WO2020032131A1 - Composé, générateur de thiol, composition, produit durci, et procédé de production de produit durci - Google Patents

Composé, générateur de thiol, composition, produit durci, et procédé de production de produit durci Download PDF

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WO2020032131A1
WO2020032131A1 PCT/JP2019/031213 JP2019031213W WO2020032131A1 WO 2020032131 A1 WO2020032131 A1 WO 2020032131A1 JP 2019031213 W JP2019031213 W JP 2019031213W WO 2020032131 A1 WO2020032131 A1 WO 2020032131A1
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group
compound
carbon atoms
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composition
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PCT/JP2019/031213
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English (en)
Japanese (ja)
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直美 佐藤
大樹 三原
良智 竹内
和司 松川
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株式会社Adeka
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Priority to KR1020207035593A priority Critical patent/KR20210042046A/ko
Priority to CN201980046590.2A priority patent/CN112424165A/zh
Priority to JP2020535850A priority patent/JP7422076B2/ja
Publication of WO2020032131A1 publication Critical patent/WO2020032131A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C07C329/02—Monothiocarbonic acids; Derivatives thereof
    • C07C329/04—Esters of monothiocarbonic acids
    • C07C329/06—Esters of monothiocarbonic acids having sulfur atoms of thiocarbonic groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/02—Monothiocarbamic acids; Derivatives thereof
    • C07C333/08—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/34—Cyanuric or isocyanuric esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

Definitions

  • the present invention relates to a compound capable of forming a composition having excellent patterning accuracy and heat resistance.
  • the thiol compound can cause a reaction such as a thiol-ene reaction (also called an ene-thiol reaction) with an acrylic monomer or the like. Further, such a polymerization reaction proceeds even in the absence of a polymerization initiator. Therefore, by adding the thiol compound together with the polymerization initiator to the acrylic monomer, the polymerization reaction of the acrylic monomer or the like by the polymerization initiator and the reaction of the acrylic monomer or the like by the thiol compound can be simultaneously performed. Utilizing such properties, thiol compounds are used for improving the sensitivity of photocurable compositions and the like (for example, Patent Document 1).
  • a coating film of the photocurable composition is exposed in a pattern, a non-cured coating film is removed with a developer, and then a heat treatment is performed.
  • a method of performing (post bake) is known.
  • a thiol compound as described in Patent Document 1 is added to a photocurable composition to form a patterned cured product, a patterned cured product excellent in heat resistance such as little shrinkage during the heat treatment is obtained. be able to.
  • the addition of the thiol compound lowers the patterning accuracy.
  • the present inventors have studied an increase in the amount of a polymerization initiator to improve heat resistance and the like. However, as in the case of adding a thiol compound, the heat resistance can be improved, but there is a problem that the patterning accuracy is reduced.
  • the present invention has been made in view of the above problems, and has as its main object to provide a compound capable of forming a composition having excellent patterning accuracy and heat resistance.
  • the inventors of the present invention have conducted intensive studies to solve the above-described problems, and as a result, until the completion of patterning, the progress of a reaction by a thiol compound such as a thiol-ene reaction is suppressed, and the above-described reaction can proceed after the completion of patterning. It has been found that the use of the compound makes it possible to form a composition excellent in both patterning accuracy and heat resistance. The present inventors have completed the present invention based on these findings.
  • the present invention is a compound represented by the following general formula (A) (hereinafter, also referred to as “compound A”).
  • R 1 is a monovalent aliphatic group having 1 to 40 carbon atoms, a monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, a monovalent having 2 to 35 carbon atoms, Represents a heterocyclic-containing group or a monovalent silyl group having 0 to 40 carbon atoms
  • X represents an aliphatic group having 1 to 40 carbon atoms, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, or a heterocyclic-containing group having 2 to 35 carbon atoms having the same valence as n.
  • One or more of methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group-containing group, and silyl group are -O-, -S-, -CO-, -O-CO- , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- Is it replaced by a group selected from NH—CO—, —NH—CO—O—, —O—CO—NH—, —NR′—, —SS— or —SO 2 —? Or an oxygen atom may be replaced by a group combining these groups under non-adjacent conditions, n represents an integer of 2 or more and 10 or less.
  • the compound A can form a composition excellent in patterning accuracy and heat resistance.
  • the compound A is preferably a compound represented by the following formula (A1), (A2), (A3), (A4), (A5) or (A6). This is because the compound A becomes a compound capable of forming a composition excellent in patterning accuracy and heat resistance by being a compound having the above structure, and in particular, a composition excellent in heat resistance can be formed.
  • R 11 and R 12 each independently represent the following general formula (101); L 11 and L 12 represent an alkylene group having 1 to 10 carbon atoms, a1 represents an integer of 1 to 20, R 21 , R 22 and R 23 each independently represent the following general formula (101) or (102); Any two or more of R 21 , R 22 and R 23 are represented by the following general formula (101), L 21 , L 22 and L 23 represent an alkylene group having 1 to 10 carbon atoms, R 24 represents a hydrogen atom or a monovalent aliphatic group having 1 to 40 carbon atoms, R 31 , R 32 , R 33 and R 34 each independently represent the following formula (101) or (102); Any two or more of R 31 , R 32 , R 33 and R 34 are represented by the following general formula (101), L 31 , L 32 , L 33 and L 34 represent an alkylene group having 1 to 10 carbon atoms, R 41 , R 42 , R 43 , R 44 , R 45 and R 46 each independently represent the following formula (10
  • R 1 is a monovalent aliphatic group having 1 to 40 carbon atoms, a monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, a monovalent having 2 to 35 carbon atoms, Represents a heterocyclic-containing group or a monovalent silyl group having 0 to 40 carbon atoms, * Represents a bond,
  • One or more of methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group-containing group, and silyl group are -O-, -S-, -CO-, -O-CO- , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- May be replaced by a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -
  • R 21 , R 22, and R 23 in the general formula (A2) are each independently the general formula (101), and R 31 , R in the general formula (A3)
  • All of R 32 , R 33 and R 34 are each independently the general formula (101), and R 41 , R 42 , R 43 , R 44 , R 45 and R 46 in the general formula (A4)
  • All are each independently the general formula (101), and all of R 51 , R 52 and R 53 in the general formula (A5) are each independently the general formula (101);
  • the compound A is preferably a compound represented by the general formula (A4) or (A6). This is because the compound A can form a composition excellent in patterning accuracy and heat resistance.
  • R 1 is a monovalent aliphatic group having 1 to 40 carbon atoms, wherein —CO—O— or —CO—NR— is substituted for the methylene group at the sulfur atom side, Is preferably an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms. This is because, when R 1 is the above-described group, the compound A can form a composition excellent in patterning accuracy and heat resistance.
  • the present invention is a thiol generator containing the above compound.
  • the thiol generator can form a composition excellent in patterning accuracy and heat resistance.
  • the present invention is a composition comprising a compound represented by the following general formula (A) and a polymerizable component having thiol reactivity (hereinafter sometimes referred to as polymerizable component B).
  • R 1 is a monovalent aliphatic group having 1 to 40 carbon atoms, a monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, a monovalent having 2 to 35 carbon atoms, Represents a heterocyclic-containing group or a monovalent silyl group having 0 to 40 carbon atoms
  • X represents an aliphatic group having 1 to 40 carbon atoms, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, or a heterocyclic-containing group having 2 to 35 carbon atoms having the same valence as n.
  • One or more of methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group-containing group, and silyl group are -O-, -S-, -CO-, -O-CO- , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- Is it replaced by a group selected from NH—CO—, —NH—CO—O—, —O—CO—NH—, —NR′—, —SS— or —SO 2 —? Or an oxygen atom may be replaced by a group combining these groups under non-adjacent conditions, n represents an integer of 2 or more and 10 or less.
  • the composition since the composition contains the compound A, the composition has excellent patterning accuracy and heat resistance.
  • the thiol-reactive polymerizable component preferably contains a radical polymerizable compound. This is because the composition has an excellent curing rate. Further, this is because crosslinking using the compound A is easy.
  • the present invention is a cured product of the above composition.
  • the cured product contains the compound A, the cured product is excellent in patterning accuracy and heat resistance.
  • the present invention provides a method for producing a cured product having a step of crosslinking the thiol-reactive polymerizable components with the compound represented by the general formula (A).
  • a cured product having excellent heat resistance can be produced by crosslinking the polymerizable component B with the compound A.
  • a compound capable of forming a composition having excellent patterning accuracy and heat resistance can be provided.
  • 4 is an example of an optical microscope observation image when wrinkles occur in a pattern.
  • 5 is an example of an SEM observation image when wrinkles are generated in a pattern.
  • 5 is an example of an SEM observation image when wrinkles are not generated in a pattern.
  • the present invention relates to a compound, a thiol generator using the same, a composition, a cured product, and a method for producing a cured product.
  • the compound, the thiol generator, the composition, the cured product, and the method for producing the cured product of the present invention will be described in detail.
  • the compound of the present invention is a compound represented by the following general formula (A) (hereinafter, also referred to as “compound A”).
  • R 1 is a monovalent aliphatic group having 1 to 40 carbon atoms, a monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, a monovalent having 2 to 35 carbon atoms, Represents a heterocyclic-containing group or a monovalent silyl group having 0 to 40 carbon atoms
  • X represents an aliphatic group having 1 to 40 carbon atoms, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, or a heterocyclic-containing group having 2 to 35 carbon atoms having the same valence as n.
  • One or more of methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group-containing group, and silyl group are -O-, -S-, -CO-, -O-CO- , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- Is it replaced by a group selected from NH—CO—, —NH—CO—O—, —O—CO—NH—, —NR′—, —SS— or —SO 2 —? Or an oxygen atom may be replaced by a group combining these groups under non-adjacent conditions, n represents an integer of 2 or more and 10 or less.
  • the compound A can form a composition excellent in patterning accuracy and heat resistance.
  • the reason that the compound A can form a composition having excellent patterning accuracy and heat resistance by having the above structure is presumed as follows.
  • the compound A since the thiol group is protected by R 1, until after the patterning completion, for example, until after the execution of step and development step of polymerizing the polymerizable component B together in the composition, the polymerizable component B
  • the progress of the cross-linking reaction for cross-linking each other can be suppressed.
  • the compound A can suppress the progress of curing of the composition beyond a desired pattern during the polymerization step or during the development step, and have excellent patterning accuracy.
  • the compound A is capable of cross-linking the polymerizable components B by releasing the protective group R 1 and generating two or more thiol groups by, for example, heat treatment or the like.
  • the crosslinking density of the cured product is improved by the progress of the crosslinking reaction.
  • a cured product that has less shrinkage during heat treatment such as post-baking that is, a cured product having excellent heat resistance.
  • the compound A can form a composition excellent in patterning accuracy and heat resistance.
  • the crosslinking reaction proceeds even in the absence of a polymerization initiator, the crosslinking reaction can proceed not only on the surface of the cured product but also on a deep portion deep in the thickness direction from the surface of the cured product.
  • the compound A facilitates formation of a patterned cured product having a small line width, and has an excellent exposure margin in which the line width does not change due to variations in exposure time.
  • the composition can be easily obtained.
  • the compound A is used for the formation of a member requiring a heat treatment as a curing treatment, whereby the formation of a member having a large film thickness can be achieved due to the effect that a cured product having excellent heat resistance can be obtained. It will be easier.
  • a pattern having a fine and high aspect ratio can be obtained.
  • the formation of a cured product becomes easy.
  • a cured product having a high aspect ratio is formed, it is easy to reduce the thickness of the coating film of the composition, and for example, it is possible to exhibit the effect that the cost can be easily reduced.
  • a method of forming a cured product having a high aspect ratio without using the compound A a method of reducing the amount of exposure can be considered.
  • the compound A when the compound A is used, the effect of easily forming a pattern-shaped cured product having a high aspect ratio makes it unnecessary to reduce the exposure dose, and the pattern-shaped pattern having a high development margin is not required.
  • a cured product can be easily obtained. From the above, the compound A is excellent in patterning accuracy and heat resistance by being used in a composition for forming a pattern-shaped cured product, and has a small line width, and a patterned cured product having a high aspect ratio. Can be obtained.
  • the compound A is excellent in exposure margin and development margin at the time of formation of a patterned cured product, and a composition excellent in process passability can be obtained. Further, by adding the compound A to the curable composition, it is possible to improve the resistance of the cured product to an alkali developer during development after curing treatment by exposure. Therefore, the composition containing the above compound can stably form a patterned cured product against variations in the alkaline development time. Thus, the development margin in the development process can be excellent, and from this result, it is easy to achieve excellent patterning accuracy.
  • the compound A exhibits excellent patterning accuracy exhibited in the polymerization step, excellent development margin exhibited in the development step, and is exhibited during the execution of a heat treatment step such as a post-bake step.
  • excellent heat resistance can be exhibited in a well-balanced manner, and as a whole, patterning accuracy and heat resistance are excellent.
  • the compound A is particularly suitable, for example, for a curable composition for forming a patterned cured product.
  • the monovalent aliphatic group having 1 to 40 carbon atoms represented by R 1 may be any group that does not contain an aromatic hydrocarbon ring and a heterocyclic ring, and is, for example, an alkyl group having 1 to 40 carbon atoms.
  • an alkenyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, a cycloalkylalkyl group having 4 to 40 carbon atoms, and one or more hydrogen atoms of these groups are described below. And the like.
  • the aliphatic group refers to a group obtained by removing any atom from an aliphatic compound.
  • alkyl group having 1 to 40 carbon atoms examples include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-pentyl, tert-pentyl, 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.
  • alkenyl group having 2 to 40 carbon atoms examples include vinyl, ethylene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, and 5-hexenyl , 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl and 4,8,12-tetradecatrienylallyl.
  • cycloalkyl group having 3 to 40 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 40 carbon atoms.
  • examples of the cycloalkyl group having 3 to 40 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo [1. 1.1] pentanyl and the like.
  • the cycloalkylalkyl group having 4 to 40 carbon atoms means a group having 4 to 40 carbon atoms in which a hydrogen atom of the alkyl group is substituted by a cycloalkyl group.
  • Examples of the cycloalkylalkyl group having 4 to 40 carbon atoms include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl , 2-cyclodecylethyl, 3-adamantylpropyl, decahydronaphthylpropyl and the like.
  • the monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms represented by R 1 may be any as long as it contains an aromatic hydrocarbon ring, and is, for example, an aryl having 6 to 35 carbon atoms. Groups, arylalkyl groups having 7 to 35 carbon atoms, and groups in which one or more hydrogen atoms of these groups are substituted with a substituent described below. Further, the aromatic hydrocarbon ring-containing group usually does not contain a heterocyclic group.
  • the aryl group having 6 to 35 carbon atoms includes phenyl, naphthyl, anthracenyl and the like.
  • the arylalkyl group having 7 to 35 carbon atoms includes benzyl, fluorenyl, indenyl, 9-fluorenylmethyl group and the like.
  • the monovalent heterocyclic group having 2 to 35 carbon atoms represented by R 1 may be any group containing a heterocyclic ring, such as 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-pyrrolidinone-1-yl , 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidin-3-yl
  • the monovalent silyl group having 0 to 40 carbon atoms represented by R 1 may be any one containing a silicon atom, and a hydrogen atom is an unsubstituted silyl group, and a hydrogen atom is substituted with another substituent. Substituted silyl groups and groups in which one or more of the hydrogen atoms of these groups are substituted with a substituent described below.
  • Examples of the substituted silyl group include a silyl group such as a monoalkylsilyl group, a monoarylsilyl group, a dialkylsilyl group, a diarylsilyl group, a trialkylsilyl group, a triarylsilyl group, a monoalkyldiarylsilyl group, and a dialkylmonoarylsilyl group.
  • a silyl group such as a monoalkylsilyl group, a monoarylsilyl group, a dialkylsilyl group, a diarylsilyl group, a trialkylsilyl group, a triarylsilyl group, a monoalkyldiarylsilyl group, and a dialkylmonoarylsilyl group.
  • Examples of the monoalkylsilyl group include a monomethylsilyl group, a monoethylsilyl group, a monobutylsilyl group, a monoisopropylsilyl group, a monodecanesilyl, a monoicosansilyl group, and a monotriacontansilyl group.
  • Examples of the monoarylsilyl group include a monophenylsilyl group, a monotolylsilyl group, a mononaphthylsilyl group, and a monoanthrylsilyl group.
  • dialkylsilyl group examples include a dimethylsilyl group, a diethylsilyl group, a dimethylethylsilyl group, a diisopropylsilyl group, a dibutylsilyl group, a dioctylsilyl group, and a didecanesilyl group.
  • diarylsilyl group examples include a diphenylsilyl group and a ditolylsilyl group.
  • Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a dimethylethylsilyl group, a triisopropylsilyl group, a tributylsilyl group, and a trioctylsilyl group.
  • Examples of the triarylsilyl group include a triphenylsilyl group and a tolylsilyl group.
  • Examples of the monoalkyldiarylsilyl group include a methyldiphenylsilyl group and an ethyldiphenylsilyl group.
  • Examples of the dialkylmonoarylsilyl group include a dimethylphenylsilyl group and a methylethylphenyl group.
  • One or more of methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group-containing group and silyl group in R 1 are -O-, -S-, -CO-, -O -CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH -, -NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -SS- or -SO 2- Or a group obtained by combining these groups under the condition that oxygen atoms are not adjacent to each other.
  • R 1 represents one or more of methylene groups in an aliphatic group, an aromatic hydrocarbon ring-containing group, a heterocycle-containing group, and a silyl group represented by —O—, —S—, —CO—, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO A group selected from -NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -SS- or -SO 2- , or an oxygen atom May be a group having a structure in which these groups are replaced with a group obtained by combining these groups under non-adjacent conditions.
  • R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the alkyl group having 1 to 8 carbon atoms includes a predetermined
  • each functional group such as an aliphatic group, an aromatic hydrocarbon ring-containing group, a heterocyclic ring-containing group, and a silyl group in R 1 is an unsubstituted unsubstituted group or a substituent.
  • Substituents that substitute one or more hydrogen atoms in a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an arylalkyl group, a heterocyclic group-containing group, and a silyl group include fluorine, chlorine, bromine, and iodine.
  • Halogen atoms such as acetyl, 2-chloroacetyl, propionyl, octanoyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, a such as n-octadecyloxycarbonyl, carbamoyl, etc.
  • acyloxy group such as acetyloxy and benzoyloxy; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl- Anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N- Diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbony
  • the number of carbon atoms in the case where the hydrogen atom of the aliphatic group having 1 to 40 carbon atoms is substituted refers to the number of carbon atoms after the hydrogen atom is substituted and before the hydrogen atom is substituted. Does not refer to the number of carbon atoms.
  • the number of carbon atoms refers to the number of carbon atoms after the methylene group is substituted, and the methylene group is substituted. It does not refer to the number of previous carbon atoms.
  • R 1 is a monovalent aliphatic group having 1 to 40 carbon atoms, and a monovalent carbon atom having 6 to 40 carbon atoms.
  • the methylene group at the sulfur atom side of the 35 aromatic hydrocarbon ring-containing group, the monovalent heterocyclic group having 2 to 35 carbon atoms or the monovalent silyl group having 0 to 40 carbon atoms is -CO-O -Or -CO-NH-, a monovalent aliphatic group having 1 to 40 carbon atoms, a monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, a monovalent carbon atom It is preferably a 2-35 heterocyclic-containing group or a monovalent silyl group having 0-40 carbon atoms.
  • R 1 is a monovalent aliphatic group having 1 to 40 carbon atoms, a monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, or a monovalent heterocyclic group having 2 to 35 carbon atoms.
  • the ring-containing group or the monovalent silyl group having 0 to 40 carbon atoms is preferably a group having a structure in which the methylene group at the sulfur atom side terminal is replaced by -CO-O- or -CO-NH-.
  • R 1 is a monovalent aliphatic group having 1 to 40 carbon atoms or a monovalent aliphatic group having 6 to 35 carbon atoms, the terminal of which is substituted with —CO—O— or —CO—NH— on the sulfur atom side. It is more preferably an aromatic hydrocarbon ring-containing group, and further, an alkyl group having 1 to 40 carbon atoms or a carbon atom having 1 to 40 carbon atoms and having a sulfur atom terminal substituted with -CO-O- or -CO-NH- It is preferably 6 to 35 arylalkyl groups.
  • an alkyl group having 1 to 40 carbon atoms in which the terminal on the sulfur atom side is substituted with —CO—O— that is, —CO—OR ′′ (where R ′′ has a substituent A C1-C39 alkyl group) or an arylalkyl group having 6-35 carbon atoms, the terminal of which is substituted on the sulfur atom side by -CO-NH-, ie, -CO-NH —R ′ ′′ (R ′ ′′ is an aryl group having 6 to 34 carbon atoms or an arylalkyl group having 6 to 34 carbon atoms, which may have a substituent) And particularly preferably a group represented by —CO—OR ′′.
  • the compound A can form a composition excellent in patterning accuracy and heat resistance. That is, in the R 1 , the methylene group at the sulfur atom side of the monovalent aliphatic group having 1 to 40 carbon atoms or the monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms is -CO. It is more preferably a group having a structure substituted with —O— or —CO—NH—, and furthermore, a sulfur atom side terminal of an alkyl group having 1 to 40 carbon atoms or an arylalkyl group having 6 to 35 carbon atoms.
  • R A group represented by an alkyl group having 1 to 39 carbon atoms which may have a group or a methylene group at the sulfur atom side of the arylalkyl group having 6 to 35 carbon atoms is -CO-NH-
  • R ′ ′′ represents an optionally substituted aryl group having 6 to 34 carbon atoms or a group having 6 to 34 carbon atoms.
  • the above R ′′ is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent.
  • it is an unsubstituted alkyl group having 1 to 8 carbon atoms, particularly preferably an unsubstituted alkyl group having 3 to 6 carbon atoms.
  • R 1 is preferably a group represented by -CO-O-C 4 H 9 , among them It R '' is tert- butyl, i.e., R 1 is preferably a -CO-O-tert- butyl group. Further, R ′ ′′ is preferably an arylalkyl group having 6 to 12 carbon atoms. When R ′′ and R ′ ′′ are the above groups, the compound A can easily control the elimination of R 1 .
  • N is an integer of 2 or more and 10 or less, but is preferably 3 or more and 8 or less from the viewpoint of obtaining a compound capable of forming a composition excellent in patterning accuracy and heat resistance. It is preferably 4 or more and 7 or less, particularly preferably 4 or more and 6 or less. This is because when the above n is within the above range, the compound A can obtain a composition having more excellent heat resistance.
  • a composition that is excellent in patterning accuracy and heat resistance has an excellent balance of crosslink density and hydrophobicity, and is capable of easily forming a composition capable of stably forming a pattern-shaped cured product against variations in alkali development time. From the viewpoint of the above, n is preferably 5 or more and 6 or less.
  • the above X is used as a linking group for linking n —SR 1 .
  • the containing group includes a monovalent aliphatic group having 1 to 40 carbon atoms, a monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, and a monovalent heterocyclic group having 2 to 35 carbon atoms, respectively. This is a group having a structure in which n-1 hydrogen atoms have been removed from the ring-containing group.
  • the monovalent aliphatic group having 1 to 40 carbon atoms, the monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms and the monovalent heterocyclic group having 2 to 35 carbon atoms include: R 1 represents a monovalent aliphatic group having 1 to 40 carbon atoms, a monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, and a monovalent heterocyclic group having 2 to 35 carbon atoms. Examples include the same groups as the ring-containing groups.
  • One or more of the methylene groups in the aliphatic group, the aromatic hydrocarbon ring-containing group and the heterocyclic group-containing group in X are -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH —CO—, —NH—CO—O—, —O—CO—NH—, —NR′—, —SS— or —SO 2 —, or oxygen
  • the group may be replaced with a group obtained by combining these groups under the condition that atoms are not adjacent to each other.
  • X represents one or more of methylene groups in an aliphatic group, an aromatic hydrocarbon ring-containing group and a heterocyclic group-containing group represented by -O-, -S-, -CO-, -O-CO -, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, Groups selected from -NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -SS- or -SO 2- , or oxygen atoms are not adjacent to each other It may be a group having a structure in which these groups are replaced by a group obtained by combining these groups under conditions.
  • R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the alkyl group having 1 to 8 carbon atoms includes a predetermined number of carbon atom
  • Examples of the divalent aliphatic group having 1 to 40 carbon atoms represented by X include groups having a structure in which one hydrogen atom has been removed from the monovalent aliphatic group having 1 to 40 carbon atoms.
  • alkylene such as methylene, ethylene, propylene, butylene, butyldiyl and the like; a group wherein the methylene chain of the alkylene is replaced by -O-, -S-, -CO-O-, -O-CO-;
  • a group containing a residue of a polyol such as propanediol, butanediol, pentanediol, or hexanediol (for example, a group represented by the general formula (X1) described below); ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexane
  • Examples thereof include a residue of dithiol such as dithio
  • Examples of the trivalent aliphatic group having 1 to 40 carbon atoms represented by X include groups having a structure in which two hydrogen atoms have been removed from the monovalent aliphatic group having 1 to 40 carbon atoms.
  • a group containing a residue of a polyol eg, a group represented by the general formula (X2) described later
  • an alkylidine such as propiridine or 1,1,3-butyridine
  • Examples include a group substituted by a substituent described below.
  • Examples of the tetravalent aliphatic group having 1 to 40 carbon atoms represented by X include groups having a structure in which three hydrogen atoms have been removed from the monovalent aliphatic group having 1 to 40 carbon atoms.
  • Examples thereof include a group containing a residue of a polyol such as pentaerythritol (for example, a group represented by general formula (X3) described later) and a group in which these groups are substituted by a substituent described later.
  • Examples of the hexavalent aliphatic group having 1 to 40 carbon atoms represented by X include groups having a structure in which five hydrogen atoms have been removed from the monovalent aliphatic group having 1 to 40 carbon atoms.
  • Examples thereof include a group containing a residue of a polyol such as dipentaerythritol (for example, a group represented by general formula (X4) described later) and a group in which these groups are substituted by a substituent described later.
  • one hydrogen atom is selected from the above monovalent aromatic hydrocarbon ring-containing groups having 6 to 35 carbon atoms.
  • the group include a group having a structure excluding, for example, an arylene group such as phenylene and naphthylene; a residue of a bifunctional phenol such as catechol and bisphenol; 2,4,8,10-tetraoxaspiro [5,5] undecane; Examples include groups in which these groups are substituted with the substituents described below.
  • Examples of the trivalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms represented by X include two hydrogen atoms from the above monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms.
  • Examples thereof include groups having a structure excluded from the above, and examples thereof include phenyl-1,3,5-trimethylene and groups in which these groups are substituted by substituents described below.
  • Examples of the divalent heterocyclic group having 2 to 35 carbon atoms represented by X include groups having a structure in which one hydrogen atom has been removed from the monovalent heterocyclic group having 2 to 35 carbon atoms.
  • groups having a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring, a triazine ring, a furan ring, a thiophene ring, an indole ring, and the like, and one or more hydrogen atoms of these groups are substituted as described below. Groups substituted by groups.
  • Examples of the trivalent heterocyclic group having 2 to 35 carbon atoms represented by X include a group having a structure in which two hydrogen atoms have been removed from the monovalent heterocyclic group having 2 to 35 carbon atoms. Examples thereof include a group having an isocyanuric ring (for example, a group having a structure represented by general formula (X5) described later), a group having a triazine ring, and one or more hydrogen atoms of these groups. Examples include a group substituted by a substituent described below.
  • Examples of the tetravalent heterocyclic group having 2 to 35 carbon atoms represented by X include a group having a structure in which three hydrogen atoms have been removed from the monovalent heterocyclic group having 2 to 35 carbon atoms. Examples thereof include a group having a glycoluril group (for example, a structure represented by general formula (X6) described later) and a group in which a hydrogen atom of this group is substituted by a substituent described later.
  • Each functional group such as an aliphatic group, an aromatic hydrocarbon ring-containing group, and a heterocyclic group-containing group in X may have a substituent, and unless otherwise specified, may have a substituent. It is an unsubstituted functional group or a functional group having a substituent.
  • Such aliphatic group, an aromatic hydrocarbon ring-containing group, the one or substituents replacing two or more hydrogen atoms of each functional group such as a heterocyclic ring-containing group, an aliphatic group in the above R 1 Has the same content as the substituent for replacing the hydrogen atom of
  • X is an aliphatic group having 1 to 40 carbon atoms or an aliphatic group having 2 to 35 carbon atoms. It is preferably a heterocyclic-containing group, particularly preferably an aliphatic group having 10 to 40 carbon atoms and a heterocyclic-containing group having 5 to 25 carbon atoms, and particularly preferably a heterocyclic group having 15 to 30 carbon atoms. It is preferably an aliphatic group or a heterocyclic group having 10 to 20 carbon atoms, and particularly preferably an aliphatic group having 25 to 30 carbon atoms or a heterocyclic group having 11 to 15 carbon atoms. Is preferred. This is because a compound capable of forming a composition excellent in patterning accuracy and heat resistance can be obtained when X is the above-described group.
  • the above-mentioned X is preferably an aliphatic group having 1 to 40 carbon atoms, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, and a group having 2 to 35 carbon atoms.
  • one or more of the methylene groups in the heterocyclic-containing group of formula (I) is -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O It may be replaced by a group selected from —CO—NH—, —NR′—, —SS— or —SO 2 —, or a combination of these groups under the condition that oxygen atoms are not adjacent to each other.
  • one or more of the methylene groups be -O-CO-, -CO-O-
  • it is replaced, in particular, n-number of methylene groups, -O-CO -, - it is preferable to have been replaced by CO-O-.
  • X is one of an methylene group in an aliphatic group having 1 to 40 carbon atoms, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, and a heterocyclic group having 2 to 35 carbon atoms.
  • the aliphatic group having 1 to 40 carbon atoms represented by X is a group having a residue of a polyol (for example, a group represented by the following general formulas (X1) to (X4)).
  • a polyol for example, a group represented by the following general formulas (X1) to (X4)
  • the heterocyclic group having 2 to 35 carbon atoms represented by X is an isocyanuric ring (structure represented by the following general formula (X5)) or a glycoluril group (represented by the following general formula (X6)) A group having the following structure).
  • the hydrogen atoms in the structures represented by the general formulas (X1) to (X6) may be substituted with a substituent.
  • the substituent replacing the hydrogen atom may be similar to those in the substituents replacing a hydrogen atom of an aliphatic group in the above R 1.
  • a1 is an integer of 1 to 20, and * represents a bonding site.
  • the above a1 is an integer of 1 to 20, preferably an integer of 2 to 10, and more preferably an integer of 3 to 5.
  • the compound A compounds represented by the following general formulas (A1) to (A6) can be preferably used.
  • the compound A is a compound represented by the following formula (A4) or (A6). This is because the compound A becomes a compound capable of forming a composition excellent in patterning accuracy and heat resistance by being a compound having the structure described above, and in particular, a composition excellent in heat resistance can be formed.
  • the compound A is a compound represented by the following general formula (A4). This is because, as well as the patterning accuracy and the heat resistance, the development margin is improved, and in particular, the patterning accuracy is also improved.
  • the reason that the compounds represented by the general formulas (A4) and (A6) are excellent in both patterning accuracy and heat resistance and, in particular, are compounds capable of forming a composition excellent in heat resistance is as follows. It is inferred as follows.
  • the compound represented by the general formula (A4) is arranged such that the number of thiol groups generated after elimination of the protecting group is as large as 6, and the thiol group extends in all directions. Therefore, by including the compound A, a region having a high crosslinking density can be formed around the compound A. As a result, excellent heat resistance is obtained.
  • the structure represented by (X4) included in the six protective thiol groups or the site where the thiol group is bonded to the compound represented by the general formula (A4) has a relatively large molecular weight, Has a structure extending in six directions from the oxygen atoms of the above, hardening shrinkage due to crosslinking is small. For this reason, it is easy to reduce shrinkage during the heat treatment.
  • the compound represented by the general formula (A4) can have excellent balance between patterning accuracy and heat resistance, and can easily exhibit particularly excellent heat resistance.
  • the compound represented by the general formula (A4) has a structure in which the compound spreads in six directions and has a large molecular weight, so that the diffusion rate in the composition is low.
  • the crosslinking between the polymerizable components does not easily proceed.
  • the patterning accuracy is improved.
  • the structure represented by (X4) included in the six protective thiol groups or the site that binds the thiol group has a relatively large molecular weight and is likely to be a highly hydrophobic site.
  • the compound represented by the general formula (A4) facilitates formation of a cured product having excellent resistance to an alkali developing solution, and a composition containing the compound has an excellent development margin.
  • the compound represented by the general formula (A4) has an excellent patterning accuracy exhibited in the polymerization step, an excellent development margin exhibited in the developing step, and an improved patterning accuracy obtained as a result.
  • excellent heat resistance and the like exhibited during a heat treatment step such as a post-bake step can be effectively exhibited in each step of the patterning step.
  • the compound represented by the general formula (A4) is particularly suitable, for example, for the curable composition for forming a patterned cured product.
  • the compound represented by the general formula (A6) has a large number of thiol groups generated after elimination of the protective group as four, and is arranged so that the thiol groups extend in all directions. Having a group.
  • the compound A by including the compound A, a region having a high crosslinking density can be formed around the compound A. As a result, excellent heat resistance is obtained.
  • the glycoluril group of the compound represented by the general formula (A6) has a rigid structure, so that curing shrinkage due to crosslinking is small. That is, it is easy to reduce shrinkage during the heat treatment.
  • the compound represented by the general formula (A4) can have excellent balance between patterning accuracy and heat resistance, and can easily exhibit particularly excellent heat resistance.
  • the compound represented by the general formula (A6) has a rigid glycoluril group and has a bulky structure, and thus has a low diffusion rate in the composition. For this reason, even if the protecting group is eliminated from some of the compounds, the crosslinking between the polymerizable components does not easily proceed. As a result, the patterning accuracy is improved.
  • R 11 and R 12 each independently represent the following general formula (101); L 11 and L 12 represent an alkylene group having 1 to 10 carbon atoms, a1 represents an integer of 1 to 20, R 21 , R 22 and R 23 each independently represent the following general formula (101) or (102); Any two or more of R 21 , R 22 and R 23 are represented by the following general formula (101), L 21 , L 22 and L 23 represent an alkylene group having 1 to 10 carbon atoms, R 24 represents a hydrogen atom or a monovalent aliphatic group having 1 to 40 carbon atoms, R 31 , R 32 , R 33 and R 34 each independently represent the following formula (101) or (102); Any two or more of R 31 , R 32 , R 33 and R 34 are represented by the following general formula (101), L 31 , L 32 , L 33 and L 34 represent an alkylene group having 1 to 10 carbon atoms, R 41 , R 42 , R 43 , R 44 , R 45 and R 46 each independently represent the following formula (10
  • R 1 is a monovalent aliphatic group having 1 to 40 carbon atoms, a monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, a monovalent having 2 to 35 carbon atoms, Represents a heterocyclic-containing group or a monovalent silyl group having 0 to 40 carbon atoms, * Represents a bond,
  • One or more of methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group-containing group, and silyl group are -O-, -S-, -CO-, -O-CO- , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- May be replaced by a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -
  • R 24 in the general formula (A2) and R 65 and R 66 in (A6) the monovalent aliphatic group used in the above R 1
  • R 1 in the general formula (101) is the same as R 1 in the general formula (A).
  • the alkylene group having 1 to 10 carbon atoms represented by 52 , L 53 , L 61 , L 62 , L 63 and L 64 has a structure in which one hydrogen atom is removed from an alkyl group having 1 to 10 carbon atoms.
  • a divalent group of As the alkyl group having 1 to 10 carbon atoms for example, those having a predetermined number of carbon atoms among the alkyl groups having 1 to 40 carbon atoms in R 1 can be used.
  • alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, butylene, and butyldiyl. Further, the alkylene group having 1 to 10 carbon atoms may be linear or branched. Examples of the linear group include a propylene group obtained by removing a hydrogen atom from the 1,2-position of propane as a group having 3 carbon atoms, and removing a hydrogen atom from the 1,3-position of propane. Trimethylene groups.
  • R 21 , R 22 and R 23 in the general formula (A2) two or more of them may be the general formula (101), but all of them are preferably the general formula (101). .
  • R 31 , R 32 , R 33 and R 34 in the general formula (A3) two or more of them may be the general formula (101), but three or more of the general formula (101) It is particularly preferable that all of the above be the general formula (101).
  • At least two of R 41 , R 42 , R 43 , R 44 , R 45, and R 46 in the general formula (A4) may be the general formula (101), but R 41 , R 42 , It is preferable that four or more of R 43 , R 44 , R 45 and R 46 have the above general formula (101), and among them, R 41 , R 42 , R 43 , R 44 , R 45 and R 46.
  • At least two of R 51 , R 52 and R 53 in the general formula (A5) may be the general formula (101), but all of R 51 , R 52 and R 53 are the same as those in the general formula (101).
  • Formula (101) is preferable.
  • R 61 , R 62 , R 63, and R 64 in the general formula (A6) may be the general formula (101), and R 61 , R 62 , R 63, and R 64 It is preferable that three or more of the above formulas are the general formula (101), and it is preferable that all of R 61 , R 62 , R 63 and R 64 be the above general formula (101).
  • R 1 in the general formula (101) is the same as the preferred structure of R 1 in the general formula (A).
  • R 24 is preferably an aliphatic group having 1 to 40 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 20 carbon atoms. It is preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl and isopropyl. It is preferably a group. This is because the compound A can form a composition excellent in patterning accuracy and heat resistance when R 24 is the above group.
  • R 65 and R 66 are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. It is preferably a hydrogen atom.
  • R 65 and R 66 are the above-described groups, the compound A can form a composition excellent in patterning accuracy and heat resistance.
  • Aa1 in the general formula (A1) is the same as a1 in the general formula (X1).
  • L 11 and L 12 are preferably an alkylene group having 1 to 5 carbon atoms, and particularly a linear alkylene group having 1 to 3 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms. Is preferred. L 11 and L 12 may be the same group or different groups, but are preferably the same group from the viewpoint of easy synthesis.
  • L 21 , L 22 and L 23 are preferably an alkylene group having 1 to 5 carbon atoms, and among them, a linear alkylene group having 1 to 3 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms is preferable. It is preferably a group.
  • L 21 , L 22 and L 23 may be the same group or different groups, but are preferably the same group from the viewpoint of easy synthesis.
  • the above L 31 , L 32 , L 33 and L 34 are preferably an alkylene group having 1 to 5 carbon atoms, and among them, a linear alkylene group having 1 to 3 carbon atoms or a branched alkylene group having 3 to 3 carbon atoms is preferable. It is preferably an alkylene group of 5.
  • L 31 , L 32 , L 33 and L 34 may be the same group or different groups, but are preferably the same group from the viewpoint of easy synthesis.
  • the above L 41 , L 42 , L 43 , L 44 , L 45 and L 46 are preferably alkylene groups having 1 to 5 carbon atoms, and among them, linear alkylene groups having 1 to 3 carbon atoms are preferable. It is preferably a group or branched 3-5 alkylene group.
  • the above L 41 , L 42 , L 43 , L 44 , L 45 and L 46 may be the same or different groups, but are the same groups from the viewpoint of easy synthesis. Is preferred.
  • Each of L 51 , L 52 and L 53 is preferably an alkylene group having 1 to 5 carbon atoms, and among them, a linear alkylene group having 1 to 3 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms is preferable. It is preferably a group.
  • L 51 , L 52 and L 53 may be the same group or different groups, but are preferably the same group from the viewpoint of easy synthesis.
  • the above L 61 , L 62 , L 63 and L 64 are preferably an alkylene group having 1 to 5 carbon atoms, and among them, a linear alkylene group having 1 to 3 carbon atoms or a branched alkylene group having 1 to 3 carbon atoms is preferable.
  • L 61 , L 62 , L 63 and L 64 may be the same group or different groups, but are preferably the same group from the viewpoint of easy synthesis.
  • the L 11, L 12, L 21 , L 22, L 23, L 31, L 32, L 33, L 34, L 41, L 42, L 43, L 44, L 45, L 46, L 51, L This is because when 52 , L 53 , L 61 , L 62 , L 63 and L 64 are within the above ranges, the compound can form a composition having more excellent patterning accuracy and heat resistance.
  • Examples of the linear alkylene group having 1 to 3 carbon atoms represented by 52 , L 53 , L 61 , L 62 , L 63 and L 64 include methylene, ethylene (ethane-1,2 and -Diyl), propylene (propane-1,3-diyl) and the like.
  • Specific examples of the branched 3 to 5 alkylene groups represented by 52 , L 53 , L 61 , L 62 , L 63 and L 64 include propane-1,1-diyl and propane-1,2 -Diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, pentane-1,1-diyl, pentane-1,2-diyl, pentane-1,3-diyl And pentane-1,4-diyl.
  • the number of thiol groups (SH groups) in the compound A that is, the number of thiol groups in the compound A that are not protected by the protecting group R 1 can form a composition having more excellent patterning accuracy and heat resistance.
  • the number of the thiol groups is preferably 2 or less, more preferably 1 or less, and 0 in the compound A, that is, the compound A does not contain a thiol group. preferable. This is because a composition excellent in patterning accuracy and heat resistance can be formed.
  • the molecular weight of the compound A is not particularly limited as long as it can form a composition excellent in patterning accuracy and heat resistance.
  • it is preferably 3000 or less, and particularly preferably 300 or more and 2500 or less.
  • it is preferably 500 or more and 2000 or less, and particularly preferably 600 or more and 1800 or less.
  • the molecular weight of the compound A is excellent in patterning accuracy and heat resistance, and from the viewpoint that the composition containing the compound is excellent in the development margin, and particularly from the viewpoint of exhibiting excellent heat resistance, is 1000. It is preferably from 1700 to 1,700, more preferably from 1,200 to 1,600, and particularly preferably from 1,300 to 1,500.
  • the molecular weight of the compound after elimination of the protecting group R 1 of the compound A is excellent in patterning accuracy and heat resistance, and includes the above compound.
  • the composition is preferably 400 or more and 1000 or less, more preferably 500 or more and 900 or less, particularly, It is preferably from 600 to 800.
  • the equivalent of the protected thiol group (SR 1 ) in the compound A that is, the value obtained by dividing the molecular weight of the compound A by the number of the protected thiol groups (SR 1 ) (the molecular weight of the compound A / the number of the protected thiol groups SR 1 ) is as follows: , And preferably 500 or less, more preferably 100 or more and 400 or less, and particularly preferably 150 or more and 300 or less.
  • the protective thiol group equivalent of the compound A is within the above range, the compound A can form a composition having excellent patterning accuracy and heat resistance.
  • the equivalent of the protective thiol group (SR 1 ) in the compound A is excellent in patterning accuracy and heat resistance, and exhibits a viewpoint that the composition containing the compound has an excellent development margin, and particularly exhibits excellent heat resistance. From the viewpoint of doing, it is preferably 200 or more and 270 or less, particularly preferably 220 or more and 260 or less, and particularly preferably 230 or more and 250 or less.
  • the thiol group equivalent of the compound after elimination of the protecting group R 1 of the compound A that is, the thiol group equivalent of the thiol compound in which the —SH group is not protected by the protecting group R 1 is excellent in patterning accuracy and heat resistance.
  • the composition containing the above compound becomes excellent in the development margin, particularly from the viewpoint of exhibiting excellent heat resistance, the composition is preferably 400 or more and 1000 or less, and 500 or more and 900 or less. Preferably, it is 600 or more and 800 or less.
  • the compound A may be one in which the protecting group R 1 is eliminated by heating.
  • the temperature at which the protective group R 1 contained in the compound A is eliminated can be, for example, 100 ° C. or more and 300 ° C. or less, and particularly preferably 120 ° C. or more and 250 ° C. or less, and more preferably 150 ° C. or more.
  • the temperature is preferably 230 ° C. or lower.
  • the desorption temperature can be a temperature at which a thermal loss of 5% by weight is indicated by differential thermal analysis.
  • a measuring method for example, using a STA (differential thermogravimetric simultaneous measuring device), about 5 mg of a sample, in a nitrogen atmosphere of 200 mL / min, under normal pressure, at a temperature rise start temperature of 30 ° C., a temperature rise end temperature of 500 ° C., and a temperature rise of 500 ° C.
  • the heat loss of the sample when the temperature is increased at a temperature rate of 10 ° C./min is measured, and the temperature at the time when the weight is reduced by 5% with respect to the sample weight at 30 ° C. can be set as the 5% weight loss temperature.
  • STA7000 manufactured by Hitachi High-Tech Science
  • STA7000 simultaneous differential thermogravimetric analyzer.
  • Specific examples of the compound A include, for example, the following compounds.
  • the method for producing the compound A is not particularly limited as long as a desired structure can be obtained.
  • the production method described above includes, for example, a method of forming an esterified product of a hydroxyl group of a polyol and a carboxylic acid containing an SH group as described in JP-A-2017-031318, and a method described in JP-A-2015-059099.
  • a thioacetic acid is added to an ethylenically unsaturated group of a compound having an ethylenically unsaturated group, the compound is reduced with a borohydride compound.
  • the compound A can be used as a thiol generator that generates an SH group by heat treatment or the like.
  • thiol added to a composition such as a curable composition containing a polymerizable component B such as a radical polymerizable component can be used. It can be used as a generator.
  • the curable composition include a thermosetting paint, a photocurable paint or varnish, a thermosetting adhesive, a photocurable adhesive, a printed circuit board, a color television, a PC monitor, a portable information terminal, and a digital camera.
  • Color filters for liquid crystal display panels for color display etc., 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
  • adhesives For manufacturing dental compositions, stereolithography resins, gel coats, photoresists for electronics, electroplating resists, etching resists, both liquid and dry films, solder resists, color filters for various display applications
  • a plasma display panel, an electroluminescent display, and an LC For forming a structure in the manufacturing process, a composition for encapsulating electric and electronic components, a solder resist, a magnetic recording material, a micromechanical component, a waveguide, an optical switch, a plating mask, an etching mask, and a color test.
  • the curable composition containing the compound A is preferably used for forming a patterned cured product having both excellent patterning accuracy and heat resistance.
  • the use of the curable composition is preferably used for a color filter, a photo spacer, a black column spacer, an electrode material, a photoresist, a solder resist, an overcoat, an insulating film, a black matrix, a partition material, and the like. be able to.
  • the compound A when the compound A is used in a photocurable composition, the compound A is used in a photocurable composition for forming a patterned cured product having a width of 200 ⁇ m or less, that is, for forming a pattern having a width of 200 ⁇ m or less.
  • the thickness of the pattern is preferably from 0.1 ⁇ m to 100 ⁇ m, more preferably from 0.3 ⁇ m to 50 ⁇ m. , Preferably 0.5 ⁇ m or more and 10 ⁇ m or less, more preferably 1 ⁇ m or more and 5 ⁇ m or less.
  • the film thickness is within the above range, the effect that the compound A has excellent patterning accuracy and heat resistance can be more effectively exhibited, and a pattern having a high aspect ratio can be stably formed. is there.
  • the thiol generator of the present invention is characterized by containing the above-mentioned compound (the above-mentioned compound A).
  • a thiol generator capable of forming a composition having excellent patterning accuracy and heat resistance can be obtained.
  • Compound A used in the thiol generator of the present invention may be any compound capable of forming a composition excellent in patterning accuracy and heat resistance, and may be only one type in the thiol generator. Two or more types may be used.
  • the thiol generator may contain, for example, two or more and five or less compound A.
  • the content of the compound A is not particularly limited as long as it can form a composition having excellent patterning accuracy and heat resistance, and is appropriately set according to the type of the thiol generator.
  • the content of the compound A can be, for example, 100 parts by mass based on 100 parts by mass of the solid content of the thiol generator, that is, the thiol generator is the compound A. Further, the content may be less than 100 parts by mass, based on 100 parts by mass of the solid content of the thiol generator, that is, the thiol generator may be a composition containing the compound A and other components. It can be more than 99.99 parts by mass.
  • the lower limit of the content is preferably 50 parts by mass or more, and particularly preferably 70 parts by mass or more, from the viewpoint of facilitating formation of a composition having excellent patterning accuracy and heat resistance. It is preferable that the content is particularly high, and it is particularly preferable that the content be 90 parts by mass or more.
  • the upper limit of the content is preferably 99 parts by mass or less, particularly preferably 95 parts by mass or less, In particular, it is preferably 90 parts by mass or less.
  • the solid content includes all components other than the solvent. Further, the content of the compound A indicates the total amount of the compound A when the compound A includes two or more kinds.
  • the compound A can be the same as the content described in the above section “A. Compound”, and the description is omitted here.
  • the thiol generator may contain other components other than the compound A.
  • examples of such other components include, for example, “2. thiol-reactive polymerizable component”, “3. polymerization initiator”, and “4. polymer having a carboxyl group” of “C. And "5. Other components”.
  • the other components include the polymerization initiator described in the section “3. Polymerization initiator”. This is because by consolidating components involved in the polymerization, reaction and the like of the polymerizable component B, it becomes easy to produce a composition containing the polymerizable component B.
  • the content of the radical polymerization initiator based on 100 parts by mass of the compound A can be the same as the content described in “3. Polymerization initiator” of “C.
  • the other components include a polymer having no polymerizable group described in “5. Other Components”, from the viewpoint of facilitating the control of the particle size of the thiol generator and the like. .
  • the content of the other components can be appropriately set according to the use of the thiol generator and the like. It is preferably at most 10 parts by mass. This is because the thiol generator can easily increase the content ratio of the compound A, and can easily form a composition having excellent patterning accuracy and heat resistance.
  • any method may be used as long as the compound A can be contained in a desired amount.
  • a method using a known mixing means can be used.
  • Examples of the use of the thiol generator include a use for adding to a composition such as a curable composition containing the polymerizable component B.
  • a composition such as a curable composition containing the polymerizable component B.
  • the specific use of the curable composition and the like can be the same as those described in the above section “A. Compound”, and thus description thereof is omitted.
  • composition of the present invention comprises a compound represented by the following general formula (A) (compound A) and a thiol-reactive polymerizable component (polymerizable component B). .
  • R 1 is a monovalent aliphatic group having 1 to 40 carbon atoms, a monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, a monovalent having 2 to 35 carbon atoms, Represents a heterocyclic-containing group or a monovalent silyl group having 0 to 40 carbon atoms
  • X represents an aliphatic group having 1 to 40 carbon atoms, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, or a heterocyclic-containing group having 2 to 35 carbon atoms having the same valence as n.
  • One or more of methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group-containing group, and silyl group are -O-, -S-, -CO-, -O-CO- , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- Is it replaced by a group selected from NH—CO—, —NH—CO—O—, —O—CO—NH—, —NR′—, —SS— or —SO 2 —? Or an oxygen atom may be replaced by a group combining these groups under non-adjacent conditions, n represents an integer of 2 or more and 10 or less.
  • the composition since the composition contains the compound A, the composition has excellent patterning accuracy and heat resistance.
  • composition of the present invention contains the compound A and the polymerizable component B.
  • each component of the composition of the present invention will be described in detail.
  • Compound A The type of the compound A is not particularly limited as long as it can form a composition having excellent patterning accuracy and heat resistance, and may be only one type or two or more types in the composition.
  • the compound A can include, for example, two or more and five or less compound A.
  • the content of the compound A is appropriately set according to the use of the composition and the like.
  • Such a content can be 0.01 to 20 parts by mass, preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the solid content of the composition. This is because a composition excellent in patterning accuracy and heat resistance can be easily formed on the composition.
  • the compound A can be the same as the content described in the above section “A. Compound”, and the description is omitted here.
  • Polymerizable component B is not particularly limited as long as it is a compound that can react with thiol and has a thiol-reactive group capable of polymerizing the polymerizable components with each other.
  • a thiol-reactive group a radical polymerizable group, a cationic polymerizable group, or the like can be preferably used.
  • the polymerizable component B may include at least one of a radical polymerizable compound having a radical polymerizable group and a cationic polymerizable compound having a cationic polymerizable group, and a radical polymerizable component comprising the radical polymerizable compound , A cationically polymerizable component comprising a cationically polymerizable compound, or a polymerizable component containing both a radically polymerizable compound and a cationically polymerizable compound.
  • the composition is polymerizable by light irradiation.
  • a photopolymerization initiator such as a photoradical polymerization initiator and a photocationic polymerization initiator
  • the composition is polymerizable by light irradiation.
  • the polymerizable component B preferably contains a radical polymerizable compound as the polymerizable compound B, and is particularly preferably a radical polymerizable component composed of the radical polymerizable compound. This is because when the polymerizable component B contains a radical polymerizable compound, the composition has an excellent curing rate. Further, this is because crosslinking using the compound A is easy.
  • the radical polymerizable compound is a compound having a radical polymerizable group.
  • examples of such a radical polymerizable compound include a radical polymerizable compound described in JP-A-2016-17609. More specifically, examples of the radical polymerizable group include compounds having an ethylenically unsaturated group such as an acryloyl group, a methacryloyl group, and a vinyl group.
  • the radical polymerizable compound a monofunctional compound having one radical polymerizable group and a polyfunctional compound having two or more radical polymerizable groups can be used.
  • a compound having an acid group and a compound having no acid group can be used as the radical polymerizable compound.
  • the acid group include a —COOH group, a —SO 3 H group, a —SO 2 NHCO— group, a phenolic hydroxy group, a —SO 2 NH— group, and a —CO—NH—CO— group.
  • Examples of the compound having an acid group include 4-hydroxystyrene, (meth) acrylic acid, ⁇ -bromo (meth) acrylic acid, ⁇ -chloro (meth) acrylic acid, ⁇ -furyl (meth) acrylic acid, ⁇ -Styryl (meth) acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, 4-hydroxyphenyl Examples include methacrylate, 3,5-dimethyl-4-hydroxybenzylacrylamide, 4-hydroxyphenylacrylamide, 4-hydroxyphenylmaleimide, 3-maleimidopropionic acid, 4-maleimidobutyric acid, and 6-maleimidohexanoic acid.
  • Examples of the compound having an acid group include, for example, an epoxy acrylate resin in which an unsaturated monobasic acid is acted on an epoxy group of an epoxy compound, and an unsaturated monobasic acid being acted on an epoxy group of an epoxy compound.
  • An acid group-containing epoxy acrylate resin such as a carboxyl group-containing epoxy acrylate resin obtained by the action of an acid anhydride is exemplified.
  • Examples of the acid group-containing epoxy acrylate resin include Ripoxy (registered trademark) SPC-2000 and SPC-3000 (manufactured by Showa Denko KK), Dicklight (registered trademark) UE-777 (manufactured by DIC), and Upika (registered trademark) manufactured by Nippon Yupika.
  • a polymer having a methacryloyl group or an acryloyl group and a carboxyl group can also be used.
  • Polymer having a carboxyl group” described below is also preferable.
  • the compound having an acid group among the polymers of the radical polymerizable compound, those having an unreacted or post-added radical polymerizable group can also be used.
  • those having an unreacted or post-added radical polymerizable group also have an acid group. It can be used as a compound having.
  • Examples of the compound having no acid group include polymerizable styrene derivatives such as styrene, vinyltoluene, ⁇ -methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide, acrylonitrile, and vinyl-n-butyl ether.
  • the radical polymerizable compound can be used together with a radical polymerization initiator such as a photoradical polymerization initiator and a thermal radical polymerization initiator.
  • a radical polymerization initiator such as a photoradical polymerization initiator and a thermal radical polymerization initiator.
  • the cationic polymerizable compound is a compound having a cationic polymerizable group.
  • a cationically polymerizable compound examples include the cationically polymerizable compounds described in JP-A-2016-17609. More specifically, examples of the cationic polymerizable compound include compounds having a cyclic ether group such as an epoxy compound having an epoxy group and an oxetane compound having an oxetane group, and vinyl ether compounds having a vinyl ether group.
  • a monofunctional compound having one cationically polymerizable group and a polyfunctional compound having two or more cationically polymerizable groups can be used.
  • a compound having an acid group and a compound having no acid group can be used.
  • a polymer having an epoxy group, an oxetanyl group or a vinyl ether group and a carboxyl group can also be used. Examples of such a polymer include polymers having a structural unit having an epoxy group, an oxetanyl group, or a vinyl ether group as a crosslinkable group, among the polymers described in “4. Polymer having a carboxyl group” described below. Etc. can also be preferably used.
  • cationic polymerizable compounds When two or more cationic polymerizable compounds are used as a mixture, they may be copolymerized in advance and used as a copolymer.
  • the cationically polymerizable compound can be used together with a cationic polymerization initiator such as a photocationic polymerization initiator and a thermal cationic polymerization initiator.
  • the content of the polymerizable component B is not particularly limited as long as it can provide excellent patterning accuracy and heat resistance.
  • the solid content of the composition of the present invention is not limited. In 100 parts by mass, it is preferably from 10 parts by mass to 90 parts by mass, particularly preferably from 20 parts by mass to 80 parts by mass, particularly from 30 parts by mass to 70 parts by mass. Is preferred. This is because the composition becomes more excellent in patterning accuracy and heat resistance.
  • the content of the polymerizable component B is not particularly limited as long as the patterning accuracy and the heat resistance can be excellent.
  • the total content of the compound A and the polymerizable component B In 100 parts by mass, the amount is preferably 70 parts by mass or more, particularly preferably 80 parts by mass or more and 99.9 parts by mass or less, particularly preferably 90 parts by mass or more and 99 parts by mass or less. .
  • the content is within the above range, the composition becomes more excellent in patterning accuracy and heat resistance.
  • any of a compound having an acid group and a compound having no acid group can be used as the polymerizable compound B. It is preferable to include both a compound having an acid group and a compound not having an acid group from the viewpoint of obtaining a composition having more excellent patterning accuracy and heat resistance. More specifically, when the polymerizable component B is a radical polymerizable component, it is preferable to include a compound having an acid group as the radical polymerizable compound from the viewpoint of obtaining a composition having more excellent patterning accuracy. From the viewpoint of making the composition more excellent in patterning accuracy and heat resistance, it is preferable to include both a compound having an acid group and a compound having no acid group as the radical polymerizable compound.
  • the content of the compound having an acid group is not particularly limited as long as the composition has excellent patterning accuracy and heat resistance. It is preferable that the content is not less than 1 part by mass and not more than 80 parts by mass. This is because the composition becomes more excellent in patterning accuracy and heat resistance.
  • the content of the compound having an acid group is preferably 20 parts by mass or more in 100 parts by mass of the polymerizable component B. Especially, it is preferable that it is 50 mass parts or more, and it is especially preferable that it is 70 mass parts or more.
  • the content of the compound having an acid group in 100 parts by mass of the polymerizable component B is preferably 70 parts by mass or less. It is preferably at most 50 parts by mass, particularly preferably at most 30 parts by mass. From the viewpoint of making the composition more excellent in patterning accuracy, the content of the compound having an acid group is 20 parts by mass or more in the total of 100 parts by mass of the compound A and the polymerizable component B. It is preferable that the content is not less than 50 parts by mass and not more than 90 parts by mass, and particularly preferably not less than 70 parts by mass and not more than 90 parts by mass.
  • the content of the compound having an acid group is 80 parts by mass or less in a total of 100 parts by mass of the compound A and the polymerizable component B. Is preferred, and in particular, it is preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less.
  • the content of the compound having an acid group is, when the polymerizable component B contains both a radically polymerizable compound and a cationically polymerizable compound, the compound having an acid group and the cationically polymerizable compound among the radically polymerizable compounds. 1 shows the total content of compounds having an acid group.
  • the number of functional groups of the polymerizable compound B that is, the number of thiol reactive groups contained in one molecule of the polymerizable compound B may be 1 or more, and a monofunctional compound having one thiol reactive group, a thiol reactive group Can be used.
  • the number of functional groups of the compound having no acid group may be one or more, but is preferably two or more, particularly preferably three or more and eight or less, and particularly preferably four or more and seven or less. Is preferred. This is because the composition has an excellent balance between patterning accuracy and heat resistance.
  • the number of functional groups of the radical polymerizable compound having no acid group is preferably And preferably 2 or more, more preferably 3 or more and 8 or less, and particularly preferably 4 or more and 7 or less.
  • the polymerizable component B preferably contains a low molecular weight compound as the polymerizable compound B from the viewpoint of patterning accuracy of the composition and the like.
  • the polymerizable component B preferably contains a high molecular weight compound as the polymerizable compound B from the viewpoint of the heat resistance of the composition and the like.
  • the polymerizable component B preferably contains both a low molecular weight compound and a high molecular weight compound as the polymerizable compound B from the viewpoint of the balance between the patterning accuracy of the composition and the heat resistance.
  • the polymerizable component B is a radical polymerizable component, from the viewpoint of patterning accuracy and the like, it is preferable that the polymerizable component B contains a low molecular weight compound as the radical polymerizable compound. From a viewpoint, it is preferable to include both a low molecular weight compound and a high molecular weight compound as the radical polymerizable compound.
  • the molecular weight of the low molecular weight compound is not particularly limited as long as a desired patterning accuracy or the like can be obtained.
  • the molecular weight can be less than 1000, preferably 50 to 500, and more preferably 50 to 300. Is preferred.
  • the molecular weight of the high molecular weight compound is not particularly limited as long as desired heat resistance and the like can be obtained.
  • the molecular weight can be 1,000 or more, preferably 1,000 to 100,000, and more preferably 1500 to 50,000. Or less, particularly preferably 2,000 or more and 10,000 or less.
  • the molecular weight indicates a weight average molecular weight (Mw).
  • the weight average molecular weight can be determined by gel permeation chromatography (GPC) as a standard polystyrene equivalent value.
  • the weight average molecular weight Mw is determined by, for example, using GPC (LC-2000plus series) manufactured by JASCO Corporation, eluting solvent as tetrahydrofuran, and polystyrene standard for calibration curve as Mw 110000, 707000, 397000, 189000, 98900, 37200, 13700, 9490, 5430, 3120, 1010, 589 (manufactured by Tosoh Corporation, TSKgel standard polystyrene), and the measurement can be performed using KF-804, KF-803, and KF-802 (manufactured by Showa Denko).
  • the measurement temperature can be 40 ° C.
  • the flow rate can be 1.0 mL / min.
  • the content of the high molecular weight compound is not particularly limited as long as it can provide excellent patterning accuracy and heat resistance.For example, from the viewpoint of the balance between patterning accuracy and heat resistance, it is appropriate. It will be adjusted. Specifically, the content of the high molecular weight compound is preferably from 1 part by mass to 90 parts by mass in 100 parts by mass of the polymerizable component B, and particularly preferably from 1 part by mass to 80 parts by mass. Is preferred. This is because the composition becomes more excellent in patterning accuracy and heat resistance.
  • the content of the high-molecular weight compound is preferably 30 parts by mass or more in 100 parts by mass of the polymerizable component B, Especially, it is preferable that it is 50 mass parts or more, and it is preferable that it is 70 mass parts or more. From the viewpoint of providing the composition with excellent coatability, the content of the high molecular weight compound is preferably 60 parts by mass or less in 100 parts by mass of the polymerizable component B, and among them, 40 parts by mass Or less, particularly preferably 20 parts by mass or less.
  • the content of the high molecular weight compound is 20 parts by mass or more in a total of 100 parts by mass of the compound A and the polymerizable component B.
  • it is preferably from 50 parts by mass to 90 parts by mass, and particularly preferably from 70 parts by mass to 90 parts by mass.
  • the content of the high molecular weight compound is preferably 80 parts by mass or less in a total of 100 parts by mass of the compound A and the polymerizable component B. In particular, it is preferably at most 50 parts by mass, particularly preferably at most 30 parts by mass.
  • the content of the high molecular weight compound is a high molecular weight compound as a radical polymerizable compound and a high molecular weight compound as a cationic polymerizable compound. It shows the total content of the compounds.
  • the composition preferably contains a polymerization initiator capable of polymerizing the polymerizable components B with each other. This is because it becomes easy to form a patterned cured product with high patterning accuracy using the above composition.
  • a polymerization initiator can be appropriately selected according to the type of the polymerizable component B.
  • a radical polymerization initiator and a cationic polymerization initiator can be used, respectively.
  • the content of the polymerization initiator may be any as long as it becomes a composition having more excellent patterning accuracy and heat resistance.
  • the content is, for example, in the solid content of 100 parts by mass of the composition of the present invention, it can be 0.01 to 30 parts by mass, and 0.1 to 20 parts by mass. Is preferably 2 to 10 parts by mass. This is because the above content makes the composition more excellent in patterning accuracy and heat resistance.
  • the content of the polymerization initiator is not particularly limited as long as a composition having excellent patterning accuracy and heat resistance can be formed. It is preferably 15 parts by mass or more and 650 parts by mass or less, and more preferably 20 parts by mass or more and 600 parts by mass or less.
  • the content of the polymerization initiator is not particularly limited as long as a composition having excellent patterning accuracy and heat resistance can be formed. It is preferably at most 0.5 part by mass, more preferably at most 0.5 part by mass and at most 45 parts by mass, preferably at least 1 part by mass and at most 40 parts by mass. When the content is in the above range, a composition excellent in patterning accuracy and heat resistance can be easily formed.
  • the radical polymerization initiator may be any one that can generate a radical and polymerize a radical polymerizable component.
  • any of a photoradical polymerization initiator and a thermal radical polymerization initiator can be used, but from the viewpoint of more effectively exhibiting the effect of excellent patterning accuracy and the like, the light
  • it is a radical polymerization initiator.
  • photoradical polymerization initiator examples include benzoins such as benzoin, benzoin methyl ether and benzoin propyl ether and benzoin butyl ether; benzyl ketals such as benzyl dimethyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone; 2,2-diethoxy-2-phenylacetophenone, 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholinyl-2- (4′-methylmercapto) benzoylpropane, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 1-hydroxycyclohexylphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, 2-hydroxy-2-benzoylpropa Acetophenones such as, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, N, N,
  • thermal radical polymerization initiator examples include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 4,4- Peroxides such as di (t-butylperoxy) butylvalerate and dicumyl peroxide; azo compounds such as 2,2'-azobisisobutyronitrile; and tetramethyltyrium disulfide.
  • Cationic polymerization initiator As the cationic polymerization initiator, any compound can be used as long as it can generate an acid under predetermined conditions.
  • a cationic photopolymerization initiator capable of generating an acid and a thermal cationic polymerization initiator capable of generating an acid by heat can be used.
  • the cationic polymerization initiator may use at least one of the photocationic polymerization initiator and the thermal cationic polymerization initiator. From the viewpoint that the damage to the peripheral member to be used due to heat can be reduced and the degree of freedom in selecting the peripheral member is increased, it is preferable that the cationic cationic polymerization initiator is used. Further, the cationic photopolymerization initiator has an advantage that the curing speed is high.
  • the cationic polymerization initiator is preferably a thermal cationic polymerization initiator from the viewpoint of facilitating formation of a cured product even in a place where light is difficult to reach.
  • a cationic polymerization initiator As such a cationic polymerization initiator, a cationic initiator described in JP-A-2016-17609 can be used.
  • the above composition preferably contains a polymer having a carboxyl group from the viewpoint of excellent developability. This is because, by including the above polymer, the composition becomes more excellent in patterning accuracy.
  • the polymer having a carboxyl group is not particularly limited as long as it has a structural unit having a carboxyl group (hereinafter, referred to as “structural unit (U1)”), and is not particularly limited. Group, an epoxy group, an oxetanyl group, a vinyl ether group, a mercapto group, a structural unit having a crosslinkable group such as an isocyanate group (hereinafter referred to as “structural unit (U2)”), and a structural unit having a silyl group (hereinafter referred to as “structure”). Unit (U3) ”).
  • the polymer having a carboxyl group may have a structural unit other than the structural units (U1) to (U3) (hereinafter, referred to as “structural unit (U4)”).
  • the structural unit (U1) is a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter, referred to as “compound (u1)”). Is preferred.
  • Examples of the compound (u1) include a monocarboxylic acid, a dicarboxylic acid, and an anhydride of a dicarboxylic acid.
  • Examples of the above monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydrophthalic acid, and 2-methacryloyloxyethylhexa. Hydrophthalic acid and the like; Examples of the dicarboxylic acid include maleic acid, fumaric acid, citraconic acid and the like; Examples of the dicarboxylic acid anhydride include the dicarboxylic acid anhydrides described above.
  • acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid or maleic anhydride is preferred from the viewpoint of copolymerization reactivity and solubility of the obtained copolymer in a developer.
  • Compound (u1) can be used alone or in combination of two or more.
  • the structural unit (U2) is preferably a structural unit derived from a polymerizable unsaturated compound having an epoxy group or an oxetanyl group (hereinafter, referred to as “compound (u2)”).
  • the compound (u2) is preferably at least one selected from the group consisting of a polymerizable unsaturated compound having an epoxy group and a polymerizable unsaturated compound having an oxetanyl group.
  • Examples of the polymerizable unsaturated compound having an epoxy group include oxiranyl (cyclo) alkyl (meth) acrylate, oxiranyl (cyclo) alkyl ⁇ -alkylacrylate, and glycidyl ether compounds having a polymerizable unsaturated bond. ;
  • Examples of the polymerizable unsaturated compound having an oxetanyl group include, for example, (meth) acrylic acid ester having an oxetanyl group.
  • the compound (u2) include:
  • Examples of the oxiranyl (meth) acrylic acid (cyclo) alkyl ester include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and (meth) acrylic acid 3, 4-epoxybutyl, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxytricyclo [ 5.2.1.02.6] decyl (meth) acrylate, and the like;
  • Examples of ⁇ -alkyl oxiranyl (cyclo) alkyl esters include glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, glycid
  • Compound (u2) can be used alone or in combination of two or more.
  • a structural unit having a (meth) acryloyloxy group can be preferably used as the structural unit having a methacryloyl group or an acryloyl group as the crosslinkable group.
  • the structural unit having the (meth) acryloyloxy group is obtained by reacting a (meth) acrylic ester having an epoxy group with a carboxyl group in the polymer.
  • the structural unit having a (meth) acryloyloxy group after the reaction is preferably a structural unit represented by the following formula (U2-1).
  • R 1000 and R 1001 are each independently a hydrogen atom or a methyl group; R 1002 is a divalent group represented by the following formula ( ⁇ ) or ( ⁇ ); Is an integer of 1 to 6, and * represents a bonding site.)
  • R 1003 is a hydrogen atom or a methyl group, and * represents a bonding site.
  • a polymer containing a polymerization inhibitor is preferably used in the presence of a suitable catalyst.
  • An unsaturated compound having an epoxy group is added to the combined solution, and the mixture is stirred for a predetermined time while being heated.
  • the catalyst include tetrabutylammonium bromide.
  • the polymerization inhibitor include p-methoxyphenol and the like.
  • the reaction temperature is preferably from 70 ° C to 100 ° C.
  • the reaction time is preferably from 8 hours to 12 hours.
  • the content ratio of the structural unit having a (meth) acryloyloxy group as a crosslinkable group is from 10 mol% to 70 mol% of all the structural units having a carboxyl group. %, More preferably from 20 mol% to 50 mol%.
  • the structural unit (U3) is preferably a structural unit derived from a polymerizable unsaturated compound having a silyl group (hereinafter, referred to as “compound (u3)”).
  • Examples of the compound (u3) include 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) ) Acryloyloxypropyltriethoxysilane and the like.
  • the above compound (u3) can be used alone or in combination of two or more.
  • the structural unit (U4) is a structural unit other than the above (U1) to (U3), and is a polymerizable unsaturated compound other than the above (u1) to (u3) (hereinafter, referred to as “compound (u4)”).
  • compound (u4) a polymerizable unsaturated compound other than the above (u1) to (u3)
  • Is preferably a structural unit derived from Examples of the compound (u4) include alkyl (meth) acrylate, cycloalkyl (meth) acrylate, aryl (meth) acrylate, aralkyl (meth) acrylate, dialkyl unsaturated dicarboxylate, Examples thereof include (meth) acrylates having a 5-membered oxygen-containing ring or a 6-membered oxygen-containing ring, vinyl aromatic compounds, conjugated diene compounds, and other polymerizable unsaturated compounds.
  • alkyl (meth) acrylates for example, methyl acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, ( Sec-butyl (meth) acrylate, t-butyl (meth) acrylate and the like;
  • cycloalkyl (meth) acrylate examples include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.02,6] decane-8-methacrylate.
  • 2-methyltetrahydropyran-2-yl acrylate and the like examples include the vinyl aromatic compound include styrene, ⁇ -methylstyrene and the like; Examples of the conjugated diene compound include 1,3-butadiene, isoprene and the like; Examples of other polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, and the like.
  • n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, tricyclo [5.2.1.02,6] decane-8 methacrylate-8 -Yl, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene and the like are preferred.
  • the above compound (u4) can be used alone or as a mixture of two or more.
  • the polymer having a carboxyl group can be synthesized by copolymerizing a mixture of the polymerizable unsaturated compounds containing the above-mentioned compounds (u1) to (u4) in the following proportions.
  • Compound (u1) preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, still more preferably 5 mol% to 15 mol%
  • Compound (u2) preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, and still more preferably 20 mol% to 30 mol%
  • Compound (u3) preferably 50 mol% or less, more preferably 1 mol% to 40 mol%, still more preferably 10 mol% to 30 mol%
  • Compound (u4) preferably 80 mol% or less, more preferably 1 mol% to 60 mol%, still more preferably 25 mol% to 50 mol%
  • a (meth) acryloyloxy group is reacted by reacting a (meth) acrylic ester having an epoxy group with a carboxyl group in a structural unit derived from the compound (u1) in the obtained copolymer. Having a structural unit.
  • the polymerizable composition containing a polymer having a carboxyl group obtained by copolymerizing a mixture of polymerizable unsaturated compounds containing the compound (u1) to the compound (u4) in the above range has good coatability. Since high resolution is achieved without impairing the pattern, it is preferable because even a fine pattern can provide a cured film whose characteristic balance is highly adjusted.
  • the weight average molecular weight (Mw) of the polymer having a carboxyl group may be any as long as a desired developability can be obtained.
  • Polymerizable component having thiol reactivity” can be used. It can be the same as the molecular weight of the high molecular weight compound in the “polymerization component”.
  • the polymer having a carboxyl group can be produced by polymerizing a mixture of the above polymerizable unsaturated compounds, preferably in a suitable solvent, preferably in the presence of a radical polymerization initiator.
  • the solvent used in the polymerization for example, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl
  • solvents can be used alone or in combination of two or more.
  • the radical polymerization initiator is not particularly limited and includes, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2 '-Azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azobis (2-methylpropionate), 2, Azo compounds such as 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) can be mentioned.
  • These radical polymerization initiators can be used alone or in combination of two or more.
  • Preferred examples of the polymer having a carboxyl group include the following polymer U-1 and polymer U-2.
  • the temperature of the solution is raised to 100 ° C., and the temperature is maintained for 1 hour to perform polymerization to obtain a solution containing a copolymer.
  • 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing the copolymer, and the mixture was stirred at 90 ° C. for 30 minutes in an air atmosphere, and then methacrylic acid was added.
  • a polymer U-1 having a weight average molecular weight Mw of 9000 obtained by adding 74 parts by mass of glycidyl acid and reacting at 90 ° C. for 10 hours can be mentioned.
  • the polymer U-1 has a structural unit (U1), a structural unit (U2) and a structural unit (U4).
  • a polymer U-2 having a weight average molecular weight Mw of 12,000 obtained by carrying out polymerization while maintaining this temperature for 5 hours can be mentioned.
  • the polymer U-2 has a structural unit (U1), a structural unit (U2), a structural unit (U3) and a structural unit (U4).
  • the content of the polymer having a carboxyl group is appropriately selected depending on the purpose of use, and is not particularly limited.
  • the content is 10 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the solid content of the composition.
  • the total content of the polymer having a carboxyl group and the polymerizable component B is appropriately selected depending on the purpose of use and is not particularly limited.
  • the total content is 10% by mass in 100 parts by mass of the solid content of the composition. It can be not less than 100 parts by mass and not more than 99 parts by mass.
  • the composition can include other components as necessary.
  • the other components include a polymer having no polymerizable group, a solvent for dissolving or dispersing the above components, and a coloring agent.
  • Polymer having no polymerizable group The polymer has no polymerizable group.
  • the polymerizable group include a radical polymerizable group and a cationic polymerizable group.
  • examples of such a polymer include polycarbonate (PC), polyethylene terephthalate (PET), polyethersulfone, polyvinylbutyral, polyphenylene ether, polyamide, polyamideimide, polyetherimide, norbornene-based resin, acrylic resin, and methacrylic resin.
  • thermoplastic resins such as isobutylene maleic anhydride copolymer resin, cyclic olefin resin, polyvinyl alcohol, polyethylene glycol, and polynivirpyrrolidone.
  • a polymer of the polymerizable component B can also be used. Further, among the above polymers having a carboxyl group, those not containing a structural unit having a crosslinkable group can be used as the polymer.
  • the weight average molecular weight (Mw) of the polymer is appropriately set according to the use of the composition and the like, and may be, for example, 1500 or more, and 1500 to 300,000.
  • the content of the polymer is appropriately selected according to the purpose of use, and is not particularly limited.
  • the content can be 10 parts by mass or more and 90 parts by mass or less per 100 parts by mass of the solid content of the composition.
  • the total content of the polymer and the polymerizable component B is appropriately selected depending on the purpose of use and is not particularly limited.
  • a total content of 10 to 99 parts by mass in 100 parts by mass of the solid content of the composition is It can be less than parts by mass.
  • the solvent is a liquid which is liquid at 25 ° C. and atmospheric pressure and is capable of dispersing or dissolving each component of the composition. Further, the solvent does not have a polymerizable group such as a radical polymerizable group and a cationic polymerizable group. Therefore, for example, among the polymerizable components B, those that are liquid at 25 ° C. and atmospheric pressure do not correspond to the above-mentioned solvents.
  • Examples of such a solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxy Ether solvents such as ethane, 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; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol
  • Terpene hydrocarbon oils Terpene hydrocarbon oils; paraffinic solvents such as mineral spirits, swazol # 310 (Cosmo Matsuyama Sekiyu KK), Solvesso # 100 (Exxon Chemical Co.); tetrasalts Halogenated aliphatic hydrocarbon solvents such as carbon, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents; aniline; triethylamine; pyridine; acetic acid; Organic solvents such as acetonitrile; carbon disulfide; N, N-dimethylformamide; N, N-dimethylacetamide; N-methylpyrrolidone; and dimethylsulfoxide.
  • paraffinic solvents such as mineral spirits, swazol # 310 (Cosmo Matsuyama Sekiyu KK), Solvesso # 100 (Exxon
  • the solvent may include water.
  • ketones, ether ester solvents and the like especially organic solvents such as propylene glycol-1-monomethyl ether-2-acetate (hereinafter also referred to as “PGMEA” or “propylene glycol monomethyl ether acetate”) and cyclohexanone are used. From the viewpoint of good compatibility with the compound A and the like.
  • PGMEA propylene glycol-1-monomethyl ether-2-acetate
  • cyclohexanone cyclohexanone
  • the content of the above solvent may be any as long as it becomes a composition having more excellent patterning accuracy and heat resistance.
  • the content can be, for example, 10 parts by mass or more and 95 parts by mass or less in 100 parts by mass of the composition of the present invention, preferably 40 parts by mass or more and 95 parts by mass or less, and more preferably 60 parts by mass or more. It is preferably 90 parts by mass or less. This is because the above content makes the composition excellent in coatability.
  • the above composition may contain a silane coupling agent as needed.
  • a silane coupling agent those having a molecular weight of 100 to 1,000 can be used.
  • a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • a silane coupling agent having an isocyanate group, a methacryloyl group, or an epoxy group such as KBE-403 is preferably used.
  • the silane coupling agents those containing a methacryloyl group, an epoxy group or the like are not contained in the polymerizable component B.
  • the composition can contain a colorant, if necessary.
  • the coloring agent include pigments, dyes, and natural pigments. These colorants can be used alone or in combination of two or more.
  • the pigment examples include a nitroso compound; a nitro compound; an azo compound; a diazo compound; a xanthene compound; a quinoline compound; an anthraquinone compound; a coumarin compound; Compound; perylene compound; diketopyrrolopyrrole compound; thioindigo compound; dioxazine compound; triphenylmethane compound; quinophthalone compound; naphthalenetetracarboxylic acid; metal complex compound of azo dye and cyanine dye; Carbon black obtained by the method, or carbon black such as acetylene black, Ketjen black or lamp black; A rack prepared or coated with an epoxy resin, a carbon black previously dispersed in a solvent in a solvent and adsorbing 20 to 200 mg / g of a resin, a carbon black having an acidic or alkaline surface treatment, Those having an average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml
  • pigments can also be used as the pigment, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71, 72; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 9 , 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139,
  • the dye examples include an azo dye, anthraquinone dye, indigoid dye, triarylmethane dye, xanthene dye, alizarin dye, acridine dye stilbene dye, thiazole dye, naphthol dye, quinoline dye, nitro dye, indamine dye, oxazine dye, and phthalocyanine dye. And dyes such as cyanine dyes. These may be used as a mixture of two or more.
  • the content of the coloring agent is not particularly limited as long as a cured product of a desired color can be obtained. In particular, it is preferably from 5 parts by mass to 60 parts by mass, and particularly preferably from 10 parts by mass to 50 parts by mass.
  • the content of the colorant is not particularly limited as long as a cured product having a desired color can be obtained. Preferably, it is preferably from 10 parts by mass to 250 parts by mass, and particularly preferably from 20 parts by mass to 200 parts by mass.
  • the other components include a colorant, an inorganic compound, a dispersant for dispersing the colorant and the inorganic compound, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, and melamine.
  • Additives can be mentioned.
  • known materials can be used, and for example, those described in International Publication WO2014 / 021023 can be used.
  • an ultraviolet absorber, an antioxidant and the like can also be used.
  • a latent ultraviolet absorber and a latent antioxidant which exhibit an ultraviolet absorbing ability and an antioxidant function by heat treatment or the like can be used.
  • a latent ultraviolet absorber and a latent antioxidant for example, those described as a latent additive described in WO 2014/021023 can be used.
  • the total content of the above additives can be 30 parts by mass or less based on 100 parts by mass of the solid content of the composition.
  • the manufacturing method of the composition may be any method as long as the above components can be blended at a desired content, and may be a method of simultaneously adding and mixing the above components. It may be a method of mixing while mixing.
  • composition and the like can be the same as the use of the composition to which the thiol generator described in the section “A. Compound” is added.
  • the cured product of the present invention is a cured product of the composition described above.
  • the cured product is excellent in patterning accuracy and heat resistance by using the above composition.
  • the cured product of the present invention uses the above-described composition.
  • the content of the composition can be the same as the content described in the section of “C. Composition”, and thus the description thereof is omitted.
  • the cured product has a polymer in which the polymerizable components B are polymerized.
  • the residual ratio of the unreacted polymerizable component B contained in the cured product is appropriately set according to the use of the cured product, and is, for example, 10 parts by mass or less in 100 parts by mass of the cured product. And preferably 1 part by mass or less. This is because the cured product has excellent heat resistance.
  • the compound A cross-links the polymerizable components B means a state where the compound A after desorbing R 1 cross-links the polymerizable components B.
  • Crosslinking refers to a state in which a thiol group generated from compound A by elimination of R 1 forms a covalent bond with a thiol-reactive group of polymerizable component B by a thiol-ene reaction or the like. .
  • the compound A crosslinks the polymerizable components B. This is because the cured product has excellent heat resistance.
  • the polymerizable component B to be crosslinked by the compound A contains at least one of the following (1) and (2). (1) Unreacted polymerizable component B remaining without polymerizing between polymerizable components B (2) Among polymers obtained by polymerizing polymerizable components B, those having a thiol-reactive group
  • the shape of the cured product in a plan view can be appropriately set according to the use of the cured product, and is preferably, for example, a pattern such as a dot or a line. This is because the effect of forming a composition excellent in patterning accuracy and heat resistance of the present invention can be more effectively exerted.
  • the method for producing the cured product is not particularly limited as long as the cured product of the composition can be formed into a desired shape.
  • a production method for example, the production method described in the section of “E. Production method of cured product” described later can be used.
  • the production method of the present invention includes a step of crosslinking.
  • each step of the production method of the present invention will be described in detail.
  • the cross-linking step in the production method of the present invention is a step of cross-linking the polymerizable components B with each other by the compound represented by the general formula (A).
  • Method as a method of cross-linking in this step release the protective group R 1 from the compound A de by thiol groups generated as long as it can crosslink the polymerizable component B together, for example, the heat treatment of the above-mentioned compound A Can be mentioned.
  • the heating temperature at which the compound A is heated may be a temperature at which R 1 can be desorbed from the compound A, and may be, for example, the same as that described in the above section “A. Compound”. .
  • the composition or a cured product thereof (a composition after a polymerization step described later) using a known heating means such as an oven can be used.
  • the cross-linking step may be performed simultaneously with the post-bake step described later.
  • the polymerizable component B crosslinked by this step contains at least one of the following (1) and (2) when this step is performed after the below-described polymerization step.
  • (1) Unreacted polymerizable component B remaining without polymerizing between polymerizable components B (2) Among polymers obtained by polymerizing polymerizable components B, those having a thiol-reactive group
  • Step of polymerizing The method for producing a cured product preferably includes a step of polymerizing the polymerizable components B with each other. This is because patterning accuracy and heat resistance are improved.
  • the method of polymerizing the polymerizable components B in the present step may be any method capable of polymerizing the polymerizable components B.
  • a composition containing a polymerization initiator together with the polymerizable component B is used as the composition. Methods can be mentioned.
  • the above polymerization method differs depending on the type of radical polymerization initiator.
  • the composition when the composition contains a photo-radical polymerization initiator as a polymerization initiator, a photo-polymerization initiator such as a photo-cationic polymerization initiator, the composition is irradiated with light to polymerize the polymerizable components B with each other.
  • a polymerization method can be used.
  • the light applied to the composition may include light having a wavelength of 300 nm to 450 nm.
  • the light source for the light irradiation include ultrahigh-pressure mercury, mercury vapor arc, carbon arc, xenon arc, and the like.
  • Laser light may be used as the irradiation light.
  • a laser light having a wavelength of 340 to 430 nm can be used.
  • a light source of the laser light a light source 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.
  • the composition may contain a sensitizing dye that absorbs the visible to infrared region.
  • the above polymerization method for example, when the composition contains a thermal radical polymerization initiator as a polymerization initiator, a thermal polymerization initiator such as a thermal cationic polymerization initiator, the composition is subjected to heat treatment, polymerizable A method of polymerizing the components B can be used.
  • the heating temperature may be any temperature at which the composition can be cured stably, and may be 60 ° C or higher, preferably 100 ° C or higher and 300 ° C or lower.
  • the heating time can be about 10 seconds to 3 hours.
  • the type of the polymerization method may include only one type, or may include two or more types.
  • the timing of performing the step of polymerizing may be before or after the step of cross-linking, but from the viewpoint of patterning accuracy and the ability to produce a patterned cured product, the step of cross-linking may be performed. Is preferably before.
  • the method for producing a cured product may include other steps as necessary.
  • the above-mentioned other steps include, after the above-mentioned polymerization step, a development step of removing a non-polymerized portion in the coating film of the composition to obtain a patterned cured product, and after the above-mentioned polymerization step, a post-baking step of heat-treating the cured product.
  • a method of applying an alkali developing solution to the unpolymerized portion for example, a method of applying an alkali developing solution to the unpolymerized portion can be mentioned.
  • the alkali developer a solution generally used as an alkali developer such as an aqueous solution of tetramethylammonium hydroxide (TMAH) or an aqueous solution of potassium hydroxide can be used.
  • TMAH tetramethylammonium hydroxide
  • the timing of performing the developing step may be any time after the step of polymerizing, but is preferably before the step of desorption from the viewpoint that patterning accuracy is high and a patterned cured product can be manufactured. .
  • the heating conditions in the post-baking step are not particularly limited as long as the strength and the like of the cured product obtained by the polymerization step can be improved.
  • the heating temperature can be 100 ° C. or more and 300 ° C. or less, and is 120 ° C. or more. It is preferable that the temperature be 150 ° C. or higher, and that the temperature be 200 ° C. to 250 ° C. for 20 minutes to 90 minutes.
  • the post-baking temperature is in the above-mentioned range, the post-baking step and the cross-linking step can be easily performed simultaneously after the polymerization step.
  • the heating conditions in the prebaking step may be any conditions as long as the solvent in the composition can be removed, and may be, for example, 70 to 150 ° C. for 30 to 300 seconds.
  • the heating conditions in the prebaking step are preferably performed at a temperature equal to or lower than the desorption temperature of the compound A, for example, from the viewpoint of facilitating the polymerization step and the crosslinking step in this order. From such a viewpoint, the heating conditions in the prebaking step are preferably lower than 150 ° C, more preferably lower than 120 ° C, particularly preferably lower than 100 ° C, and preferably 90 ° C or lower. Preferably, there is.
  • the composition in the step of forming the coating film As a method of applying the composition in the step of forming the coating film, a known method such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, and immersion can be used.
  • the coating film can be formed on a substrate.
  • the base material can be appropriately set according to the use of the cured product and the like, and examples thereof include those containing soda glass, quartz glass, a semiconductor substrate, metal, paper, plastic, and the like. After the cured product is formed on the substrate, the cured product may be peeled off from the substrate or used by transferring from the substrate to another adherend.
  • the present invention is not limited to the above embodiment.
  • the above embodiment is an exemplification, and has substantially the same configuration as the technical idea described in the scope of the claims of the present invention. It is included in the technical scope of the invention.
  • Example 1 A mixture of 0.01 mol of a polyfunctional thiol (TS-G, manufactured by Shikoku Chemicals), 0.05 mol of di-tert-butyl dicarbonate and 30 g of pyridine represented by the following formula (A6-1 ′) is added at room temperature under a nitrogen atmosphere. 0.002 mol of 4-dimethylaminopyridine was added, and the mixture was stirred at 60 ° C. for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, and 200 g of chloroform was added to perform oil / water separation. The organic layer was dried over anhydrous sodium sulfate, dried under reduced pressure at 60 ° C. for 3 hours, and the solvent was distilled off to obtain a compound represented by the following formula (A6-1). It was confirmed by 1 H-NMR that the obtained compound was a compound represented by the following formula (A6-1). The results are shown in Table 1 below.
  • Example 7 0.06 mol of a polyfunctional thiol (TS-G manufactured by Shikoku Chemicals) represented by the following formula (A6-1 ′) is charged into a 500 mL two-necked round bottom flask, dried under reduced pressure and replaced with nitrogen, and then dried. 42 mL of DMF (manufactured by Kanto Chemical) and 0.83 mL of triethylamine were added, and the mixture was cooled to 0 ° C. Next, 0.24 mol of phenyl isocyanate (manufactured by Kanto Kagaku) was added with stirring, and after stirring for 30 minutes, the temperature was returned to room temperature.
  • T-G polyfunctional thiol
  • the polymer U-1 has the above-mentioned structural unit (U1), structural unit (U2) and structural unit (U4).
  • the polymer U1 is a radical polymerizable compound and has an acid group.
  • Examples 2-1 to 2-22 and Comparative Examples 2-1 to 2-9 Compound A, thiol compound, polymerizable component B, polymerization initiator, pigment dispersion, coupling agent, and solvent were mixed according to the formulations shown in Tables 2 to 4 below, and the mixture was stirred at 25 ° C. for 1 hour to obtain a composition. I got The following materials were used for each component. In addition, the compounding quantity in a table
  • Compound A A-1: The compound represented by the general formula (A6-1) prepared in Example 1 A-2: The compound A- represented by the general formula (A4-1) prepared in Example 2 3: Compound A-4 represented by the above general formula (A3b-1) produced in Example 3: Compound A-5 represented by the above general formula (A2-1) produced in Example 4: Compound A-6 represented by the above general formula (A5-1) produced in Example 5: Compound A-7 represented by the above general formula (A3a-1) produced in Example 6: Example Compound A-8 represented by the above general formula (A6-2) produced in Example 7: Compound A-9 represented by the above general formula (A4-2) produced in Example 8: Compound A-10 produced by the above general formula (A2-2) produced: Compound represented by the above general formula (A5-2) produced in Example 10
  • A-1 ′ Compound represented by the above formula (A6-1 ′)
  • A-2 ′ Compound A-3 ′ represented by the above formula (A4-1 ′): Compound represented by the above formula (A3b-1 ′)
  • C-1 a compound represented by the following formula (C1) (photoradical polymerization initiator, oxime esters)
  • C-2 Compound represented by the following formula (C2) (photoradical polymerization initiator, oxime esters)
  • C-3 Irgacure TPO manufactured by BASF (photo-radical polymerization initiator, acylphosphine oxides)
  • C-4 a compound represented by the following formula (C4) (photoradical polymerization initiator, acetophenones)
  • the obtained pattern was observed with an optical microscope, and the line width of a portion corresponding to the mask opening was measured.
  • ⁇ when the line width was more than ⁇ 5 and ⁇ 10 ⁇ m, and ⁇ when the line width exceeded ⁇ 10 ⁇ m.
  • Tables 2 and 3 The results are shown in Tables 2 and 3 below.
  • the line width is controlled so that there is no difference from the set line width, and it can be determined that the patterning accuracy is good.
  • FIGS. 1 and 2 show examples of an optical microscope observation image and an SEM observation image when a wrinkle occurs in a pattern
  • FIGS. 4 and 4 show examples of an optical microscope observation image and an SEM observation image when a wrinkle occurs in a pattern.
  • FIG. 1 and 2 show examples of an optical microscope observation image and an SEM observation image when a wrinkle occurs in a pattern
  • FIGS. 4 and 4 show examples of an optical microscope observation image and an SEM observation image when a wrinkle occurs in a pattern.
  • FIG. When wrinkles occur a striped pattern presumed to be caused by uneven thickness is observed as shown in FIGS. ⁇ : No wrinkles were observed.
  • ⁇ Wrinkles were observed. If there is no wrinkle, it can be determined that the pattern form is good.
  • Compound A in which the thiol group is protected by R 1 has a higher patterning accuracy and heat resistance than Examples in which a thiol compound was used instead of Compound A and Examples in which the thiol compound was not contained. It was confirmed that an excellent composition could be formed.
  • Compound A is a compound represented by the above general formula (A6) such as the above formulas (A6-1) and (A6-2), and the above general formula (A4) such as (A4-1) and (A4-2). It was confirmed that the compound represented by the formula can form a composition having particularly excellent patterning accuracy and heat resistance.
  • Examples 2-23 to 2-28 and Comparative Examples 2-10 to 2-15 Compound A, thiol compound, polymerizable component B, polymerization initiator, pigment dispersion, coupling agent, and solvent are mixed according to the formulations shown in Tables 5 and 6 below, and the mixture is stirred at 25 ° C. for 1 hour to obtain a composition. I got The above-mentioned materials were used for each component. In addition, the compounding quantity in a table
  • surface represents the mass part of each component.
  • compositions of Examples and Comparative Examples were spin-coated on a glass substrate so that the film thickness after post-baking was 3 ⁇ m, and prebaked at 90 ° C. for 120 seconds using a hot plate. Cool at 60 ° C for 60 seconds. Thereafter, exposure was performed using a superhigh pressure mercury lamp through a photomask (mask opening 30 ⁇ m) (exposure gap 300 ⁇ m, exposure amount 40 mJ / cm 2 ). Using a 0.04% by mass aqueous KOH solution as a developer, spray development was performed at 23 ° C. and a discharge pressure of 0.15 MPa, and the time required for the cured portion located at the opening of the mask to separate from the substrate was measured.
  • the evaluation was performed according to the following criteria. ⁇ : The time until peeling was 100 seconds or more from the start of development. ⁇ : The time until peeling was 80 seconds or more and less than 100 seconds from the start of development. X: The time until peeling was more than 60 seconds and less than 80 seconds from the start of development.
  • a composition having more excellent development margin was obtained in the case where it was present. Since the equivalent of the protected thiol group in the compound A is A-2> A-6, it is assumed that the crosslink density is higher when A-6 is used. However, since A-2 having a hexafunctionality and a high molecular weight has high hydrophobicity, a cured product having higher resistance to an alkali developing solution can be obtained. It is presumed that a stable cured product was formed even after long-term exposure.
  • Example 2-24 and Comparative Examples 2-11 and 2-14 were spin-coated on a glass substrate so that the thickness after prebaking was 4.0 ⁇ m, to form a coating film.
  • pre-baking at 90 ° C. for 120 seconds using a hot plate
  • cooling was performed at 23 ° C. for 60 seconds.
  • exposure was performed with an exposure gap of 300 ⁇ m through a photomask using an ultrahigh pressure mercury lamp.
  • the exposed coating film is developed using a 0.04 mass% KOH aqueous solution as a developing solution for 60 seconds, washed well with water, and post-baked at 230 ° C. for 20 minutes using a clean oven to fix the pattern.
  • a sample for evaluation was obtained.
  • the sample for evaluation was produced combining the following levels as a photomask opening width and exposure amount.
  • Mask opening width (5 levels): 2.0 ⁇ m, 10.0 ⁇ m, 30.0 ⁇ m, 50.0 ⁇ m, 100.0 ⁇ m
  • the obtained pattern was observed with an optical microscope, and the line width corresponding to the mask opening width was measured. The results are shown in Table 7 below. The line width is controlled so that there is no difference from the set line width, and it can be determined that the patterning accuracy is good.
  • Heat resistance 3 An evaluation sample was obtained using the same method as that described in “8. Patterning accuracy 2”. The film thickness of the obtained pattern was measured using DEKTAKXT manufactured by Bruker. The results are shown in Table 7 below. It can be judged that the heat resistance is good as there is no difference with respect to the thickness after prebaking.

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  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

Le problème à résoudre par la présente invention concerne la fourniture d'un composé qui peut former une composition ayant une excellente précision de formation de motifs et une excellente résistance à la chaleur. La présente invention concerne un composé représenté par la formule générale suivante (1). (Dans la formule, R1 représente un groupe aliphatique monovalent en C1-C40, un groupe contenant un cycle hydrocarboné aromatique en C6-C35 monovalent, un groupe contenant un hétérocycle en C2-C35 monovalent ou un groupe silyle en C0-C40 monovalent, X représente un groupe aliphatique en C1-C40 ayant une valence du même nombre que n, un groupe contenant un cycle hydrocarboné aromatique en C6-C35, ou un groupe contenant un hétérocycle en C2-C35, et n représente un nombre entier de 2 à 10.)
PCT/JP2019/031213 2018-08-09 2019-08-07 Composé, générateur de thiol, composition, produit durci, et procédé de production de produit durci WO2020032131A1 (fr)

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KR1020207035593A KR20210042046A (ko) 2018-08-09 2019-08-07 화합물, 티올 발생제, 조성물, 경화물 및 경화물의 제조 방법
CN201980046590.2A CN112424165A (zh) 2018-08-09 2019-08-07 化合物、硫醇产生剂、组合物、固化物及固化物的制造方法
JP2020535850A JP7422076B2 (ja) 2018-08-09 2019-08-07 化合物、チオール発生剤、組成物、硬化物及び硬化物の製造方法

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TW202017901A (zh) 2020-05-16
JPWO2020032131A1 (ja) 2021-08-26

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