atoms examples include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl and 2-pentenyl.
• alkylidene group having 1 to 4 carbon atoms examples include methylidene, ethylidene, propylidene and butylidene.
• Examples of the alicyclic hydrocarbon group include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and the like.
• the alkyl group, alkoxy group, alkenyl group, alkylidene group, alicyclic hydrocarbon group, etc. may have a substituent.
• the content of the compound having an acid value can be appropriately set according to the use of the composition, etc., and can be 10 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the resin component, and can be 15 parts by mass or more. It is preferably 85 parts by mass or less, and particularly preferably 20 parts by mass or more and 80 parts by mass or less. This is because when the content is within the above range, the composition can be used as a negative photosensitive composition with excellent sensitivity.
• compounds having an ethylenically unsaturated bond and not having an acid value include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth) ) glycidyl acrylate, compound no. A1 to No.
• A4 methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, dimethyl (meth)acrylate aminoethyl, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, (meth)acrylate ) e
• vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; indene, 1 -Indenes such as methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Polymer molecules such as polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate and polysiloxane Macromonomers having a mono(meth)acryloyl group at the chain end; (meth)acrylonitrile, ethylene, propylene, butylene, vinyl chloride, other vinyl compounds such as vinyl acetate, polymethyl methacrylate macromonomer, polystyrene macromonomer, etc.
• (Meth)acrylic acid copolymers reacted with isocyanate compounds having unsaturated bonds such as MOI and AOI, vinyl chloride, vinylidene chloride, divinyl succinate, Diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinylimidazole, vinyloxazoline, vinylcarbazole, vinylpyrrolidone, vinylpyridine, hydroxyl group-containing vinyl monomers and vinyl urethane compounds of polyisocyanate compounds, hydroxyl group-containing vinyl monomers and reaction products of vinyl epoxy compounds of polyepoxy compounds, hydroxyl group-containing polyfunctional acrylates such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and polyfunctional isocyanates such as tolylene diisocyanate and hexamethylene diisocyanate.
• isocyanate compounds having unsaturated bonds such as MOI and AOI, vinyl chloride, vinyliden
• the number of radically polymerizable groups contained in the compound having no acid value may be 1 or more, preferably 2 or more and 10 or less, and preferably 3 or more and 8 or less.
• the compound having no acid value may be a mixture of compounds having different numbers of polymerizable groups. This is because the composition facilitates adjustment of the curing speed and the hardness of the cured product.
• the compound having no acid value is, for example, a mixture of a compound having 3 polymerizable groups and a compound having 4 polymerizable groups, a compound having 5 polymerizable groups and 6 polymerizable groups. can be a mixture of compounds of
• the content of the compound having no acid value can be appropriately set according to the use of the composition, etc., but it can be 10 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the resin component, and 15 parts by mass. It is preferably from 20 parts by mass to 85 parts by mass, and particularly preferably from 20 parts by mass to 80 parts by mass. This is because when the content is within the above range, the composition can be used as a negative composition with excellent sensitivity.
• the radically polymerizable compound can be used alone or in combination of two or more.
• a compound having an ethylenically unsaturated bond and an acid value and a compound having an ethylenically unsaturated bond and having no acid value can be used in combination.
• two or more radically polymerizable compounds are used in combination, they may be pre-copolymerized and used as a copolymer.
• the cationically polymerizable compound may be a compound having one or more cationically polymerizable groups.
• the cationic polymerizable group include cyclic ether groups such as epoxy groups and oxetane groups, vinyl ether groups, and the like. That is, examples of cationic polymerizable compounds include cyclic ether compounds such as epoxy compounds and oxetane compounds, and vinyl ether compounds.
• the cationic polymerizable compound is usually used together with a cationic polymerization initiator.
• the epoxy compounds include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C 12 -C 13 mixed alkyl glycidyl ether, phenyl-2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl glycidyl
• Epoxidized polyolefin can also be used as the epoxy compound.
• An epoxidized polyolefin is a polyolefin obtained by modifying a polyolefin with an epoxy group-containing monomer to introduce an epoxy group. It can be produced by copolymerizing ethylene or an ⁇ -olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and optionally other monomers by either a copolymerization method or a grafting method. Ethylene or ⁇ -olefins having 3 to 20 carbon atoms, epoxy group-containing monomers and other monomers may be polymerized singly or in combination with other monomers.
• the double bond of non-conjugated polybutadiene having a hydroxyl group at the end can be epoxidized by the peracetic acid method, and one having a hydroxyl group in the molecule may be used.
• hydroxyl groups can be urethanized with isocyanate, and epoxy groups can be introduced by reacting a primary hydroxyl group-containing epoxy compound.
• Examples of the ethylene or ⁇ -olefin having 3 to 20 carbon atoms include ethylene, propylene, butylene, isobutylene, 1,3-butadiene, 1,4-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3 -butadiene, piperylene, 3-butyl-1,3-octadiene and isoprene.
• Examples of the epoxy group-containing monomers include glycidyl esters of ⁇ , ⁇ -unsaturated acids, vinylbenzyl glycidyl ethers and allyl glycidyl ethers.
• Examples of glycidyl esters of ⁇ , ⁇ -unsaturated acids include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate, with glycidyl methacrylate being particularly preferred.
• Examples of the other monomers include unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene; (meth)acrylic acid, ⁇ -chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, Fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)phthalate ) acryloyloxyethyl], ⁇ -carboxypolycaprolactone mono(meth)acrylate, polymer mono(meth)acrylate having a carboxy group and a hydroxyl group at both ends, hydroxyethyl (meth)acrylate malate, hydroxypropyl (meth)acrylate ) Unsatur
• styrene 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfone unsaturated aromatic compounds such as acids, vinylbenzyl methyl ether and vinylnaphthalene; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; allyl alcohol and crotyl alcohol.
• vinyl alcohols such as; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether and isobutyl vinyl ether; Unsaturated imides such as phenylmaleimide and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; polymer molecules such as polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate and polysiloxane Macromonomers having a mono(meth)acryloyl group at the chain end; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinylimidazole, vinyloxazoline , vinylcarbazole, vinylpyrrolidone, vinylpyridine, vinyl urethane compounds of hydroxyl group-containing vinyl monomers and polyisocyanate compounds,
• Epolead PB3600 Epolead PB4700 (manufactured by Daicel); BF-1000, FC-3000 (manufactured by ADEKA); Bondfast 2C, Bondfast E, Bondfast CG5001.
• oxetane compound examples include 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[( 3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6 -bis(3-ethyl-3-oxetanylmethoxy)hex
• vinyl ether compound examples include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, and 2-hydroxyethyl.
• the anionically polymerizable compound may be any compound having one or more anionically polymerizable groups.
• the anionic polymerizable group include an epoxy group, a lactone group, and a (meth)acrylic group. That is, examples of the anionically polymerizable compound include epoxy compounds, lactone compounds, compounds having a (meth)acrylic group, and the like. Examples of the lactone compound include ⁇ -propiolactone and ⁇ -caprolactone.
• the anionically polymerizable compound is usually used together with an anionic polymerization initiator.
• the epoxy compound the epoxy compounds exemplified as the cationic polymerizable compound can be used.
• the compound having a (meth)acrylic group those exemplified as the radically polymerizable compound can be used.
• the cationically polymerizable compound and the anionically polymerizable compound can be used alone or in combination of two or more.
• the molecular weight of the polymerizable compound is appropriately set depending on the use of the composition, etc., and can be 50 or more, and can be 50 or more and 3,000 or less.
• the molecular weight is represented by a weight average molecular weight (Mw).
• the content of the polymerizable compound as long as the composition can be used as a curable composition, the compound A, the compound B and 1 part by mass in a total of 100 parts by mass of the polymerizable compound 99 parts by mass or less, preferably 50 parts by mass or more and 99 parts by mass or less, and particularly preferably 80 parts by mass or more and 99 parts by mass or less.
• the content is in the above range, the composition is easy to use as a curable composition, and the effect of improving durability such as light resistance and heat resistance of the curable composition. can be more effectively exhibited.
• the polymer does not have a polymerizable group.
• any polymer containing a repeating structure may be used, and examples thereof include photosensitive resins having photosensitivity and non-photosensitive resins having no photosensitivity.
• the composition of the present invention can be used as a photosensitive composition by containing a photosensitive resin as a resin component.
• the photosensitive resin has photosensitivity. For example, it is used together with an acid generator, and dissolves in a developer by the action of an acid such as cleavage of a chemical bond such as an ester group or an acetal group.
• an acid such as cleavage of a chemical bond such as an ester group or an acetal group.
• Examples include positive resins that change in the direction of increasing properties. Since the composition contains a positive resin as a resin component, the solubility of the light-irradiated portion in an alkaline developer is increased. Therefore, the composition can be used as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation, more specifically as a positive composition.
• a polymer obtained by introducing an acid-labile group capable of controlling alkali dissolution can be used as the positive resin.
• Such polymers include polyhydroxystyrene and its derivatives; polyacrylic acid and its derivatives; polymethacrylic acid and its derivatives; hydroxystyrene, acrylic acid, methacrylic acid and their derivatives.
• Copolymer 2 or more copolymers selected from hydroxystyrene, styrene and their derivatives; 3 or more copolymers selected from cycloolefin and its derivatives, maleic anhydride, and acrylic acid and its derivatives Coalescing; three or more copolymers selected from cycloolefins and derivatives thereof, maleimide, and acrylic acid and derivatives thereof; polynorbornene; one or more high molecular weight polymers selected from the group consisting of metathesis ring-opening polymers etc.
• Examples of the acid-labile group include a tertiary alkyl group, a trialkylsilyl group, an oxoalkyl group, an aryl group-substituted alkyl group, a heteroalicyclic group such as a tetrahydropyran-2-yl group, a tertiary alkylcarbonyl group, a tertiary An alkylcarbonylalkyl group, an alkyloxycarbonyl group, and the like can be mentioned.
• positive resin examples include resins described in JP-A-2003-192665, claim 3 of JP-A-2004-323704, and JP-A-10-10733.
• a known acid generator can be used as the acid generator used together with the positive resin.
• Specific examples of the acid generator include a photocationic polymerization initiator and a thermal cationic polymerization initiator, which will be described later.
• Non-photosensitive resin is not photosensitive, and may be polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-( meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin and the like. Polymers of the above polymerizable compounds can also be used as the non-photosensitive resin.
• the weight-average molecular weight (Mw) of the polymer is appropriately set depending on the use of the composition, etc., and can be 1500 or more, and can be 1500 or more and 300000 or less. can do.
• the content of the resin component is appropriately set according to the application of the composition, etc., and is 1 part by mass or more and 99 parts by mass or less per 100 parts by mass of the solid content. It is preferably 10 parts by mass or more and 95 parts by mass or less, and particularly preferably 15 parts by mass or more and 90 parts by mass or less. This is because the composition can stably retain the compound A and the compound B when the content is within the above range.
• the content of the resin component can be 1 part by mass or more and 99 parts by mass or less in a total of 100 parts by mass of the compound A, the compound B and the resin component, and is 30 parts by mass or more and 99 parts by mass or less. It is preferably 50 parts by mass or more and 99 parts by mass or less. This is because the composition can stably retain the compound A and the compound B when the content is within the above range. Moreover, it is because the effect of improving durability, such as light resistance, and favorable sensitivity of a curable composition can be exhibited more effectively.
• the total content of the resin component, the compound A and the compound B can be 1 part by mass or more in 100 parts by mass of the composition, and more preferably 10 parts by mass or more and 90 parts by mass or less.
• composition can produce a cured product having excellent durability, and has good sensitivity, thereby facilitating production of the cured product.
• the type of the resin component may be only one type, or may be a combination of two or more types.
• the resin component may contain either one of the polymerizable compound and the polymer, or both.
• the content of the polymerizable compound can be appropriately set according to the application of the composition, etc. It can be 1 part by mass or more and 99 parts by mass or less.
• composition of the present invention may optionally contain other components in addition to the compound A, the compound B and the resin component.
• the other components include polymerization initiators, colorants, solvents, chain transfer agents, sensitizers, surfactants, silane coupling agents, melamine compounds, acid catalysts, base catalysts, and the like.
• the polymerization initiator is included as a curable component and is usually used together with a polymerizable compound.
• the polymerization initiator may be any one as long as it can polymerize the polymerizable compound.
• a polymerization initiator and the like are included.
• the polymerization initiator is preferably a photopolymerization initiator from the viewpoint of effectively exhibiting the effect that even when the composition contains compound A and compound B, the composition can be easily cured.
• the photopolymerization initiator may be one capable of polymerizing a polymerizable compound by receiving light irradiation, and may be a photoradical polymerization initiator, a photocationic polymerization initiator, or a photoanion polymerization initiator. agents and the like.
• the photo-radical polymerization initiator is not particularly limited as long as it generates radicals upon irradiation with light, and conventionally known compounds can be used.
• the radical photopolymerization initiator acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds, oxime ester-based compounds, and the like can be preferably exemplified.
• acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2 -methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azidobenzal Acetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) -butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl
• benzyl-based compounds examples include benzyl and the like.
• benzophenone-based compounds examples include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide.
• thioxanthone-based compounds examples include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.
• oxime ester compound a compound represented by the following general formula (IV) is particularly exemplified because of its good sensitivity and heat resistance.
• R 71 and R 72 are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, group or a heterocyclic ring-containing group having 2 to 20 carbon atoms
• R 73 and R 74 each independently represent a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, -R 75 , -OR 76 , -SR 77 , -NR 78 R 79 , -COR 80 , -SOR 81 , —SO 2 R 82 or —CONR 83 R 84 , wherein R 73 and R 74 may combine with each other to form a ring, R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R
• oxime ester compounds examples include ethanone-1-[9-ethyl-6-(2-methylbenzoyl-9H-carbazol-3-yl]-1-(O-acetyloxime), 1-[9-ethyl- 6-benzoyl-9H-carbazol-3-yl-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1 -one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, ethanone-1-[9 -ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-
• an indole oxime ester compound having an indole structure can also be used.
• indole-based oxime ester compounds include oxime ester compounds represented by the following general formula (V) described in International Publication No. 2017/051680.
• R 201 and R 202 each independently represent -R 211 , -OR 211 , -COR 211 , -SR 211 , -CONR 212 R 213 or -CN;
• R 211 , R 212 and R 213 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom represents a heterocyclic ring-containing group of numbers 2 to 20,
• the hydrogen atoms of the groups represented by R 211 , R 212 and R 213 are further represented by -R 221 , -OR 221 , -COR 221 , -SR 221 , -NR 222 R 223 , -CONR 222 R 223 , -NR 222 OR 223 , —NCOR 222 OCOR 223 , —NR 222 COR 221
• R 211 , R 212 , R 213 , R 221 , R 222 , R 223 and R 224 may have branched side chains and may be cyclic alkyl
• R 203 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic ring-containing group having 2 to 20 carbon atoms.
• alkyl portion of the group represented by R 203 may have branched side chains and may be cyclic alkyl, and R 203 and R 207 and R 203 and R 208 together are each may form a ring
• R 203 1 to 20 carbon atoms represented by R 203 , R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 221 , R 222 , R 223 and R 224 in the general formula (V) , an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms, R Among the groups exemplified as 1, etc., those having a predetermined number of carbon atoms can be mentioned.
• radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(cyclopentadienyl)-bis[2,6-difluoro-3-(pyr-1 -yl)] and titanocene compounds such as titanium.
• radical polymerization initiators include Adeka Optomer N-1414, N-1717, N-1919, Adeka Arkles NCI-831, NCI-930 (manufactured by ADEKA), IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, and IRGACURE OXE. 01, IRGACURE OXE 02, OXE 03, OXE 04, IRGACURE784 (manufactured by BASF), TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (manufactured by Tronly), etc. be done.
• One or more of these photoradical polymerization initiators can be blended and used according to the desired performance.
• photocationic polymerization initiator one that generates an acid upon exposure to light can be used, and known photocationic polymerization initiators can be used.
• photocationic polymerization initiator include known compounds such as onium salt compounds, sulfone compounds, sulfonate ester compounds, quinonediazide compounds, sulfonimide compounds, and diazomethane compounds.
• photoanionic polymerization initiator those that generate a base upon exposure to light can be used, and known photoanionic polymerization initiators can be used.
• photoanionic polymerization initiator include acetophenone O-aroyloxime and nifedipine.
• Thermal polymerization initiator may be one capable of polymerizing a polymerizable compound by heating, and examples thereof include radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, and the like. .
• thermal radical polymerization initiator those that generate radicals by heating can be used, and known thermal radical polymerization initiators can be used.
• Preferred examples of the thermal radical polymerization initiator include azo compounds, peroxides and persulfates.
• azo compounds examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl isobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1' -azobis(1-acetoxy-1-phenylethane) and the like.
• peroxides examples include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butylperoxypivalate and di(4-t-butylcyclohexyl)peroxydicarbonate.
• persulfate examples include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.
• thermal cationic polymerization initiator those that generate cationic species or Lewis acids by heating can be used, and known thermal cationic polymerization initiators can be used.
• the thermal cationic polymerization initiator include salts such as sulfonium salts, thiophenium salts, thiolanium salts, benzylammonium, pyridinium salts and hydrazinium salts; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone reaction of the polyamines with various epoxy resins such as glycidyl ethers
• Polyvalent carboxylic acids oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3- Aliphatic dicarboxylic acids such as methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid and dimer acid; Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Tricarboxylic acids such as trimellitic acid, trimesic acid and trimers such as
• thermal cationic polymerization initiator such as Adeka Opton CP-77, Adeka Opton CP-66 (manufactured by ADEKA), CI-2639, CI-2624 (manufactured by Nippon Soda Co., Ltd.), and San-Aid SI-60L. , San-Aid SI-80L, San-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.), and the like.
• thermal anionic polymerization initiator those that generate a base by heat can be used, and known thermal anionic polymerization initiators can be used.
• the anionic polymerization initiator include aliphatic amine-based compounds, aromatic amine-based compounds, secondary or tertiary amine-based compounds, imidazole-based compounds, polymercaptan-based compounds, and boron trifluoride-amine complexes. , dicyandiamide, organic acid hydrazides, and the like can be used.
• the content of the polymerization initiator may be any one that can impart desired curability and photosensitivity, and is 0.1 parts by mass or more and 30 parts by mass in 100 parts by mass of solid content parts by mass or less, preferably 0.3 parts by mass or more and 10 parts by mass or less. This is because when the content is within the above range, the composition has good sensitivity and can be easily produced into a cured product.
• the content of the polymerization initiator may be any one that can impart desired curability and photosensitivity, and may be 0.001 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable compound. It is preferably 0.01 to 10 parts by mass, and preferably 0.1 to 5 parts by mass. This is because when the content is within the above range, the composition has good sensitivity and can be easily produced into a cured product.
• the colorant may be any one that can impart desired coloration to the cured product, and includes dyes and pigments.
• the dye compounds having absorption at 380 to 1200 nm can be used, and azo compounds, anthraquinone compounds, indigoid compounds, triarylmethane compounds, xanthene compounds, alizarin compounds, acridine compounds, stilbene compounds, thiazole compounds, naphthol compounds, Quinoline compounds, nitro compounds, indamine compounds, oxazine compounds, phthalocyanine compounds, cyanine compounds, diimmonium compounds, cyanoethenyl compounds, dicyanostyrene compounds, rhodamine compounds, perylene compounds, polyenenaphtlactam compounds, coumarin compounds, squarylium compounds, croconium compounds, spiropyran compounds , spirooxazine compounds, merocyanine compounds, oxonol compounds, styryl
• pigments inorganic pigments and organic pigments can be used, and nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, and isoindoline compounds.
• pigments can also be used as the inorganic pigments or organic pigments. 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109; Pigment Green Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.
• the content of the coloring agent can be 0.01 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the solid content of the composition.
• Solvent Any solvent can be used as long as it is capable of dissolving or dispersing the above components, 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 ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate , n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, ester solvents such as texanol; ethylene glycol monomethyl ether, cellosolve solvents such as ethylene glycol monoethyl ether; methanol, ethanol, iso- or n-propanol, Alcoholic solvents such as iso- or n-butanol, amyl alcohol, diacetone alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2
• the content of the solvent can be appropriately set according to the use of the composition, etc., but preferably the amount of components (solid content) other than the solvent in the composition is 1% by mass or more and 99% by mass or less. In particular, it is preferably 10% by mass or more and 90% by mass or less, and particularly preferably 30% by mass or more and 70% by mass or less. This is because when the content is within the above range, the composition is excellent in coatability and the like.
• chain transfer agent and sensitizer any one can be used as long as it can adjust the sensitivity and the like of the composition, and sulfur atom-containing compounds are generally used.
• sulfur atom-containing compounds are generally used.
• Surfactant those capable of improving the dispersion stability and coatability of the composition can be used.
• Surfactants anionic surfactants such as higher fatty acid alkali salts, alkylsulfonates and alkylsulfates, cationic surfactants such as higher amine halides and quaternary ammonium salts, polyethylene glycol alkyl ethers, polyethylene Surfactants such as nonionic surfactants such as glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants and silicone surfactants can be used, and these may be used in combination.
• the silane coupling agent is a silane compound having a reactive group that chemically bonds with an inorganic material such as glass and a reactive group that chemically bonds with an organic material such as a synthetic resin. A material capable of improving adhesion and the like can be used.
• the silane coupling agent include silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. Among them, silane coupling agents having an isocyanate group, a methacryloyl group, an epoxy group, such as KBE-9007, KBM-502, and KBE-403, are preferred. used for
• Melamine compound As the melamine compound, those capable of improving curability can be used, and nitrogen such as (poly)methylolmelamine, (poly)methylolglycoluril, (poly)methylolbenzoguanamine, (poly)methylolurea, etc.
• nitrogen such as (poly)methylolmelamine, (poly)methylolglycoluril, (poly)methylolbenzoguanamine, (poly)methylolurea, etc.
• Compounds in which all or part (at least two) of the active methylol groups (CH 2 OH groups) in the compound are alkyl-etherified.
• the alkyl group constituting the alkyl ether includes a methyl group, an ethyl group and a butyl group, which may be the same or different.
• methylol groups that are not alkyl-etherified may be self-condensed within one molecule, or may be condensed between two molecules to form an oligomer component.
• hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used.
• alkyl-etherified melamine such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferred.
• Acid Catalyst and Base Catalyst are capable of promoting elimination of the protective group R9 of the phenolic hydroxyl group of compound A.
• the composition contains an acid catalyst or a base catalyst, it becomes possible to eliminate the protective group R9 in the compound A at a lower temperature than when the composition does not contain an acid catalyst or a base catalyst. .
• the acid catalyst examples include inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid; organic acids such as formic acid, acetic acid, oxalic acid, citric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and monoisopropyl phosphate. mentioned.
• the base catalyst examples include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia; amine compounds (organic bases) such as trimethylamine, triethylamine, monoethanolamine, and diethanolamine.
• the content of the acid catalyst and the base catalyst is appropriately set according to the type of each and the desired desorption temperature, etc. parts or more and 10 parts by mass or less.
• composition further includes, as the other components, p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, a thermal polymerization inhibitor such as phenothiazine; a plasticizer; an adhesion promoter; Filler; antifoaming agent; leveling agent; surface conditioner; Additives such as ultraviolet absorbers; dispersing aids; aggregation inhibitors; catalysts; effect accelerators; cross-linking agents;
• the total content of the other components may be 30 parts by mass or less per 100 parts by mass of the solid content of the composition.
• the composition contains a phenolic antioxidant and an ultraviolet absorber in addition to the compound A and the compound B to the extent that a cured product having desired durability can be obtained and the cured product can be easily produced. Although it may be present, it is preferably not substantially included.
• substantially free means that it is 1 part by mass or less in 100 parts by mass of the solid content of the composition, preferably 0.01 part by mass or less, and 0.005 part by mass or less. is more preferably 0.001 parts by mass or less, and particularly preferably 0.0001 parts by mass or less.
• the content of the phenolic antioxidant and the ultraviolet absorber is preferably 1 part by mass or less with respect to a total of 100 parts by mass of the compound A and the compound B, and may be 0.01 part by mass or less. It is more preferably 0.005 parts by mass or less, particularly preferably 0.001 parts by mass or less, and most preferably 0.0001 parts by mass or less. This is because it becomes possible to obtain a cured product having excellent durability.
• Examples of the ultraviolet absorber include ultraviolet absorbers having a phenolic hydroxyl group. Specifically, 2-hydroxybenzophenones, 2-(2′-hydroxyphenyl)benzotriazoles, benzoates, triaryltriazines, etc. described in JP-A-2017-008221, JP-A-2002-97224 benzotriazole-based UV absorbers, benzophenone-based UV absorbers, and the like described in .
• phenolic antioxidant examples include those commonly used as antioxidants having a phenolic hydroxyl group. Specifically, JP-A-6-179798, JP-A-11-71355, phenol-based antioxidants described in JP-A-2002-97224, etc., alkyl substitution described in JP-A-7-109380 Examples include phenolic antioxidants.
• the viscosity of the composition can be 200 mPa ⁇ s or less, and can be 1 mPa ⁇ s or more and 200 mPa ⁇ s or less, from the viewpoint of having coatability. This is because the composition is excellent in coatability.
• the viscosity refers to a value measured at 25° C. using a rotational viscometer (such as Physica MCR301 manufactured by Anton Paar) according to JIS Z 8803:2011.
• the method for producing the composition may be any method as long as it is possible to blend the respective components in the desired content, and may be a method of adding and mixing the respective components at the same time, while sequentially adding the respective components. A method of mixing may also be used.
• the composition may be a mixture of compound A and compound B, and may further contain a solvent if necessary.
• the total content of compound A and compound B varies depending on the content of the solvent and the like, but it is preferably 0.01 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition, It is more preferably 0.05 parts by mass or more and 15 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 10 parts by mass or less.
• the compound A and the compound B can be stably dispersed in the composition when the content is as described above.
• a composition containing compound A and compound B in such amounts can produce a cured product having excellent durability, and has good sensitivity, which facilitates the production of a cured product.
• the composition may contain the compound A, the compound B and the resin component, and may further contain other components as necessary.
• compositions include thermosetting paints, photocurable paints or varnishes, thermosetting adhesives, photocurable adhesives, printed circuit boards, color televisions, PC monitors, personal digital assistants, digital cameras and the like.
• Color filters for liquid crystal display panels color filters for CCD image sensors, photo spacers, black column spacers, electrode materials for plasma display panels, touch panels, touch sensors, powder coatings, printing inks, printing plates, adhesives, dental Compositions, resins for stereolithography, gel coats, photoresists for electronics, electroplating resists, etching resists, both liquid and dry films, solder resists, for making color filters for various display applications or plasma displays.
• the application is not limited to applications that require durability when used as a product, and can be suitably used for members that are exposed to ultraviolet irradiation during the manufacturing process.
• the member that is irradiated with ultraviolet rays or the like in the manufacturing process include members that are irradiated with ultraviolet rays or the like in order to improve surface wettability, adhesion, or the like.
• Examples of members that require improved wettability, improved adhesion, and the like include members that are laminated with other members. Color filters, photo spacers, brightness enhancement plates, light guide plates, TFT substrates, alignment films, liquid crystal layers, insulating films, acoustic elements such as speakers, and imaging devices Examples include members that require surface modification and prevention of member deterioration during the manufacturing process, such as lenses, keypads, and magnetic heads for HDDs.
• Examples of members that require surface modification and prevention of member deterioration during the manufacturing process include members that are laminated with other members via an adhesive, and members that are coated with other members with paint or the like.
• it can be used as a structural member for various purposes such as transportation equipment such as interior and exterior members of automobiles and aircraft, home appliances such as refrigerators and washing machines, and housing building materials.
• the exposed base material may be subjected to ultraviolet irradiation or the like in order to modify the surface of the exposed base material.
• ultraviolet irradiation or the like it can also be preferably used for members that are used together with members that require surface modification or the like in the manufacturing process. Examples of the applications include plastic films, glass, silicon wafers, various engineering plastics, optical lenses, metal surfaces, plating, ceramics, and members used together with members requiring surface cleaning and surface modification such as molds. be done.
• compound A and compound B are preferably used in the production of thin film members from the viewpoint that their addition amount can be easily increased due to their excellent dispersion stability.
• the thin film member can be a member having a film thickness of 100 ⁇ m or less, preferably 50 ⁇ m or less, particularly preferably 20 ⁇ m or less.
• the cured product of the present invention is characterized by being a cured product of the above composition containing a polymerizable compound. More specifically, the cured product of the present invention is a cured product of a composition containing the compound A, the compound B and the polymerizable compound. Since the above-described composition is used, the cured product has good sensitivity, is easy to produce, and has excellent durability.
• composition used for the cured product contains the compound A, the compound B and the polymerizable compound, but may contain components other than the compound A, the compound B and the polymerizable compound. .
• it may contain a resin component other than the polymerizable compound, other components, and the like. The contents of each of these components are as described in the section "A. Composition".
• the cured product may be a cured product of the composition, and the protective group (that is, R 9 ) in the compound A contained in the cured product may or may not be eliminated. is preferably eliminated. This is because the cured product has excellent durability.
• the cured product usually contains at least a compound in which the protective group is eliminated from the compound A.
• the cured product can contain a compound derived from the protecting group that has been eliminated from the compound A.
• the cured product usually contains an unreacted polymerizable compound.
• the residual rate of the polymerizable compound contained in the cured product is appropriately set according to the application of the cured product, etc., but is preferably 10 parts by mass or less with respect to 100 parts by mass of the cured product. It is more preferably 1 part by mass or less.
• the cured product may be substantially solvent-free.
• the content of the solvent contained in the cured product is preferably 1 part by mass or less, and preferably 0.5 part by mass or less per 100 parts by mass of the cured product.
• the elastic modulus of the cured product is usually higher than that of the composition, and can be 10 ⁇ 3 MPa or more, and can be 10 MPa or more. This is because the cured product can stably retain the compound A, the compound B, and the like with the above elastic modulus.
• the upper limit of the elastic modulus can be appropriately set depending on the intended use of the cured product, and can be, for example, 10 6 MPa or less.
• the elastic modulus refers to the compression elastic modulus, and is a value measured at 23° C. according to JIS K 7181. For example, a cubic test piece with a side length of 6 mm is prepared or cut out as a measurement sample, and measurement can be performed at a test speed of 1 ⁇ 0.2 mm/min according to JIS K 7181.
• the shape of the cured product in plan view can be appropriately set according to the intended use of the cured product, and can be, for example, a pattern such as a dot shape or a line shape.
• the thickness of the cured product can be appropriately set according to the use of the cured product, and the compound A and the compound B have excellent dispersion stability, so that the amount added can be easily increased.
• the method for producing the cured product is not particularly limited as long as it is a method capable of forming the cured product of the composition into a desired shape.
• a production method the production method described in the section "C. Production method of cured product” described later can be mentioned, so the explanation here is omitted.
• the method for producing a cured product of the present invention is characterized by having a step of forming a cured product of the composition described above. More specifically, the method for producing a cured product of the present invention has a step of forming a cured product of a composition containing the compound A, the compound B and the polymerizable compound.
• the production method facilitates the production of a cured product by using the composition described above. Moreover, a cured product having excellent durability can be easily obtained by performing a step of removing the protecting group R9 contained in the compound A after the above step.
• Step of Forming Cured Product is a step of molding and curing the composition described above.
• the method for forming the cured product of the composition may be any method as long as it is capable of forming a cured product having a desired shape, and varies depending on the components contained in the composition.
• the composition contains a photopolymerization initiator as a polymerization initiator together with a polymerizable compound, the composition formed as a coating film on a substrate is irradiated with light to polymerize. and a method of polymerizing a chemical compound.
• the wavelength of the light to be irradiated can be 300 nm to 450 nm, depending on the type of photopolymerization initiator.
• Light sources include ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, and the like. Laser light may also be used, and for example, one containing light with a wavelength of 340 to 430 nm can be used.
• a light source for laser light a laser that emits light in the visible to infrared region, such as an argon ion laser, a helium neon laser, a YAG laser, and a semiconductor laser, can be used. When these laser beams are used, the composition may contain a sensitizing dye that absorbs light in the visible to infrared region.
• the composition contains a thermal polymerization initiator as a polymerization initiator together with a polymerizable compound
• the composition formed as a coating film on a substrate is subjected to heat treatment to polymerize. and a method of polymerizing a chemical compound.
• the heating temperature is preferably a temperature that can suppress the elimination of the protective group from compound A, and can be 60°C or higher, preferably 100°C or higher and 300°C or lower.
• the heating temperature can be the temperature of the coating surface of the composition.
• the heating time can be about 10 seconds to 3 hours.
• the step of forming the cured product may include only one method, or may include two or more methods.
• composition used in the step of forming the cured product contains the compound A, the compound B and the polymerizable compound, and contains components other than the compound A, the compound B and the polymerizable compound. There may be. For example, it may contain a resin component other than the polymerizable compound, other components, and the like. The contents of each of these components are as described in the section "A. Composition”.
• Step of Removing Protecting Group The production method may include a step of removing the protecting group R 9 contained in the compound A after the step of forming the cured product. By including such steps, a cured product having excellent durability can be easily obtained.
• the method for removing the protecting group R 9 contained in the compound A may be any method as long as the protecting group can be stably removed, and examples thereof include a method of heat-treating the cured product.
• the heating temperature may be any temperature at which the protecting group R9 is eliminated.
• the heating temperature can be set to the desorption temperature observed when the protecting group R9 alone is used, or lower.
• the heating temperature can be 50°C or higher and 250°C or lower, preferably 60°C or higher and 200°C or lower, and particularly preferably 80°C or higher and 200°C or lower. This is because the deterioration of the resin component and the like, the deterioration of the substrate supporting the cured product, and the like can be suppressed at the heating temperature.
• the temperature of the cured product can be the temperature of the surface of the cured product.
• the production method may optionally include other steps in addition to the step of forming the cured product and the step of removing the protective group.
• Examples of the other steps include a step of applying the composition onto a substrate.
• known methods such as spin coater, roll coater, bar coater, die coater, curtain coater, various types of printing, and dipping can be used.
• the base material can be appropriately selected according to the intended use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, and the like.
• the cured product may be peeled off from the base material, or may be transferred from the base material to another adherend.
• the present invention includes the following aspects.
• R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, a group, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic ring-containing group having 2 to 20 carbon atoms or -O-R 9 , wherein at least one of R 1 and R 2 is -O-R 9 , R 3 and R 4 each independently represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 4 carbon atoms.
• R 9 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or 2 to 2 carbon atoms.
• the methylene group in the alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group and trialkylsilyl group is a carbon-carbon double bond, -O-, -S-, -CO-, -O -CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO—S—, —CO—NH—, —NH—CO—, —NH—CO—O—, —NR′—, >P ⁇ O, —S—S— or —SO 2 — or combinations thereof 2 optionally substituted with a valent group, R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, The alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group
• R 1 ' and R 2 ' are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkyl group having 1 to 40 carbon atoms, an alkyl group having 1 to 40 carbon atoms, , an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic ring-containing group having 2 to 20 carbon atoms or —OR 9 , wherein at least one of R 1 ' and R 2 ' is —OR is 9 ; R 5 and R 6 each independently represent a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to represents a 20 arylalkyl group or a heterocyclic ring-containing group having 2 to 20 carbon atoms, R
• the methylene group in the alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group and trialkylsilyl group is a carbon-carbon double bond, -O-, -S-, -CO-, -O -CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO—S—, —CO—NH—, —NH—CO—, —NH—CO—O—, —NR′—, >P ⁇ O, —S—S— or —SO 2 — or combinations thereof 2 optionally substituted with a valent group, R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, The alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group
• R 1 ′′ and R 2 ′′ are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkyl group having 1 to 40 carbon atoms, an alkyl group having 6 to 20 carbon atoms, aryl group, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic ring-containing group having 2 to 20 carbon atoms or —OR 9 , wherein at least one of R 1 ′′ and R 2 ′′ is —OR is 9 ; R 7 and R 8 each independently represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 7 to 20 carbon atoms.
• R 9 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or 2 to 2 carbon atoms.
• the methylene group in the alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group and trialkylsilyl group is a carbon-carbon double bond, -O-, -S-, -CO-, -O -CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO—S—, —CO—NH—, —NH—CO—, —NH—CO—O—, —NR′—, >P ⁇ O, —S—S— or —SO 2 — or combinations thereof 2 optionally substituted with a valent group, R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, The alkyl group, aryl group, arylalkyl group, heterocyclic ring-containing group, alkenyl group
• R 95 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms
• R 96 represents a residue or a carbonate group obtained by removing a hydrogen atom from the carboxy group of a monovalent to trivalent organic carboxylic acid
• n1 represents an integer of 1-3. However, n1 is 2 when R96 is a carbonate group.
• R 97 represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms
• R 98 represents an alkenylcarbonyl group.
• composition according to any one of [1] to [4], comprising a polymerizable compound comprising a polymerizable compound.
• a method for producing a cured product comprising the step of forming a cured product of the composition according to [5].
• the present invention is not limited to the above embodiments.
• the above embodiment is an example, and any device that has substantially the same configuration as the technical idea described in the claims of the present invention and achieves the same effect is the present invention. It is included in the technical scope of the invention.
• the phenol compound used was a compound in which two —COO-tert-butyl groups in A1-1 below were substituted with hydrogen atoms.
• Examples 1 to 9 and Comparative Examples 1 to 8 Compound A, a hindered amine compound, an ultraviolet absorber, a polymerizable compound having an acid value, a polymerizable compound having no acid value, a photopolymerization initiator, a colorant dispersant, a dye, and a silane cup according to the formulations shown in Table 2 below.
• a composition was obtained by blending a ring agent, a leveling agent, and a solvent.
• compound A, compound B (or ultraviolet absorber) and solvent were mixed to prepare composition a.
• compound A and compound B (or ultraviolet absorber) was adjusted to 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of composition a. Thereafter, components other than these were further blended to obtain a composition having the composition shown in Table 2. In addition, the following materials were used for each component. In addition, the compounding quantity in a table
• A'-1 compound represented by the following formula (A'-1)
• A'-2 compound represented by the following formula (A'-2)
• A'-3 represented by the following formula (A'-3)
• A'-4 a compound represented by the following formula (A'-4)
• C-1 Radically polymerizable compound (Lipoxy SPC-1000 manufactured by Showa Denko Co., Ltd., solid content 29% by mass PGMEA solution)
• C-2 Radically polymerizable compound (Showa Denko Lipoxy SPC-3000, solid content 42.4% by mass PGMEA solution)
• E-1 A compound represented by the following formula (E1) (oxime ester photoradical polymerization initiator)
• F-1 NPCF-52417 (manufactured by Nippon Pigment Co., Ltd., PGMEA solution with a solid content of 21.2% by mass)
• F-2 NPCF-60001 (manufactured by Nippon Pigment Co., Ltd., PGMEA solution with a solid content of 19.0% by mass)
• F-3 a compound represented by the following formula (F3)
• compositions prepared in Examples and Comparative Examples were evaluated. Table 2 shows the results.
• each composition of Examples and Comparative Examples was spin-coated on a glass substrate (500 rpm, 7 seconds) to form a coating film having a thickness of 2.2 ⁇ m after drying (after pre-baking).
• pre-baking was performed at 90° C. for 120 seconds, and further exposure was performed using a high-pressure mercury lamp as a light source (accumulated light quantity: 150 mJ/cm 2 ) to obtain a cured product.
• post-baking was performed at 230° C. for 30 minutes to obtain an evaluation sample.
• the resulting evaluation sample was subjected to a light resistance test for 160 hours using SUNTEST XXL+ manufactured by ATLAS.
• the Eab * values before and after the test were obtained using a color difference meter, the Eab* value change ( ⁇ Eab * ) before and after the test was calculated, and the light resistance was evaluated according to the following criteria.
• the results are shown in Table 2 below.
• a smaller ⁇ Eab * that is, a light resistance evaluation of “A”, indicates that the cured product has excellent light resistance.
• Photolithography sensitivity
• a coating film was formed in the same manner as in “1. 300 ⁇ m, exposure amount 40 mJ/cm 2 ). After development using a 0.04% by mass KOH aqueous solution as a developer, the film was thoroughly washed with water and post-baked at 230° C. for 30 minutes using a clean oven to fix the pattern. The obtained pattern was observed with an optical microscope, and the line width of the portion corresponding to the mask opening was measured and evaluated according to the following criteria. The results are shown in Table 2 below. If the difference with respect to the set line width is smaller, that is, if the photolithographic property is "A", it can be judged that the line width is controlled and the sensitivity is good.
• A The line width is within the range of ⁇ 2.5 ⁇ m based on the mask opening of 30 ⁇ m.
• B The line width exceeds ⁇ 2.5 ⁇ m based on the mask opening of 30 ⁇ m.
• - Deposits were present in the composition and could not be evaluated.
• compositions of Examples had better results in both light resistance and photolithography than the compositions of Comparative Examples, and were superior in durability and sensitivity.
• compositions of Examples could be sufficiently cured with inhibition of curing being suppressed, and it was found that the production of cured products was easy.

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