JP7422076B2 - Compound, thiol generator, composition, cured product, and method for producing cured product - Google Patents

Description

The present invention relates to a compound capable of forming a composition with excellent patterning accuracy and heat resistance.

A 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.
Moreover, such a polymerization reaction proceeds even in the absence of a polymerization initiator.
Therefore, by adding a thiol compound to the acrylic monomer together with a polymerization initiator, the polymerization reaction of the acrylic monomer etc. by the polymerization initiator and the reaction of the acrylic monomer etc. by the thiol compound can be carried out simultaneously.
Utilizing such properties, thiol compounds are used to improve the sensitivity of photocurable compositions (for example, Patent Document 1).

Japanese Patent Application Publication No. 2006-154774

A method for forming a patterned cured product using a photocurable composition is to expose a coating film of the photocurable composition to light in a pattern, remove the uncured coating film with a developer, and then heat treatment. (post-bake) is known.
When 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 with excellent heat resistance such as less shrinkage during the heat treatment is obtained. be able to.
However, there was a problem in that the patterning accuracy decreased due to the addition of the thiol compound.
In addition, the present inventors investigated increasing the amount of polymerization initiator added in order to improve heat resistance and the like. However, similar to the case of adding a thiol compound, although heat resistance can be improved, there is a problem in that patterning accuracy is reduced.

The present invention has been made in view of the above problems, and its main purpose is to provide a compound capable of forming a composition with excellent patterning accuracy and heat resistance.

The present inventors conducted intensive studies to solve the above problems, and found that the progress of reactions caused by thiol compounds, such as thiol-ene reactions, is suppressed until after patterning is completed, and the above reactions can proceed after patterning is completed. It has been found that by using the compound, it is possible to form a composition that is excellent in both patterning accuracy and heat resistance.
The present inventors have completed the present invention based on these findings.

That is, the present invention is a compound represented by the following general formula (A) (hereinafter also referred to as "compound A").

(In the formula, 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, and a monovalent group having 2 to 35 carbon atoms. Represents a heterocycle-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 heterocycle-containing group having 2 to 35 carbon atoms and having the same valence as n; ,
One or more methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocycle-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 there a case where it is substituted with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S-, or -SO ₂ -? , or may be replaced with a group that combines these groups with the conditions that oxygen atoms are not adjacent,
n represents an integer of 2 or more and 10 or less. )

According to the present invention, by having the above structure, the compound A can form a composition with excellent patterning accuracy and heat resistance.

In the present invention, the compound A is preferably a compound represented by the following general formula (A1), (A2), (A3), (A4), (A5) or (A6). Since the compound A has the above structure, it becomes a compound that can form a composition with excellent patterning accuracy and heat resistance, and in particular, it becomes possible to form a composition with excellent heat resistance.

(In the formula, 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 from 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 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 general formula (101) or (102),
Any two or more of R ³¹ , R ³² , R ³³ and R ³⁴ are 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 general formula (101) or (102),
Any two or more of R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are the following general formula (101),
L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ and L ⁴⁶ represent an alkylene group having 1 to 10 carbon atoms,
R ⁵¹ , R ⁵² and R ⁵³ each independently represent the following general formula (101) or (102),
Any two or more of R ⁵¹ , R ⁵² and R ⁵³ are the following general formula (101),
L ⁵¹ , L ⁵² and L ⁵³ represent an alkylene group having 1 to 10 carbon atoms,
R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent the following general formula (101) or (102),
Any two or more of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are the following general formula (101),
L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ represent an alkylene group having 1 to 10 carbon atoms,
R ⁶⁵ and R ⁶⁶ each independently represent a hydrogen atom or a monovalent aliphatic group having 1 to 40 carbon atoms,
One or more methylene groups in the aliphatic group 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- It may be substituted with a group selected from CO-NH-, -NR'-, -SS- or -SO ₂ -, or these groups are combined under the condition that oxygen atoms are not adjacent to each other. It may be replaced by a group. )

(In the formula, 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, and a monovalent group having 2 to 35 carbon atoms. Represents a heterocycle-containing group or a monovalent silyl group having 0 to 40 carbon atoms,
* represents the joint location,
One or more methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocycle-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 there a case where it is substituted with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S-, or -SO ₂ -? , or may be replaced by a group combining these groups with oxygen atoms not adjacent to each other. )

In the present invention, R ²¹ , R ²² and R ²³ in the general formula (A2) each independently represent the general formula (101), and R ³¹ , R in the general formula (A3) ³² , R ³³ and R ³⁴ each independently represent the above general formula (101), and R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ in the above general formula (A4) All are each independently the above general formula (101), and all of R ⁵¹ , R ⁵² and R ⁵³ in the above general formula (A5) are each independently the above general formula (101), It is preferable that all of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ in the above general formula (A6) each independently represent the above general formula (101).
The above ^R21 , ^R22 , ^R23 , ^{R31 , R32} , R33, ^R34 , ^R41 , ^{R42 ,} R43, ^R44 , ^R45 , ^R46 , ^R51 , ^R52 , ^R53 , R This is because when ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are the above-mentioned groups, the compound A can form a composition with better patterning accuracy and heat resistance.

In the present invention, the compound A is preferably a compound represented by the general formula (A4) or (A6). This is because the above-mentioned compound A enables formation of a composition with excellent patterning accuracy and heat resistance.

In the present invention, R ¹ is a monovalent aliphatic group having 1 to 40 carbon atoms or a monovalent aliphatic group in which the terminal methylene group on the sulfur atom side is substituted with -CO-O- or -CO-NR- is preferably an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms. This is because when R ¹ is the group described above, the compound A can form a composition with better patterning accuracy and heat resistance.

The present invention is a thiol generator containing the above-mentioned compound.

According to the present invention, by including the compound A, the thiol generator can form a composition with excellent patterning accuracy and heat resistance.

The present invention is a composition having a compound represented by the following general formula (A) and a polymerizable component having thiol reactivity (hereinafter sometimes referred to as polymerizable component B).

(In the formula, 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, and a monovalent group having 2 to 35 carbon atoms. Represents a heterocycle-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 heterocycle-containing group having 2 to 35 carbon atoms and having the same valence as n; ,
One or more methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocycle-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 there a case where it is substituted with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S-, or -SO ₂ -? , or may be replaced with a group that combines these groups with the conditions that oxygen atoms are not adjacent,
n represents an integer of 2 or more and 10 or less. )

According to the present invention, since the composition contains the compound A, it has excellent patterning accuracy and heat resistance.

In the present invention, it is preferable that the polymerizable component having thiol reactivity includes a radically polymerizable compound. This is because the above composition has an excellent curing speed. This is also because crosslinking using the above compound A is easy.

The present invention is a cured product of the above composition.

According to the present invention, since the cured product contains the compound A, it has excellent patterning accuracy and heat resistance.

The present invention provides a method for producing a cured product, which includes a step of crosslinking the thiol-reactive polymerizable components with each other using a compound represented by the general formula (A).

According to the present invention, by crosslinking the polymerizable component B with the compound A, a cured product with excellent heat resistance can be produced.

In the present invention, it is preferable to have a step of polymerizing the above-mentioned polymerizable components having thiol reactivity. This is because the patterning accuracy and heat resistance are excellent.

According to the present invention, it is possible to provide a compound that can form a composition with excellent patterning accuracy and heat resistance.

An example of an optical microscope observation image where wrinkles occur in the pattern. An example of an SEM observation image when wrinkles occur in the pattern. An example of an optical microscope observation image when there are no wrinkles in the pattern. An example of an SEM observation image when there are no wrinkles in the pattern.

The present invention relates to a compound, a thiol generator using the same, a composition, a cured product, and a method for producing the cured product.
Hereinafter, the compound, thiol generator, composition, cured product, and method for producing the cured product of the present invention will be explained in detail.

A. Compound First, the compound of the present invention will be explained.
The compound of the present invention is a compound represented by the following general formula (A) (hereinafter also referred to as "compound A").

(In the formula, 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, and a monovalent group having 2 to 35 carbon atoms. Represents a heterocycle-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 heterocycle-containing group having 2 to 35 carbon atoms and having the same valence as n; ,
One or more methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocycle-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 there a case where it is substituted with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S-, or -SO ₂ -? , or may be replaced with a group that combines these groups with the conditions that oxygen atoms are not adjacent,
n represents an integer of 2 or more and 10 or less. )

According to the present invention, by having the above structure, the compound A can form a composition with excellent patterning accuracy and heat resistance.
The reason why the compound A, having the above structure, can form a composition with excellent patterning accuracy and heat resistance is surmised as follows.

Since the thiol group of the compound A is protected by ^R1 , the polymerizable component B of the compound A can be used until after patterning is completed, for example, until after the step of polymerizing the polymerizable components B in the composition and the development step. The progress of the crosslinking reaction that crosslinks them can be suppressed.
As a result, the compound A can suppress the curing of the composition from proceeding beyond the desired pattern during the polymerization step or during the development step, resulting in excellent patterning accuracy.
In addition, the compound A enables a crosslinking reaction in which the polymerizable components B are crosslinked with each other by removing the protective group R ¹ and generating two or more thiol groups, for example, by heat treatment or the like. As the crosslinking reaction progresses, the crosslinking density of the cured product improves.
As a result, it is possible to obtain a cured product that exhibits less shrinkage during heat treatment such as post-baking, that is, a cured product that has excellent heat resistance.
From the above, the compound A can form a composition with excellent patterning accuracy and heat resistance.
Moreover, since the crosslinking reaction proceeds even in the absence of a polymerization initiator, it can proceed not only on the surface of the cured product but also in a deep part from the surface of the cured product in the thickness direction. As a result, the difference in crosslinking density between the front side and the backside of the cured product becomes small, and, for example, the occurrence of warping and wrinkles due to the difference in crosslinking density is suppressed.
In addition, due to the effect of providing excellent patterning accuracy, the above compound A facilitates the formation of a patterned cured product with a narrow line width, and has an excellent exposure margin with less variation in line width due to variations in exposure time. compositions can be easily obtained.
Furthermore, due to the effect that it is possible to obtain a cured product with excellent heat resistance, the above compound A can be used to form a member that requires heat treatment as a curing treatment, thereby making it possible to form a member with a thick film thickness. It becomes easier.
Furthermore, by simultaneously achieving the effect of facilitating the formation of a pattern-like cured product with a narrow line width and the effect of facilitating the formation of a thick film thickness, for example, it is possible to easily form a pattern-like cured product with a fine line width and a high aspect ratio. It becomes easier to form a cured product. In addition, when forming a cured product with a high aspect ratio, the coating film of the composition can be easily made into a thin film, and, for example, it is possible to exhibit the effect that it is easy to achieve cost reduction.
Further, as a method of forming a cured product having a high aspect ratio without using the above-mentioned compound A, a method of reducing the exposure amount may also be considered. In this case, it is assumed that the degree of curing of the cured product will decrease and the development margin will decrease as a result. On the other hand, when the above compound A is used, it is easy to form a patterned cured product with a high aspect ratio, so there is no need to reduce the exposure amount, and a patterned product with a high development margin can be formed. A cured product can be easily obtained.
From the above, the above compound A can be used in a composition for forming a patterned cured product, and has excellent patterning accuracy and heat resistance, and a patterned cured product with a narrow line width and a patterned cured product with a high aspect ratio. A composition suitable for the formation of a composition can be obtained. Moreover, the above compound A provides a composition with excellent exposure margin and development margin when forming a patterned cured product, and excellent process passability.
In addition, by adding Compound A to the curable composition, it is possible to improve the resistance of the cured product to an alkaline developer during development after curing treatment by exposure. Therefore, the composition containing the above compound can stably form a patterned cured product despite variations in alkali development time. For this reason, it is possible to obtain an excellent development margin in the developing process, and from this result, it is easy to obtain excellent patterning accuracy.
From the above, Compound A exhibits excellent patterning accuracy during the polymerization process, excellent development margin during the development process, and excellent development margin during the subsequent heat treatment process such as the post-bake process. This allows for excellent heat resistance to be exhibited in a well-balanced manner, resulting in excellent patterning accuracy and heat resistance as a whole. For this reason, the compound A is particularly suitable for, for example, a curable composition for forming a patterned cured product.

The monovalent aliphatic group having 1 to 40 carbon atoms represented by R ¹ above may be any group that does not contain an aromatic hydrocarbon ring or a heterocycle, such as an alkyl group having 1 to 40 carbon atoms. group, 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 of the hydrogen atoms of these groups are as described below. Examples include groups substituted with substituents.
In the present invention, an aliphatic group refers to a group obtained by removing an arbitrary atom from an aliphatic compound.

Examples of the alkyl group having 1 to 40 carbon atoms include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-pentyl, tert-pentyl, cyclopentyl, and hexyl. , 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl, adamantyl, etc. It will be done.

Examples of the alkenyl group having 2 to 40 carbon atoms include vinyl, ethylene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl. , 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl and 4,8,12-tetradecatrienylallyl.

The above-mentioned 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 above-mentioned 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 above-mentioned cycloalkylalkyl group having 4 to 40 carbon atoms means a group having 4 to 40 carbon atoms in which the hydrogen atom of an alkyl group is substituted with a cycloalkyl group. Examples of the cycloalkylalkyl group having 4 to 40 carbon atoms include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, and 2-cyclononylethyl. , 2-cyclodecylethyl, 3-adamantylpropyl and decahydronaphthylpropyl.

The monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, represented by R ¹ above, may be any group containing an aromatic hydrocarbon ring, such as aryl having 6 to 35 carbon atoms. groups, arylalkyl groups having 7 to 35 carbon atoms, and groups in which one or more of the hydrogen atoms of these groups are substituted with substituents described below.
Further, the aromatic hydrocarbon ring-containing group usually does not contain a heterocyclic group.

Examples of the aryl group having 6 to 35 carbon atoms include phenyl, naphthyl, anthracenyl, and the like.

Examples of the arylalkyl group having 7 to 35 carbon atoms include benzyl, fluorenyl, indenyl, and 9-fluorenylmethyl groups.

The monovalent heterocycle-containing group having 2 to 35 carbon atoms represented by R ¹ above may be any group containing a heterocycle, 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-piperidon-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidin-3-yl, and one or more of the hydrogen atoms of these groups are as described below. Examples include groups substituted with substituents.

The monovalent silyl group having 0 to 40 carbon atoms represented by R ¹ above may be one containing a silicon atom, such as a silyl group in which the hydrogen atom is unsubstituted, or a silyl group in which the 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 substituents described below, and the like.
Examples of the substituted silyl groups include monoalkylsilyl groups, monoarylsilyl groups, dialkylsilyl groups, diarylsilyl groups, trialkylsilyl groups, triarylsilyl groups, monoalkyldiarylsilyl groups, and dialkylmonoarylsilyl groups. Can be mentioned.
Examples of the monoalkylsilyl group include a monomethylsilyl group, a monoethylsilyl group, a monobutylsilyl group, a monoisopropylsilyl group, a monodecanesilyl group, a monoicosanesilyl group, a monotriacontanesilyl group, and the like.
Examples of the monoarylsilyl group include a monophenylsilyl group, a monotolylsilyl group, a mononaphthylsilyl group, and a monoanthrylsilyl group.
Examples of the dialkylsilyl group include dimethylsilyl group, diethylsilyl group, dimethylethylsilyl group, diisopropylsilyl group, dibutylsilyl group, dioctylsilyl group, didecanesilyl group, and the like.
Examples of the diarylsilyl group include diphenylsilyl group and ditolylsilyl group.
Examples of the trialkylsilyl group include trimethylsilyl group, triethylsilyl group, dimethylethylsilyl group, triisopropylsilyl group, tributylsilyl group, trioctylsilyl group, and the like.
Examples of the triarylsilyl group include a triphenylsilyl group and a tritolylsilyl 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 the methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocycle-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 -, even if substituted with a group selected from It may be substituted with a group that is a combination of these groups under the condition that the oxygen atoms are not adjacent to each other.
That is, in R ¹ , one or more methylene groups in an aliphatic group, an aromatic hydrocarbon ring-containing group, a heterocycle-containing group, and a silyl group are -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 in which these groups are not adjacent to each other.
The above 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 atoms among the alkyl groups represented by R ¹ Here are some things that meet the criteria.

Unless otherwise specified, each functional group such as an aliphatic group, an aromatic hydrocarbon ring-containing group, a heterocycle-containing group, and a silyl group in R ¹ above is an unsubstituted group having no substituent or a substituent. It is a group having
A substituent that substitutes one or more hydrogen atoms in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocycle-containing group, and silyl group, more specifically, the alkyl group and alkenyl group described above. , a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an arylalkyl group, a heterocycle-containing group, and a silyl group. Examples of substituents that replace one or more hydrogen atoms 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, Acyl groups such as n-octadecyloxycarbonyl and carbamoyl; Acyloxy groups 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, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, Substituted amino groups such as sulfamoylamino, N,N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamido group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group Examples include salts of groups, imido groups, carbamoyl groups, sulfonamide groups, phosphonic acid groups, phosphoric acid groups, carboxyl groups, sulfo groups, phosphonic acid groups, and phosphoric acid groups.
In addition, the number of carbon atoms when the hydrogen atoms of the aliphatic group having 1 to 40 carbon atoms are substituted refers to the number of carbon atoms after the hydrogen atoms are substituted, and the number of carbon atoms before the hydrogen atoms are substituted. It does not refer to the number of carbon atoms in The same applies to cases where hydrogen atoms in other groups are substituted.
In addition, the number of carbon atoms when the methylene group in the aliphatic group having 1 to 40 carbon atoms is substituted refers to the number of carbon atoms after the methylene group is substituted, and the number of carbon atoms after the methylene group is substituted. It does not refer to the previous number of carbon atoms. The same applies to cases where methylene groups in other groups are substituted.

From the viewpoint of obtaining a compound capable of forming a composition with excellent patterning accuracy and heat resistance, R ¹ is a monovalent aliphatic group having 1 to 40 carbon atoms, and a monovalent aliphatic group having 6 to 40 carbon atoms. 35 aromatic hydrocarbon ring-containing group, monovalent heterocycle-containing group having 2 to 35 carbon atoms, or monovalent silyl group having 0 to 40 carbon atoms, the methylene group at the end on the sulfur atom side is -CO-O Monovalent aliphatic group having 1 to 40 carbon atoms, monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, monovalent carbon atom number substituted with - or -CO-NH- It is preferably a group containing 2 to 35 heterocycles or a monovalent silyl group having 0 to 40 carbon atoms.
That is, the above 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. Preferably, the ring-containing group or the monovalent silyl group having 0 to 40 carbon atoms has a structure in which the methylene group at the end on the sulfur atom side is replaced with -CO-O- or -CO-NH-.

The above 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 on the sulfur atom side being substituted with -CO-O- or -CO-NH-. More preferably, it is an aromatic hydrocarbon ring-containing group, and furthermore, an alkyl group having 1 to 40 carbon atoms or having a carbon atom number substituted with -CO-O- or -CO-NH- at the terminal on the sulfur atom side. Preferably it is an arylalkyl group of 6 to 35. In particular, an alkyl group having 1 to 40 carbon atoms whose terminal end on the sulfur atom side is substituted with -CO-O-, that is, -CO-O-R'' (where R'' has a substituent) A group represented by an alkyl group having 1 to 39 carbon atoms) or an arylalkyl group having 6 to 35 carbon atoms whose terminal end on the sulfur atom side is substituted with -CO-NH-, that is, -CO-NH - Be a group represented by 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) is preferable, and a group represented by -CO-OR'' is especially preferable. This is because, when R ¹ is the group described above, the compound A can form a composition with better patterning accuracy and heat resistance.
That is, in R ¹ above, the methylene group at the terminal on 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 A group having a structure substituted with -O- or -CO-NH- is more preferable, and furthermore, a group having a structure substituted with -O- or -CO-NH- is more preferable, and furthermore, a group having a structure substituted with -O- or -CO-NH- is more preferable, and furthermore, a group with a structure substituted with -O- or -CO-NH- is more preferable, and furthermore, a group with a structure substituted with sulfur atom side of an alkyl group having 1 to 40 carbon atoms or an arylalkyl group having 6 to 35 carbon atoms is preferable. The methylene group preferably has a structure substituted with -CO-O- or -CO-NH-. In particular, a group having a structure in which the methylene group at the end on the sulfur atom side of an alkyl group having 1 to 40 carbon atoms is substituted with -CO-O-, that is, -CO-O-R''(R'' is a substituted The methylene group at the end on the sulfur atom side of the group represented by (alkyl group having 1 to 39 carbon atoms which may have a group) or the arylalkyl group having 6 to 35 carbon atoms is -CO-NH- A group having a structure substituted with, i.e., -CO-NH-R'''(R''' is an aryl group having 6 to 34 carbon atoms which may have a substituent, or a group having 6 to 34 carbon atoms) A group represented by an arylalkyl group) is preferable, and a group represented by -CO-OR'' is especially preferable.

In the present invention, the above R'' is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, particularly 1 to 20 carbon atoms which may have a substituent. It is preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an unsubstituted alkyl group having 1 to 8 carbon atoms, and particularly preferably an unsubstituted alkyl group having 3 to 6 carbon atoms. are preferable, and particularly preferable are iso-propyl, n-butyl, sec-butyl, tert-butyl, iso-butyl, n-pentyl, iso-pentyl, and tert-pentyl, especially n- Butyl, sec-butyl, tert-butyl, iso-butyl, tert-butyl, that is, R ¹ is preferably a group represented by -CO-O-C ₄ H ₉ , especially R'' It is preferred that is tert-butyl, that is, R ¹ is a -CO-O-tert-butyl group.
Furthermore, R''' is preferably an arylalkyl group having 6 to 12 carbon atoms. This is because when the R'' and R''' are the groups described above, in the compound A, the elimination of R ¹ can be easily controlled.

The above n is an integer of 2 or more and 10 or less, but from the viewpoint of obtaining a compound capable of forming a composition with excellent patterning accuracy and heat resistance, it is preferably 3 or more and 8 or less, and particularly, It is preferably 4 or more and 7 or less, particularly preferably 4 or more and 6 or less. This is because when n is within the above range, the compound A can provide a composition with better heat resistance.
In the present invention, it is possible to easily form a composition that has excellent patterning accuracy and heat resistance, has an excellent balance between crosslinking density and hydrophobicity, and can stably form a patterned cured product despite variations in alkali development time. From the viewpoint that n is preferably 5 or more and 6 or less.

The above X is used as a linking group that connects n -SR ^1s .
An aliphatic group having 1 to 40 carbon atoms, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, and a heterocycle having 2 to 35 carbon atoms and having the same valence as n, represented by X above. The containing groups are, respectively, 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 heterocarbon group having 2 to 35 carbon atoms. It is a group with a structure obtained by removing n-1 hydrogen atoms from a ring-containing group.
The monovalent aliphatic group having 1 to 40 carbon atoms, monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, and monovalent heterocycle-containing group having 2 to 35 carbon atoms include: 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 heterocarbon group having 2 to 35 carbon atoms, represented by R ¹ above. Groups similar to ring-containing groups can be mentioned.
One or more of the methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, and heterocycle-containing group in X above are -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH It may be substituted with a group selected from -CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S- or -SO ₂ -, or oxygen It may be replaced by a combination of these groups provided that the atoms are not adjacent to each other.
That is, in X, one or more of the methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, and heterocycle-containing group is -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'-, -S-S-, or -SO ₂ -, or oxygen atoms are not adjacent It may also be a group whose structure is replaced with a group that is a combination of these groups under certain conditions.
The above 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 has a predetermined number of carbon atoms among the alkyl groups represented by R Here are some things that meet the criteria.

Examples of the divalent aliphatic group having 1 to 40 carbon atoms represented by X above include a group having a structure obtained by removing one hydrogen atom from the above monovalent aliphatic group having 1 to 40 carbon atoms. , for example, alkylene such as methylene, ethylene, propylene, butylene, butyldiyl; a group in which the methylene chain of the above alkylene is replaced with -O-, -S-, -CO-O-, -O-CO-; ethanediol, A group containing a residue of a polyol such as propanediol, butanediol, pentanediol, hexanediol (for example, a group represented by general formula (X1) described below); ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexane Examples include residues of dithiol such as dithiol, and groups in which these groups are substituted with substituents described below.
Examples of the trivalent aliphatic group having 1 to 40 carbon atoms represented by X above include a group having a structure obtained by removing two hydrogen atoms from the above monovalent aliphatic group having 1 to 40 carbon atoms. , for example, alkylidines such as propyridine and 1,1,3-butyridine; groups containing polyol residues such as trimethylolpropane (for example, groups represented by general formula (X2) described later); and groups containing these groups. Examples include groups substituted with substituents described below.
Examples of the tetravalent aliphatic group having 1 to 40 carbon atoms represented by X above include a group having a structure obtained by removing three hydrogen atoms from the above 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 the general formula (X3) described below), and a group in which these groups are substituted with a substituent described below.
Examples of the hexavalent aliphatic group having 1 to 40 carbon atoms represented by X above include a group having a structure obtained by removing 5 hydrogen atoms from the above monovalent aliphatic group having 1 to 40 carbon atoms. Examples include groups containing a residue of a polyol such as dipentaerythritol (for example, a group represented by general formula (X4) described below), and groups in which these groups are substituted with substituents described below.

The divalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms represented by X above is one hydrogen atom from the above monovalent aromatic hydrocarbon ring containing group having 6 to 35 carbon atoms. Examples include arylene groups such as phenylene and naphthylene; residues of bifunctional phenols such as catechol and bisphenol; 2,4,8,10-tetraoxaspiro[5,5]undecane, etc. Examples include groups in which these groups are substituted with substituents described below.
The trivalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms represented by X above includes two hydrogen atoms from the monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms. Examples include groups having structures removed, such as phenyl-1,3,5-trimethylene and groups in which these groups are substituted with substituents described below.

The divalent heterocycle-containing group having 2 to 35 carbon atoms represented by X above is a group having a structure obtained by removing one hydrogen atom from the monovalent heterocycle-containing group having 2 to 35 carbon atoms. For example, groups having a pyridine ring, pyrimidine ring, piperidine ring, piperazine ring, triazine ring, furan ring, thiophene ring, indole ring, etc., and one or more of the hydrogen atoms of these groups are substituted as described below. Examples include groups substituted with groups.
The trivalent heterocycle-containing group having 2 to 35 carbon atoms represented by X above is a group having a structure obtained by removing two hydrogen atoms from the monovalent heterocycle-containing group having 2 to 35 carbon atoms. For example, a group having an isocyanuric ring (for example, a group having a structure represented by the general formula (X5) described below), a group having a triazine ring, and one or more hydrogen atoms of these groups Examples include groups substituted with substituents described below.
The tetravalent heterocycle-containing group having 2 to 35 carbon atoms represented by X above has a structure obtained by removing three hydrogen atoms from the monovalent heterocycle-containing group having 2 to 35 carbon atoms. Examples include a group having a glycoluril group (for example, a structure represented by general formula (X6) described below) and a group in which a hydrogen atom of this group is substituted with a substituent described below.

Each of the functional groups such as an aliphatic group, an aromatic hydrocarbon ring-containing group, and a heterocycle-containing group in X above may have a substituent, and unless otherwise specified, the functional groups may have a substituent. It is an unsubstituted functional group or a functional group having a substituent.
Examples of substituents that substitute one or more hydrogen atoms of each functional group such as an aliphatic group, an aromatic hydrocarbon ring-containing group, or a heterocycle-containing group include the aliphatic group in R ¹ above, etc. The content can be the same as that of the substituent that replaces the hydrogen atom.

In the present invention, from the viewpoint of obtaining a compound capable of forming a composition with excellent patterning accuracy and heat resistance, the above-mentioned X is an aliphatic group having 1 to 40 carbon atoms or a A heterocycle-containing group is preferable, and among them, an aliphatic group having 10 to 40 carbon atoms and a heterocycle containing group having 5 to 25 carbon atoms are particularly preferable. It is preferably an aliphatic group or a heterocycle-containing group having 10 to 20 carbon atoms, especially an aliphatic group having 25 to 30 carbon atoms or a heterocycle-containing group having 11 to 15 carbon atoms. is preferred. This is because when the above-mentioned X is the above-mentioned group, a compound capable of forming a composition with better patterning accuracy and heat resistance can be obtained.

In the present invention, from the viewpoint of ease of synthesis of compound A, the above-mentioned X has 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 heterocycle-containing group 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 substituted with a group selected from -CO-NH-, -NR'-, -SS- or -SO ₂ -, or these groups may be combined under the condition that oxygen atoms are not adjacent to each other. It is preferable that one or more of the methylene groups be replaced with -O-CO-, -CO-O-, and especially n Preferably, the methylene group is replaced with -O-CO- or -CO-O-.
That is, the above X is one of methylene groups among aliphatic groups having 1 to 40 carbon atoms, aromatic hydrocarbon ring-containing groups having 6 to 35 carbon atoms, and heterocycle-containing groups having 2 to 35 carbon atoms. or two or more 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'-, - A group having a structure substituted with a group selected from SS- or -SO ₂ -, or a combination of these groups with oxygen atoms not adjacent to each other is preferable, and among them, a methylene group is preferable. It is preferable that one or more of the methylene groups is replaced with -O-CO- or -CO-O-, and in particular, n methylene groups are replaced with -O-CO- or -CO- A group substituted with O- is preferable.

In the present invention, the aliphatic group having 1 to 40 carbon atoms represented by X above is a group having a polyol residue (for example, a group represented by the following general formulas (X1) to (X4)). It is preferable that there be.
In addition, the heterocycle-containing group having 2 to 35 carbon atoms represented by A group having a structure) is preferable.
This is because when the above-mentioned X is the above-mentioned group, a compound capable of forming a composition with better patterning accuracy and heat resistance can be obtained. Further, the above compound A is easy to synthesize.
Note that the hydrogen atoms in the structures represented by the above general formulas (X1) to (X6) may be substituted with a substituent. The substituent that replaces the hydrogen atom can have the same content as the substituent that replaces the hydrogen atom such as the aliphatic group in R ¹ above.

(In the formula, a1 is an integer from 1 to 20, and * represents the bonding point.)

The above a1 is an integer of 1 to 20, preferably an integer of 2 to 10, and particularly preferably an integer of 3 to 5.

More specifically, compounds represented by the following general formulas (A1) to (A6) can be preferably used as the above compound A.
In the present invention, it is particularly preferable that the compound A is a compound represented by the following general formula (A4) or (A6). Since the compound A has the above structure, it becomes a compound that can form a composition with excellent patterning accuracy and heat resistance, and in particular, it becomes possible to form a composition with excellent heat resistance.
In the present invention, it is particularly preferable that the compound A is a compound represented by the following general formula (A4). This is because not only patterning accuracy and heat resistance but also development margin are improved, resulting in particularly excellent patterning accuracy.

The reason why the compounds represented by the above general formulas (A4) and (A6) are excellent in both patterning accuracy and heat resistance, and can form compositions with particularly excellent heat resistance. , it is inferred as follows.
In the compound represented by the general formula (A4), the number of thiol groups generated after removal of the protecting group is as large as six, and the thiol groups are arranged so as to extend in all directions. Therefore, by including the compound A, a region with high crosslinking density can be formed around the compound A. As a result, it has excellent heat resistance.
In addition, the structure represented by (X4) contained in the six protected thiol groups or the site that binds the thiol group, which the compound represented by the above general formula (A4) has, has a relatively large molecular weight and a central By having a structure that spreads in six directions from the oxygen atom, curing shrinkage due to crosslinking is small. Therefore, it is easy to minimize shrinkage during heat treatment. For this reason, the compound represented by the above general formula (A4) can be made to have an excellent balance between patterning accuracy and heat resistance, and can easily exhibit particularly excellent heat resistance. .
Moreover, the compound represented by the above general formula (A4) has a structure that spreads in six directions and has a large molecular weight, so that the diffusion rate in the composition is low. Therefore, even if the protecting group is removed from some compounds, crosslinking between the polymerizable components is difficult to proceed. As a result, the patterning accuracy becomes more excellent.
Furthermore, the structure represented by (X4) included in the six protected thiol groups or the site to which the thiol groups are bonded has a relatively large molecular weight and is likely to be a highly hydrophobic site. Therefore, the compound represented by the above general formula (A4) facilitates the formation of a cured product with excellent resistance to an alkaline developer, and the composition containing the above compound has an excellent development margin.
As described above, the compound represented by the general formula (A4) has excellent patterning accuracy exhibited in the polymerization process, excellent development margin exhibited in the development process, and improvement in patterning accuracy obtained as a result. Furthermore, the excellent heat resistance exhibited during the subsequent heat treatment process such as the post-bake process can be effectively exhibited in each step of the patterning process.
For this reason, the compound represented by the above general formula (A4) is particularly suitable for, for example, a curable composition for forming a patterned cured product.
In addition, the compound represented by the general formula (A6) has a large number of thiol groups (4) generated after the removal of the protecting group, and the thiol groups are arranged so as to extend in all directions, and the rigid glycoluril It has a group. Therefore, by including the compound A, a region with high crosslinking density can be formed around the compound A. As a result, it has excellent heat resistance.
Moreover, the glycoluril group that the compound represented by the above general formula (A6) has has a rigid structure, so that curing shrinkage due to crosslinking is small. That is, it becomes easy to reduce shrinkage during heat treatment. For this reason, the compound represented by the above general formula (A4) can be made to have an excellent balance between patterning accuracy and heat resistance, and can easily exhibit particularly excellent heat resistance. .
Further, the compound represented by the above general formula (A6) has a rigid glycoluril group and has a bulky structure, so that the diffusion rate in the composition is low. Therefore, even if the protecting group is removed from some compounds, crosslinking between the polymerizable components is difficult to proceed. As a result, the patterning accuracy becomes more excellent.

(In the formula, 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 from 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 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 general formula (101) or (102),
Any two or more of R ³¹ , R ³² , R ³³ and R ³⁴ are 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 general formula (101) or (102),
Any two or more of R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are the following general formula (101),
L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ and L ⁴⁶ represent an alkylene group having 1 to 10 carbon atoms,
R ⁵¹ , R ⁵² and R ⁵³ each independently represent the following general formula (101) or (102),
Any two or more of R ⁵¹ , R ⁵² and R ⁵³ are the following general formula (101),
L ⁵¹ , L ⁵² and L ⁵³ represent an alkylene group having 1 to 10 carbon atoms,
R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent the following general formula (101) or (102),
Any two or more of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are the following general formula (101),
L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ represent an alkylene group having 1 to 10 carbon atoms,
R ⁶⁵ and R ⁶⁶ each independently represent a hydrogen atom or a monovalent aliphatic group having 1 to 40 carbon atoms,
One or more methylene groups in the aliphatic group 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- It may be substituted with a group selected from CO-NH-, -NR'-, -SS- or -SO ₂ -, or these groups are combined under the condition that oxygen atoms are not adjacent to each other. It may be replaced by a group. )

(In the formula, 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, and a monovalent group having 2 to 35 carbon atoms. Represents a heterocycle-containing group or a monovalent silyl group having 0 to 40 carbon atoms,
* represents the joint location,
One or more methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocycle-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 there a case where it is substituted with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S-, or -SO ₂ -? , or may be replaced by a group that combines these groups with oxygen atoms not being adjacent to each other. )

The monovalent aliphatic group having 1 to 40 carbon atoms represented by R ²⁴ in the above general formula (A2) and R ⁶⁵ and R ⁶⁶ in (A6) includes the monovalent aliphatic group having 1 to 40 carbon atoms used in the above R ¹ . Examples include the same aliphatic groups having 1 to 40 carbon atoms.
R ¹ in the above general formula (101) is the same as R ¹ in the above general formula (A).

The above L11 ^{, L12 , L21} , ^L22 , ^L23 , L31, ^L32 , ^L33 , ^L34 , ^L41 , ^L42 , ^L43 , ^L44 , ^L45 , ^L46 , ^L51 , L 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 obtained by removing one hydrogen atom from an alkyl group having 1 to 10 carbon atoms. Examples include divalent groups.
As the alkyl group having 1 to 10 carbon atoms, for example, an alkyl group having a predetermined number of carbon atoms among the alkyl groups having 1 to 40 carbon atoms in R ¹ above can be used.
More specific examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, butylene, butyldiyl, and the like.
Further, the alkylene group having 1 to 10 carbon atoms may be linear or branched. As a straight chain group, for example, as a group having 3 carbon atoms, there can be mentioned a propylene group in which hydrogen atoms are removed from the 1st and 2nd positions of propane; Examples include the trimethylene group.

Two or more of R ²¹ , R ²² and R ²³ in the above general formula (A2) may be represented by the above general formula (101), but it is preferable that all of them are represented by the above general formula (101). .
Two or more of R ³¹ , R ³² , R ³³ and R ³⁴ in the above general formula (A3) may be represented by the above general formula (101), but three or more of them may be represented by the above general formula (101). Preferably, all of them are of the above general formula (101).
Two or more of R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ in the above general formula (A4) may be represented by the above 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 are represented by the above general formula (101), especially R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ It is preferable that all of the above formula (101) be satisfied.
Two or more of R ⁵¹ , R ⁵² and R ⁵³ in the above general formula (A5) may be represented by the above general formula (101), but all of R ⁵¹ , R ⁵² and R ⁵³ may be the above general formula (101). Formula (101) is preferable.
Two or more of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ in the above general formula (A6) may be represented by the above general formula (101), but R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ It is preferable that three or more of them are represented by the above general formula (101), and it is preferable that all of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are represented by the above general formula (101).
The above R ²¹ , R ²² and R ²³ , R ³¹ , R ³² , R ³³ and R ³⁴ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁵¹ , R ⁵² and R ⁵³ , R This is because when ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are the above-mentioned groups, the compound A can form a composition with better patterning accuracy and heat resistance.

The preferred structure for R ¹ in the above general formula (101) is the same as the preferred structure for R ¹ in the above general formula (A).

In the present invention, R ²⁴ is preferably an aliphatic group having 1 to 40 carbon atoms, particularly 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, iso-propyl, etc. It is preferable that it is a group. This is because when R ²⁴ is the group described above, the compound A can form a composition with better patterning accuracy and heat resistance.
In the present invention, R ⁶⁵ and R ⁶⁶ are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Preferably, a hydrogen atom is particularly preferable. This is because when R ⁶⁵ and R ⁶⁶ are the groups described above, the compound A can form a composition with better patterning accuracy and heat resistance.

a1 in the above general formula (A1) is the same as a1 in the above general formula (X1).

The above L ¹¹ and L ¹² are preferably alkylene groups having 1 to 5 carbon atoms, particularly linear alkylene groups having 1 to 3 carbon atoms or branched alkylene groups having 3 to 5 carbon atoms. It is preferable.
The above L ¹¹ and L ¹² may be the same group or different groups, but from the viewpoint of ease of synthesis, it is preferable that they are the same group.
The above L ²¹ , L ²² and L ²³ are preferably an alkylene group having 1 to 5 carbon atoms, particularly a linear alkylene group having 1 to 3 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms. It is preferable that it is a group.
The above L ²¹ , L ²² and L ²³ may be the same group or different groups, but from the viewpoint of ease of synthesis, they are preferably the same group.
The above L ³¹ , L ³² , L ³³ and L ³⁴ are preferably alkylene groups having 1 to 5 carbon atoms, and particularly, linear alkylene groups having 1 to 3 carbon atoms or branched 3- to 3-carbon alkylene groups. It is preferable that it is an alkylene group of 5.
The above L ³¹ , L ³² , L ³³ and L ³⁴ may be the same group or different groups, but from the viewpoint of ease of synthesis, they are preferably the same group.
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, especially linear alkylene groups having 1 to 3 carbon atoms. It is preferably a group or a branched 3 to 5 alkylene group.
The above L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ and L ⁴⁶ may be the same group or different groups, but from the viewpoint of ease of synthesis, they are the same group. It is preferable.
The above L ⁵¹ , L ⁵² and L ⁵³ are preferably an alkylene group having 1 to 5 carbon atoms, particularly a linear alkylene group having 1 to 3 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms. It is preferable that it is a group.
The above L ⁵¹ , L ⁵² and L ⁵³ may be the same group or different groups, but from the viewpoint of ease of synthesis, they are preferably the same group.
The above L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ are preferably alkylene groups having 1 to 5 carbon atoms, particularly linear alkylene groups having 1 to 3 carbon atoms or branched 3 to 3 carbon atoms. It is preferable that it is an alkylene group of 5.
The above L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ may be the same group or different groups, but from the viewpoint of ease of synthesis, they are preferably the same group.
The above L11 ^{, L12 , L21} , ^L22 , ^L23 , L31, ^L32 , ^L33 , ^L34 , ^L41 , ^L42 , ^L43 , ^L44 , ^L45 , ^L46 , ^L51 , L This is because when ⁵² , L ⁵³ , L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ are within the above-mentioned ranges, the compound can form a composition with better patterning accuracy and heat resistance.
The above L11 ^{, L12 , L21} , ^L22 , ^L23 , L31, ^L32 , ^L33 , ^L34 , ^L41 , ^L42 , ^L43 , ^L44 , ^L45 , ^L46 , ^L51 , L ⁵² , L ⁵³ , L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ , linear alkylene groups having 1 to 3 carbon atoms are specifically methylene, ethylene (ethane-1,2 -diyl), propylene (propane-1,3-diyl), and the like.
The above L11 ^{, L12 , L21} , ^L22 , ^L23 , L31, ^L32 , ^L33 , ^L34 , ^L41 , ^L42 , ^L43 , ^L44 , ^L45 , ^L46 , ^L51 , L ⁵² , L ⁵³ , L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ , the branched 3-5 alkylene groups are specifically propane-1,1-diyl, 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 , pentane-1,4-diyl and the like.

The number of thiol groups (SH groups) in the above compound A, that is, the number of thiol groups in compound A that are not protected by the protecting group R ¹ , makes it possible to form a composition with better patterning accuracy and heat resistance. It is sufficient as long as it becomes , and the smaller the number, the more preferable.
The number of thiol groups in the compound A is preferably 2 or less, preferably 1 or less, and 0, that is, the compound A does not contain a thiol group. preferable. This is because it becomes possible to form a composition with excellent patterning accuracy and heat resistance.

The molecular weight of the compound A may be any molecular weight as long as it can form a composition with excellent patterning accuracy and heat resistance. For example, it is preferably 3,000 or less, and particularly preferably 300 or more and 2,500 or less. In particular, it is preferably 500 or more and 2000 or less, and particularly preferably 600 or more and 1800 or less.
In addition, the molecular weight of the compound A is 1000, from the viewpoint that the composition containing the compound has excellent patterning accuracy and heat resistance, and has an excellent development margin, particularly from the viewpoint that it exhibits excellent heat resistance. It is preferably 1,700 or more, more preferably 1,200 or more and 1,600 or less, particularly preferably 1,300 or more and 1,500 or less.
The molecular weight of the compound after the removal of the protecting group R ¹ of compound A, that is, the molecular weight of the thiol compound whose -SH group is not protected by the protecting group R ¹ , has excellent patterning accuracy and heat resistance, and contains the above compound. From the viewpoint that the composition has an excellent development margin, particularly from the viewpoint of exhibiting excellent heat resistance, it is preferably 400 or more and 1000 or less, more preferably 500 or more and 900 or less, and particularly, It is preferably 600 or more and 800 or less.

The equivalent of the protected thiol group (SR ¹ ) in the above compound A, that is, the value obtained by dividing the molecular weight of compound A by the number of protected thiol groups (SR ¹ ) (molecular weight of compound A/number of protected thiol groups SR ¹ ) is , 500 or less, particularly preferably 100 or more and 400 or less, particularly preferably 150 or more and 300 or less. This is because when the protected thiol group equivalent of the compound A is within the above-mentioned range, the compound can form a composition with better patterning accuracy and heat resistance.
The equivalent of the protected thiol group (SR ¹ ) in the above compound A has excellent patterning accuracy and heat resistance, and also exhibits particularly excellent heat resistance from the viewpoint that a composition containing the above compound has an excellent development margin. From the viewpoint of
The thiol group equivalent of the compound after the removal of the protecting group R ¹ of compound A, that is, the thiol group equivalent of the thiol compound whose -SH group is not protected by the protecting group R ¹ , has excellent patterning accuracy and heat resistance. From the viewpoint that the composition containing the above compound has an excellent development margin, particularly from the viewpoint of exhibiting excellent heat resistance, it is preferably 400 or more and 1000 or less, and preferably 500 or more and 900 or less. It is preferably 600 or more and 800 or less.

The above-mentioned compound A may be one in which the protecting group R ¹ is removed by heating.
The temperature at which the protecting group R ¹ contained in the compound A is eliminated can be, for example, 100°C or higher and 300°C or lower, particularly preferably 120°C or higher and 250°C or lower, and 150°C or higher. 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 shown by differential thermal analysis.
The measurement method is, for example, using STA (differential thermogravimetry simultaneous measurement apparatus), using approximately 5 mg of the sample, under a nitrogen atmosphere of 200 mL/min, under normal pressure, heating start temperature 30 ° C., heating end temperature 500 ° C. The thermal loss of the sample is measured when the temperature is raised at a temperature rate of 10° C./min, and the temperature at which the weight of the sample is reduced by 5% relative to the sample weight at 30° C. can be defined as the 5% weight loss temperature.
As the simultaneous differential thermogravimetric measurement device, STA7000 (manufactured by Hitachi High-Tech Science) can be used.

Specific examples of the compound A include the compounds shown below.

The method for producing the above compound A is not particularly limited as long as it can obtain the desired structure. The above production method includes, for example, a method of forming an esterified product of a hydroxy group of a polyol and a carboxylic acid containing an SH group, as described in JP-A No. 2017-031318, and a method as described in JP-A No. 2015-059099. As described above, a thiol group-containing compound can be converted into a thiol group-containing compound by a known method such as an addition reaction of thioacetic acid to the ethylenically unsaturated group of a compound having an ethylenically unsaturated group, and then reduction with a borohydride compound. Examples include a method in which a thiol group-containing compound is produced and then reacted with an acid anhydride, an acid chloride, a Boc-forming reagent, an alkyl halide compound, a silyl chloride compound, an allyl ether compound, or the like.

The above-mentioned compound A can be used as a thiol generator that generates an SH group by heat treatment, etc., and is, for example, a thiol generator added to a composition such as a curable composition containing a polymerizable component B such as a radically polymerizable component. It can be used as a generator.
The above-mentioned curable composition is used in thermosetting paints, photocurable paints or varnishes, thermosetting adhesives, photocurable adhesives, printed circuit boards, color televisions, PC monitors, mobile information terminals, and digital cameras. Color filters for liquid crystal display panels with color displays, 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 for producing 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. Alternatively, resists for forming structures in the manufacturing process of plasma display panels, electroluminescent displays, and LCDs, compositions for encapsulating electrical and electronic components, solder resists, magnetic recording materials, micromechanical components, waveguides, Optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, screen printing stencils, materials for producing three-dimensional objects by stereolithography, holographic recording materials, image recording materials, microelectronic circuits , bleaching materials, bleaching materials for image recording materials, bleaching materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, printed circuit boards It can be used for various purposes such as a photoresist material used to form a dielectric layer in sequential lamination, a photoresist material for 3D mounting, or a protective film, and there are no particular restrictions on its use.
In addition, the curable composition containing the compound A is preferably used to form a patterned cured product that is excellent in both patterning accuracy and heat resistance, and in particular, is patterned by photolithography and cured in a pattern. It is preferably used in photocurable compositions used in the formation of objects.
More specifically, the curable composition is preferably used for color filters, photo spacers, black column spacers, electrode materials, photoresists, solder resists, overcoats, insulating films, black matrices, partition materials, etc. be able to.
In the present invention, when the compound A is used in a photocurable composition, it is used in a photocurable composition for forming a patterned cured product with a width of 200 μm or less, that is, for forming a pattern with a width of 200 μm or less. It is preferable to use the photocurable composition for forming a pattern of 0.1 μm or more and 150 μm or less, especially for forming a pattern of 0.5 μm or more and 100 μm or less. The photocurable composition is preferably used in a photocurable composition for forming a pattern of 1 μm or more and 50 μm or less. By being used for pattern formation with the above-mentioned width, the effects of the above-mentioned compound A in terms of excellent patterning accuracy and heat resistance, as well as the effect of facilitating the formation of a patterned cured product with a narrow line width, can be more effectively exhibited. It is. Further, it is possible to stably form a pattern with a high aspect ratio.
Further, when the above compound A is used in a photocurable composition for pattern formation, the film thickness of the pattern is preferably 0.1 μm or more and 100 μm or less, and preferably 0.3 μm or more and 50 μm or less. , preferably 0.5 μm or more and 10 μm or less, and preferably 1 μm or more and 5 μm or less. By having the above-mentioned film thickness within the above-mentioned range, the effects of the excellent patterning accuracy and heat resistance of the above-mentioned compound A can be more effectively exhibited, and a pattern with a high aspect ratio can be stably formed. be.

B. Thiol Generator Next, the thiol generator of the present invention will be explained.
The thiol generator of the present invention is characterized by containing the above-mentioned compound (the above-mentioned compound A).

According to the present invention, by containing the above-mentioned compound A, the thiol generator becomes capable of forming a composition with excellent patterning accuracy and heat resistance.

1. Compound The type of compound A used in the thiol generator of the present invention may be one that can form a composition with excellent patterning accuracy and heat resistance, and only one type may be used in the thiol generator. , there may be two or more types. The thiol generator can contain, for example, two or more and five or less types of compounds A.

The content of the compound A may be any content that can form a composition with excellent patterning accuracy and heat resistance, and is appropriately set depending on the type of thiol generator and the like.
The content of the compound A may be, for example, 100 parts by mass in 100 parts by mass of the solid content of the thiol generator, that is, the thiol generator may be the compound A.
Further, the above content may be less than 100 parts by mass in 100 parts by mass of the solid content of the thiol generator, that is, the thiol generator may be a composition containing the above compound A and other components, for example, 20 parts by mass. It can be more than 99.99 parts by mass or less.
In the present invention, from the viewpoint of facilitating the formation of a composition with excellent patterning accuracy and heat resistance, the lower limit of the above content is preferably 50 parts by mass or more, particularly 70 parts by mass or more. The amount is preferably 90 parts by mass or more, particularly preferably 90 parts by mass or more.
In addition, from the viewpoint of facilitating particle size control of the thiol generator, etc., 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.
Note that the solid content includes all components other than the solvent.
Moreover, the content of the above-mentioned compound A indicates the total amount of compound A when two or more types of compound A are included.

Note that the above Compound A can be the same as described in the section of "A. Compound" above, so the explanation here will be omitted.

2. Other Components The thiol generator may contain components other than the compound A.
Examples of such other components include "2. Polymerizable component having thiol reactivity", "3. Polymerization initiator", and "4. Polymer having carboxyl group" in "C. Composition" described later. ” and “5. Other components”.
Among others, the other components preferably include the polymerization initiator described in the section "3. Polymerization initiator" above. This is because by consolidating the components involved in the polymerization, reaction, etc. of the polymerizable component B, it becomes easier 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 may be the same as described in "3. Polymerization initiator" of "C. Composition" described later.
From the viewpoint of facilitating particle size control of the thiol generator, etc., the above-mentioned other components preferably include a polymer having no polymerizable group as described in "5. Other components". .
The content of the other components can be set as appropriate depending on the use of the thiol generator, but for example, it can be 50 parts by mass or less in 100 parts by mass of the solid content of the thiol generator. It is preferably 10 parts by mass or less. This is because the above-mentioned thiol generator makes it easy to increase the content ratio of compound A, and it becomes easy to form a composition with excellent patterning accuracy and heat resistance.

3. Manufacturing method The thiol generator may be manufactured by any method as long as it can contain the compound A in a desired amount.
When the above-mentioned thiol generator contains Compound A and other components, a method using known mixing means can be mentioned.

Examples of uses of the thiol generator include adding it to compositions such as curable compositions containing polymerizable component B.
The specific uses of the curable composition can be the same as those described in the section "A. Compound" above, so the explanation here will be omitted.

C. Composition Next, the composition of the present invention will be explained.
The composition of the present invention is characterized by having a compound represented by the following general formula (A) (compound A) and a polymerizable component having thiol reactivity (polymerizable component B). .

(In the formula, 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, and a monovalent group having 2 to 35 carbon atoms. Represents a heterocycle-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 heterocycle-containing group having 2 to 35 carbon atoms and having the same valence as n; ,
One or more methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocycle-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 there a case where it is substituted with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S-, or -SO ₂ -? , or may be replaced with a group that combines these groups with the conditions that oxygen atoms are not adjacent,
n represents an integer of 2 or more and 10 or less. )

According to the present invention, since the composition contains the compound A, it has excellent patterning accuracy and heat resistance.

The composition of the present invention contains the above compound A and polymerizable component B.
Each component of the composition of the present invention will be explained in detail below.

1. Compound A
The compound A may be of any type as long as it can form a composition with excellent patterning accuracy and heat resistance, and the composition may contain only one type or two or more types. The above compound A can include, for example, two or more types and five or less types of compounds A.

The content of the compound A is appropriately set depending on the use of the composition.
Such a content may be 0.01 parts by mass or more and 20 parts by mass or less, and preferably 0.05 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the solid content of the composition. This is because it becomes easier to form a composition with excellent patterning accuracy and heat resistance.

Note that the above Compound A can be the same as described in the section of "A. Compound" above, so the explanation here will be omitted.

2. Polymerizable component B
The 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 that allows the polymerizable components to polymerize with each other.
As such a thiol-reactive group, a radically polymerizable group, a cationically polymerizable group, etc. can be preferably used.
The polymerizable component B may contain at least one of a radically polymerizable compound having a radically polymerizable group and a cationically polymerizable compound having a cationically polymerizable group, and the radically polymerizable component B is composed of a radically polymerizable compound. , a cationically polymerizable component consisting of a cationically polymerizable compound, or a polymerizable component containing both a radically polymerizable compound and a cationically polymerizable compound.
Since the polymerizable component B is the above-mentioned component, for example, when used in combination with a photopolymerization initiator such as a photoradical polymerization initiator or a photocationic polymerization initiator, the composition can be polymerizable by light irradiation. This is because a patterned cured product can be formed with high patterning accuracy through the step of polymerizing the components and the development step.
In the present invention, it is particularly preferable that the polymerizable component B contains a radically polymerizable compound as the polymerizable compound B, and particularly preferably a radically polymerizable component consisting of a radically polymerizable compound. This is because the composition has an excellent curing speed when the polymerizable component B contains a radically polymerizable compound. This is also because crosslinking using the above compound A is easy.

(1) Radical polymerizable compound The above-mentioned radical polymerizable compound is a compound having a radical polymerizable group.
Examples of such radically polymerizable compounds include radically polymerizable compounds described in JP-A No. 2016-176009.
More specifically, examples of the radically polymerizable group include compounds having an ethylenically unsaturated group such as an acryloyl group, a methacryloyl group, and a vinyl group.
As the radically polymerizable compound, a monofunctional compound having one radically polymerizable group and a polyfunctional compound having two or more radically polymerizable groups can be used.

As the radically polymerizable compound, a compound having an acid group and a compound not having an acid group can be used.
Examples of the acid group include -COOH group, -SO ₃ H group, -SO ₂ NHCO- group, phenolic hydroxy group, -SO ₂ NH- group, -CO-NH-CO- group, and the like.
Examples of compounds having the above acid group include 4-hydroxystyrene, (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, and β-furyl(meth)acrylic acid. - Styryl (meth)acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-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, 6-maleimidohexanoic acid, and the like.
Examples of the above-mentioned compounds having acid groups include epoxy acrylate resins obtained by reacting an unsaturated monobasic acid with the epoxy group of an epoxy compound, and polybasic resins obtained by reacting an unsaturated monobasic acid with the epoxy group of an epoxy compound, and Examples include acid group-containing epoxy acrylate resins such as carboxyl group-containing epoxy acrylate resins obtained by the action of acid anhydrides.
Examples of the acid group-containing epoxy acrylate resin include Ripoxy (registered trademark) SPC-2000 and SPC-3000 manufactured by Showa Denko Co., Ltd., Dicklite (registered trademark) UE-777 manufactured by DIC Corporation, and U-Pica (registered trademark) manufactured by Nippon U-Pica Co., Ltd. Trademark) 4015, etc.
Furthermore, as the compound having an acid group, a polymer having a methacryloyl group or an acryloyl group and a carboxyl group can also be used. As such a polymer, among the polymers described in "4. Polymer having a carboxyl group" described later, a polymer having a structural unit having a methacryloyl group or an acryloyl group as a crosslinkable group is also preferable. Can be used.
As the compound having an acid group, among polymers of radically polymerizable compounds, those having an unreacted or subsequently added radically polymerizable group can also be used. For example, among polymers of compounds with acid groups, and polymers of compounds with acid groups and compounds without acid groups, those with unreacted or subsequently added radically polymerizable groups also contain acid groups. It can be used as a compound having

Examples of the above-mentioned compounds without acid groups include polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene, acrylamide, acrylonitrile, and vinyl-n-butyl ether. Vinyl alcohol ethers, (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth)acrylic acid glycidyl ester , (meth)acrylic acid esters such as pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, 2 , 2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, maleic anhydride, maleic acid monoester, phenylmaleimide, N-substituted maleimide such as cyclohexylmaleimide can be mentioned.

The radically polymerizable compound can be used together with a radical polymerization initiator such as a photoradical polymerization initiator or a thermal radical polymerization initiator.

(2) Cationically polymerizable compound A cationically polymerizable compound is a compound having a cationically polymerizable group.
Examples of such cationically polymerizable compounds include cationically polymerizable compounds described in JP-A No. 2016-176009.
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.
As the cationically polymerizable compound, a monofunctional compound having one cationically polymerizable group or a polyfunctional compound having two or more cationically polymerizable groups can be used.
As the cationic polymerizable compound, a compound having an acid group or a compound not having an acid group can be used.
As the cationic polymerizable compound, 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 polymers include polymers having a structural unit having an epoxy group, oxetanyl group, or vinyl ether group as a crosslinkable group among the polymers described in "4. Polymers having a carboxyl group" described below. etc. can also be preferably used.
When using a mixture of two or more cationic polymerizable compounds, they may be copolymerized in advance and used as a copolymer.
The cationic polymerizable compound can be used together with a cationic polymerization initiator such as a photocationic polymerization initiator or a thermal cationic polymerization initiator.

(3) Others The content of the polymerizable component B is not particularly limited as long as it can provide excellent patterning accuracy and heat resistance, for example, the solid content of the composition of the present invention. In 100 parts by mass, it is preferably 10 parts by mass or more and 90 parts by mass or less, particularly preferably 20 parts by mass or more and 80 parts by mass or less, particularly 30 parts by mass or more and 70 parts by mass or less. is preferred. This is because the composition has better patterning accuracy and heat resistance.
Further, the content of the polymerizable component B is not particularly limited as long as it can provide excellent patterning accuracy and heat resistance. For example, the content of the polymerizable component B is the sum of the compound A and polymerizable component B. In 100 parts by mass, it is preferably 70 parts by mass or more, particularly preferably 80 parts by mass or more and 99.9 parts by mass or less, and particularly preferably 90 parts by mass or more and 99 parts by mass or less. . This is because when the content is within the above range, the composition has better patterning accuracy and heat resistance.

As the polymerizable component B, both a compound having an acid group and a compound not having an acid group can be used.However, from the viewpoint of obtaining a composition with better patterning accuracy, it is preferable to use an acid group. In order to obtain a composition with excellent patterning accuracy and heat resistance, it is preferable to contain both a compound having an acid group and a compound not having an acid group.
More specifically, when the polymerizable component B is a radically polymerizable component, it is preferable that the radically polymerizable compound contains a compound having an acid group, from the viewpoint of providing a composition with better patterning accuracy. From the viewpoint of obtaining a composition with excellent patterning accuracy and heat resistance, it is preferable that the radically polymerizable compound includes both a compound having an acid group and a compound not having an acid group.

The content of the acid group-containing compound may be any content as long as it provides a composition with excellent patterning accuracy and heat resistance, but it is not less than 1 part by mass and not more than 95 parts by mass in 100 parts by mass of the polymerizable component B. The content is preferably 1 part by mass or more and 80 parts by mass or less. This is because the composition has better patterning accuracy and heat resistance.
In the present invention, from the viewpoint of improving the patterning accuracy of the composition, the content of the acid group-containing compound is preferably 20 parts by mass or more in 100 parts by mass of the polymerizable component B. Among these, it is preferably 50 parts by mass or more, particularly preferably 70 parts by mass or more.
From the viewpoint of making the composition more excellent in heat resistance, the content of the compound having an acid group is preferably 70 parts by mass or less in 100 parts by mass of the polymerizable component B, and in particular, It is preferably 50 parts by mass or less, particularly preferably 30 parts by mass or less.
Furthermore, 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 100 parts by mass in total of the compound A and polymerizable component B. The content is preferably 50 parts by mass or more and 90 parts by mass or less, particularly preferably 70 parts by mass or more and 90 parts by mass or less.
From the viewpoint of making the composition more excellent in heat resistance, 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 polymerizable component B. The amount is preferably 50 parts by mass or less, particularly preferably 30 parts by mass or less.
In addition, when the polymerizable component B contains both a radically polymerizable compound and a cationic polymerizable compound, the content of the compound having an acid group is determined based on the content of the compound having an acid group and the cationic polymerizable compound among the radically polymerizable compounds. This shows the total content of compounds having acid groups.

The number of functional groups of the polymerizable compound B, that is, the number of thiol-reactive groups in one molecule of the polymerizable compound B, may be 1 or more, and monofunctional compounds having one thiol-reactive group, thiol-reactive groups A polyfunctional compound having two or more of these can be used.
The number of functional groups of the compound having no acid group may be 1 or more, preferably 2 or more, particularly preferably 3 or more and 8 or less, particularly 4 or more and 7 or less. is preferred. This is because the above composition has an excellent balance of patterning accuracy, heat resistance, etc.
More specifically, when the polymerizable component B is a radically polymerizable component, from the viewpoint of balance between patterning accuracy and heat resistance, the number of functional groups of the radically polymerizable compound that does not have an acid group is , is preferably 2 or more, particularly preferably 3 or more and 8 or less, 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.
The polymerizable component B preferably contains a high molecular weight compound as the polymerizable compound B from the viewpoint of heat resistance of the composition.
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 balance of patterning accuracy and heat resistance of the composition.
More specifically, when the polymerizable component B is a radically polymerizable component, from the viewpoint of patterning accuracy, etc., it is preferable to include a low molecular weight compound as the radically polymerizable compound, which improves patterning accuracy and heat resistance. From this point of view, it is preferable that the radically polymerizable compound includes both a low molecular weight compound and a high molecular weight compound.
The molecular weight of the low molecular weight compound may be any molecular weight as long as the desired patterning accuracy etc. can be obtained, for example, it can be less than 1000, preferably 50 or more and 500 or less, especially 50 or more and 300 or less. It is preferable.
Further, the molecular weight of the high molecular weight compound may be any one that can provide desired heat resistance, for example, it can be 1,000 or more, preferably 1,000 or more and 100,000 or less, particularly 1,500 or more and 50,000 or less. It is preferably below, particularly preferably 2000 or more and 10000 or less.
Hereinafter, when the compound is a polymer, the molecular weight indicates the 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 can be calculated using, for example, GPC (LC-2000plus series) manufactured by JASCO Corporation, using tetrahydrofuran as the elution solvent, and using polystyrene standards for the calibration curve as Mw1110000, 707000, 397000, 189000, 98900, 37200, 13700, 9490, 5430, 3120, 1010, and 589 (TSKgel standard polystyrene manufactured by Tosoh) and measurement columns KF-804, KF-803, and KF-802 (manufactured by Showa Denko). Further, the measurement temperature can be 40° C., and the flow rate can be 1.0 mL/min.

The content of the above-mentioned 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 balance between patterning accuracy and heat resistance, It is subject to adjustment.
Specifically, the content of the high molecular weight compound is preferably 1 part by mass or more and 90 parts by mass or less, particularly 1 part by mass or more and 80 parts by mass or less, in 100 parts by mass of polymerizable component B. It is preferable. This is because the composition has better patterning accuracy and heat resistance.
In the present invention, from the viewpoint of making the composition more excellent in 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, Among these, it is preferably 50 parts by mass or more, and preferably 70 parts by mass or more.
From the viewpoint of making the composition excellent in coating properties, 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, particularly 40 parts by mass. It is preferably at most 20 parts by mass, particularly preferably at most 20 parts by mass.
Further, from the viewpoint of making the composition more excellent in heat resistance, 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 polymerizable component B. The content is preferably 50 parts by mass or more and 90 parts by mass or less, particularly preferably 70 parts by mass or more and 90 parts by mass or less.
From the viewpoint of making the composition excellent in coating properties, 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 polymerizable component B. Among them, it is preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less.
In addition, when the polymerizable component B contains both a radically polymerizable compound and a cationic polymerizable compound, the content of the high molecular weight compound is the high molecular weight compound as the radically polymerizable compound and the high molecular weight as the cationic polymerizable compound. It shows the total content of compounds.

3. Polymerization Initiator The composition preferably contains a polymerization initiator that can polymerize the polymerizable components B together.
This is because it becomes easy to form a patterned cured product with high patterning accuracy using the above composition.
Such a polymerization initiator can be appropriately selected depending on the type of polymerizable component B.
When the polymerizable component B contains a radical polymerizable compound and a cationic polymerizable compound, a radical polymerization initiator and a cationic polymerization initiator can be used as the polymerization initiator, respectively.

The content of the polymerization initiator may be any content that provides a composition with better patterning accuracy and heat resistance.
The above content can be, for example, 0.01 parts by mass or more and 30 parts by mass or less, and 0.1 parts by mass or more and 20 parts by mass or less, in 100 parts by mass of the solid content of the composition of the present invention. is preferable, and preferably 2 parts by mass or more and 10 parts by mass or less. This is because, with the above content, the composition has better patterning accuracy and heat resistance.
The content of the polymerization initiator may be one that can form a composition with excellent patterning accuracy and heat resistance, but it should be 10 parts by mass or more and 700 parts by mass or less based on 100 parts by mass of compound A. is preferable, and especially preferably 15 parts by weight or more and 650 parts by weight or less, and particularly preferably 20 parts by weight or more and 600 parts by weight or less. This is because when the content is within the above range, it becomes easy to form a composition with excellent patterning accuracy and heat resistance.
Further, the content of the polymerization initiator may be any one as long as it can form a composition with excellent patterning accuracy and heat resistance; It is preferably at most 0.5 parts by mass and at most 45 parts by mass, more preferably at least 1 part by mass and at most 40 parts by mass. This is because when the content is within the above range, it becomes easy to form a composition with excellent patterning accuracy and heat resistance.

(1) Radical Polymerization Initiator The radical polymerization initiator may be any one that can generate radicals and polymerize radically polymerizable components.

As such a radical polymerization initiator, both 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, it is preferable to use a photoradical polymerization initiator. A radical polymerization initiator is preferable.
Examples of the photoradical polymerization initiator include benzoins such as benzoin, benzoin methyl ether, 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-morpholyl-2-(4'-methylmercapto)benzoylpropane, 2-methyl -1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 1-hydroxycyclohexylphenylketone, 1-hydroxy-1-benzoylcyclohexane, 2-hydroxy-2-benzoylpropane, 2-hydroxy Acetophenones such as -2-(4'-isopropyl)benzoylpropane, N,N-dimethylaminoacetophenone, 1,1-dichloroacetophenone, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane; 2-methylanthraquinone, 1 - Anthraquinones such as chloroanthraquinone and 2-amyl anthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; acetophenone dimethyl ketal, benzyl dimethyl ketal Ketals such as benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone and 4-benzoyl-4'-methyldiphenyl sulfide; benzophenones such as 2,4,6- Oxides such as trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; Carbazoles such as 3-(2-methyl-2-morpholinopropionyl)-9-methylcarbazole; benzyl; α-Dicarbonyls such as methyl benzoyl formate; JP 2000-80068, JP 2001-233842, JP 2005-97141, JP 2006-516246, Japanese Patent No. 3860170, Patent Oxime esters such as compounds described in No. 3798008, WO2006/018973, JP2011-132215, and WO2015/152153; p-methoxyphenyl-2,4-bis(trichloromethyl)-s -triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl-4,6-bis(trichloromethyl)-triazine Triazines such as methyl)-s-triazine and 2-(p-butoxystyryl)-s-triazine; benzoyl peroxide, 2,2'-azobisisobutyronitrile, ethylanthraquinone, 1,7-bis(9 '-acridinyl)heptane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, benzophenone, phenylbiphenyl ketone, 4-benzoyl-4'-methyldiphenyl sulfide, 2-(p-butoxystyryl)-5 -trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-dimethylbenzphenazine, benzophenone/Michler's ketone, hexaarylbiimidazole/mercaptobenzimidazole, thioxanthone/amine and the like.

Examples of the thermal radical polymerization initiator include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, and 4,4-di(t-butylperoxy)-3,3,5-trimethylcyclohexane. Examples include peroxides such as di(t-butylperoxy)butylvalerate and dicumyl peroxide; azo compounds such as 2,2'-azobisisobutyronitrile; and tetramethylthiraum disulfide.

(2) Cationic polymerization initiator Any compound can be used as the cationic polymerization initiator as long as it can generate acid under predetermined conditions. A photocationic polymerization initiator capable of generating an acid, and a thermal cationic polymerization initiator capable of generating an acid by heat can be used.
As the cationic polymerization initiator, at least one of the photocationic polymerization initiator and the thermal cationic polymerization initiator can be used. A cationic photopolymerization initiator is preferable from the viewpoint of reducing heat damage to the peripheral members used and increasing the degree of freedom in selecting peripheral members. Further, the photocationic polymerization initiator has the advantage of fast curing speed.
Further, the cationic polymerization initiator is preferably a thermal cationic polymerization initiator from the viewpoint of facilitating the formation of a cured product even in a place where light is difficult to reach.

As such a cationic polymerization initiator, a cationic initiator described in JP-A No. 2016-176009 can be used.

4. Polymer Having a Carboxyl Group The above composition preferably contains a polymer having a carboxyl group from the viewpoint of providing excellent developability. This is because by including the polymer, the composition has better patterning accuracy.

The carboxyl group-containing polymer is not particularly limited as long as it has a structural unit having a carboxyl group (hereinafter referred to as "structural unit (U1)"), but may also include a methacryloyl group, an acryloyl group, a vinyl structural unit (hereinafter referred to as "structural unit (U2)"), and a structural unit having a silyl group (hereinafter referred to as "structural unit (U2)"). It is preferable to have a structural unit selected from the unit (U3).
The carboxyl group-containing polymer may have a structural unit (hereinafter referred to as "structural unit (U4)") other than the structural units (U1) to (U3).

The above structural unit (U1) is a structural unit derived from at least one type selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as "compound (u1)"). is preferred.
Examples of the compound (u1) include monocarboxylic acids, dicarboxylic acids, dicarboxylic acid anhydrides, and the like. Examples of the above-mentioned monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid, and 2-methacryloyloxyethylsuccinic acid. Hydrophthalic acid etc.;
Examples of the dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, etc.;
Examples of the dicarboxylic acid anhydrides include the dicarboxylic acid anhydrides described above.

Among these, acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, or maleic anhydride is preferred in terms of copolymerization reactivity and solubility of the resulting copolymer in a developer. preferable.
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 (meth)acrylate (cyclo)alkyl ester, α-alkyl acrylate oxiranyl (cyclo)alkyl ester, and glycidyl ether compounds having a polymerizable unsaturated bond. ;
Examples of the polymerizable unsaturated compound having an oxetanyl group include (meth)acrylic esters having an oxetanyl group.

Specific examples of the above compound (u2) include:
Examples of the (meth)acrylic acid oxiranyl (cyclo)alkyl ester include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, (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, etc.;
Examples of the α-alkyl acrylic acid oxiranyl (cyclo)alkyl ester include α-ethylacrylate glycidyl, α-n-propylacrylate glycidyl, α-n-butylacrylate glycidyl, α-ethylacrylate 6,7-epoxy heptyl, 3,4-epoxycyclohexyl α-ethyl acrylate, etc.;
Examples of glycidyl ether compounds having a polymerizable unsaturated bond include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc.;
Examples of (meth)acrylic acid esters having an oxetanyl group include 3-((meth)acryloyloxymethyl)oxetane, 3-((meth)acryloyloxymethyl)-3-ethyloxetane, 3-((meth)acryloyloxy methyl)-2-methyloxetane, 3-((meth)acryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-((meth)acryloyloxyethyl)oxetane, 3-methyl-3-(meth)acryloyl Examples include oxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, and the like.

Among these specific examples, in particular, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxytricyclo[5.2. 1.02.6]decyl methacrylate, 3,4-epoxytricyclo[5.2.1.02.6]decyl acrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl-3-methacryloyloxy Methyl oxetane or 3-ethyl-3-methacryloyloxymethyl oxetane is preferred from the viewpoint of polymerizability.
Compound (u2) can be used alone or in combination of two or more.

Among the above structural units (U2), as the structural unit having a methacryloyl group or an acryloyl group as a crosslinkable group, a structural unit having a (meth)acryloyloxy group can be preferably used.
The above structural unit having a (meth)acryloyloxy group is obtained by reacting a (meth)acrylic acid ester having an epoxy group with a carboxyl group in a polymer. The structural unit having a (meth)acryloyloxy group after the reaction is preferably a structural unit represented by the following formula (U2-1).

(In the formula, 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 (α) or the following formula (β), and c is an integer from 1 to 6, and * represents the joining point.)

(In the formula, R ¹⁰⁰³ is a hydrogen atom or a methyl group, and * represents a bonding site.)

Regarding the structural unit represented by the above formula (U2-1), for example, when a copolymer having a carboxyl group is reacted with a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate, the structural unit represented by the formula (U2-1 ) in R ¹⁰⁰² becomes formula (α). On the other hand, when a copolymer having a carboxyl group is reacted with 3,4-epoxycyclohexylmethyl methacrylate, R ¹⁰⁰² in formula (U2-1) becomes formula (β).

In the reaction between the carboxyl group in the above-mentioned polymer and an unsaturated compound such as (meth)acrylic acid ester having an epoxy group, a polymer containing a polymerization inhibitor is preferably used in the presence of an appropriate catalyst as necessary. An unsaturated compound having an epoxy group is added to the combined solution, and the mixture is stirred for a predetermined period of time under heating. Examples of the above-mentioned catalyst include tetrabutylammonium bromide and the like. Examples of the polymerization inhibitor include p-methoxyphenol. The reaction temperature is preferably 70°C to 100°C. The reaction time is preferably 8 hours to 12 hours.

In the structural unit ratio of the polymer having a carboxyl group, the content ratio of the structural unit having a (meth)acryloyloxy group as a crosslinkable group is 10 mol% to 70 mol of the total structural units of the polymer having a carboxyl group. %, more preferably 20 mol% to 50 mol%.
When the ratio of structural units having (meth)acryloyloxy groups is within the above range, heat resistance and development defects during development are reduced, and generation of development residues can be suppressed.

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, and 3-(meth)acryloyloxypropyltrimethoxysilane. ) acryloyloxypropyltriethoxysilane and the like.
The above compound (u3) can be used alone or in combination of two or more.

The above 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)"). It is preferable that it is a structural unit derived from.
Examples of the compound (u4) include (meth)acrylic acid alkyl ester, (meth)acrylic acid cycloalkyl ester, (meth)acrylic acid aryl ester, (meth)acrylic acid aralkyl ester, unsaturated dicarboxylic acid dialkyl ester, Examples include (meth)acrylic acid esters, vinyl aromatic compounds, conjugated diene compounds, and other polymerizable unsaturated compounds having a 5-membered oxygen-containing heterocycle or a 6-membered oxygen-containing heterocycle. Specific examples of these include (meth)acrylic acid alkyl esters such as methyl acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, ( sec-butyl meth)acrylate, t-butyl (meth)acrylate, etc.;
Examples of the (meth)acrylic acid cycloalkyl ester include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and tricyclo[5.2.1.02,6]decane-8- (meth)acrylate. yl, 2-(tricyclo[5.2.1.02,6]decane-8-yloxy)ethyl (meth)acrylate, isobornyl (meth)acrylate, etc.;
As the (meth)acrylic acid aryl ester, for example, phenyl acrylate, etc.;
As the (meth)acrylic acid aralkyl ester, for example, benzyl (meth)acrylate, etc.;
Examples of unsaturated dicarboxylic acid dialkyl esters include diethyl maleate, diethyl fumarate, etc.;
Examples of (meth)acrylic acid esters having an oxygen-containing 5-membered heterocycle or an oxygen-containing 6-membered heterocycle include tetrahydrofuran-2-yl (meth)acrylate, tetrahydropyran-2-yl (meth)acrylate, and (meth)acrylate. ) 2-methyltetrahydropyran-2-yl acrylate, etc.;
As a vinyl aromatic compound, for example, styrene, α-methylstyrene, etc.;
As a conjugated diene compound, for example, 1,3-butadiene, isoprene, etc.;
Examples of other polymerizable unsaturated compounds include 2-hydroxyethyl (meth)acrylate, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.

From the viewpoint of copolymerization reactivity, the above compound (u4) includes n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, and tricyclo[5.2.1.02,6]decane-8 methacrylate. -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 in combination of two or more.

The above-mentioned carboxyl group-containing polymer can be synthesized by copolymerizing a mixture of 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%, even more preferably 5 mol% to 15 mol%
Compound (u2): preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, even more preferably 20 mol% to 30 mol%
Compound (u3): preferably 50 mol% or less, more preferably 1 mol% to 40 mol%, even more preferably 10 mol% to 30 mol%
Compound (u4): preferably 80 mol% or less, more preferably 1 mol% to 60 mol%, even more preferably 25 mol% to 50 mol%

In addition, by reacting a (meth)acrylic acid ester having an epoxy group with the carboxyl group in the structural unit derived from compound (u1) in the obtained copolymer, a (meth)acryloyloxy group can be formed. It can have a structural unit having the following structure.

A polymerizable composition containing a polymer having a carboxyl group obtained by copolymerizing a mixture of polymerizable unsaturated compounds containing compounds (u1) to (u4) in the above range has good coating properties. This method is preferable because high resolution can be achieved without impairing the image quality, and a cured film with highly balanced properties can be provided even with a high-definition pattern.

The weight average molecular weight (Mw) of the polymer having a carboxyl group may be any weight average molecular weight (Mw) as long as the desired developability can be obtained. The molecular weight can be the same as the molecular weight of the high molecular weight compound in the polymerization component. By using the above polymer, high resolution can be achieved without sacrificing good coating properties, so even with a high-definition pattern, a cured film with highly balanced properties can be provided. becomes.

A 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.

Examples of the solvent used in the above polymerization include 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 Examples include ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, and 3-methoxybutanol. These solvents can be used alone or in combination of two or more.

The radical polymerization initiator is not particularly limited, and examples thereof include 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, Examples include azo compounds such as 2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators can be used alone or in combination of two or more.

Preferred examples of the carboxyl group-containing polymer include the following polymer U-1 and polymer U-2.

[Polymer U-1]
A flask equipped with a cooling tube and a stirrer was charged with 4 parts by mass of 2,2'-azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate, followed by 55 parts by mass of methacrylic acid, 45 parts by mass of benzyl methacrylate, In addition, 2 parts by mass of α-methylstyrene dimer as a molecular weight regulator was charged, and the temperature of the solution was raised to 80° C. while stirring gently. After maintaining the temperature at 80° C. for 4 hours, the temperature of the solution is raised to 100° C., and this temperature is maintained for 1 hour for polymerization to obtain a solution containing the copolymer. Next, 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 this copolymer, and after stirring at 90°C for 30 minutes in an air atmosphere, methacrylic Examples include 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.
The polymer U-1 has a structural unit (U1), a structural unit (U2), and a structural unit (U4).

[Polymer U-2]
A flask equipped with a cooling tube and a stirrer was charged with 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate, and further 18 parts by mass of methacrylic acid and 5.2 parts by mass of tricyclomethacrylate. .1.02.6] 25 parts by mass of decane-8-yl, 5 parts of styrene, 20 parts by mass of 3-acryloxypropyltrimethoxysilane and 32 parts by mass of glycidyl methacrylate were charged, the atmosphere was replaced with nitrogen, and the mixture was gently stirred. while increasing the temperature of the solution to 80°C. Polymer U-2 having a weight average molecular weight Mw of 12,000 obtained by polymerizing 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, but for example, it should be 10 parts by mass or more and 90 parts by mass or less in 100 parts by mass of solid content of the composition. Can be done.
Further, 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. It can be set to 99 parts by mass or more and 99 parts by mass or less.

5. Other Components In addition to the compound A, polymerizable component B, and polymerization initiator, the composition may contain other components as necessary.
Examples of the above-mentioned other components include a polymer having no polymerizable group, a solvent for dissolving or dispersing each of the above-mentioned components, and a coloring agent.

(1) Polymer without polymerizable group The above polymer does not have polymerizable group.
Here, examples of the polymerizable group include a radically polymerizable group and a cationic polymerizable group.
Examples of such polymers include polycarbonate (PC), polyethylene terephthalate (PET), polyether sulfone, polyvinyl butyral, polyphenylene ether, polyamide, polyamideimide, polyetherimide, norbornene resin, acrylic resin, and methacrylic resin. , isobutylene maleic anhydride copolymer resin, cyclic olefin resin, polyvinyl alcohol, polyethylene glycol, polynivirpyrrolidone, and other thermoplastic resins.
As the above polymer, a polymer of the above polymerizable component B can also be used.
Further, as the above-mentioned polymer, among the above-mentioned carboxyl group-containing polymers, those that do not contain a structural unit having a crosslinkable group can also be used.

The weight average molecular weight (Mw) of the above polymer is appropriately set depending on the use of the composition, etc., and can be, for example, 1,500 or more, and 1,500 or more and 300,000 or less.
The content of the above-mentioned polymer is appropriately selected depending on the purpose of use and is not particularly limited, but can be, for example, 10 parts by mass or more and 90 parts by mass or less in 100 parts by mass of solid content of the composition.
Further, the total content of the polymer and polymerizable component B is appropriately selected depending on the purpose of use and is not particularly limited, but for example, the total content is 10 parts by mass or more in 100 parts by mass of the solid content of the composition. It can be less than or equal to parts by mass.

(2) Solvent The above-mentioned solvent is liquid at 25° C. and atmospheric pressure, and is capable of dispersing or dissolving each component of the composition.
Moreover, the above-mentioned solvent does not have a polymerizable group such as a radically polymerizable group or a cationic polymerizable group.
Therefore, for example, among the polymerizable components B, those that are liquid at 25° C. and atmospheric pressure do not fall under the above-mentioned solvent.
Examples of such solvents 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, and 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; Alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; ethylene Ether ester solvents such as glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate; BTX solvents such as benzene, toluene, and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; Terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; Mineral spirit, Swasol #310 ( paraffinic solvents such as Cosmo Matsuyama Oil Co., Ltd.) and Solvesso #100 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; chlorobenzene, etc. Halogenated aromatic hydrocarbon solvent; carbitol solvent; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide; N-methylpyrrolidone; dimethylsulfoxide, etc. Examples include organic solvents.
Moreover, the above-mentioned solvent may contain water.
Among these, organic solvents such as ketones, ether ester solvents, especially propylene glycol-1-monomethyl ether-2-acetate (hereinafter also referred to as "PGMEA" or "propylene glycol monomethyl ether acetate") and cyclohexanone are used. , is preferable from the viewpoint of good compatibility with Compound A and the like.
The above solvents can be used alone or as a mixed solvent of two or more.

The content of the above-mentioned solvent may be any content as long as it provides a composition with better patterning accuracy and heat resistance.
The above content can be, for example, 10 parts by mass or more and 95 parts by mass or less, preferably 40 parts by mass or more and 95 parts by mass or less, and 60 parts by mass or more, in 100 parts by mass of the composition of the present invention. It is preferably 90 parts by mass or less. This is because with the above content, the composition has excellent coating properties.

(3) Silane coupling agent The above composition can contain a silane coupling agent as necessary.
As such a silane coupling agent, one having a molecular weight of 100 or more and 1000 or less can be used, and for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, KBE-9007, KBM-502, A silane coupling agent having an isocyanate group, a methacryloyl group, or an epoxy group, such as KBE-403, is preferably used.
Among the above-mentioned silane coupling agents, even those containing methacryloyl groups, epoxy groups, etc. are not included in the polymerizable component B.

(4) Colorant The above composition may contain a colorant, if necessary.
Examples of the coloring agent include pigments, dyes, natural pigments, and the like. These colorants can be used alone or in combination of two or more.

Examples of the pigments include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindoline compounds; quinacridone compounds; Compounds; perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compounds; quinophthalone compounds; naphthalenetetracarboxylic acid; metal complex compounds of azo dyes and cyanine dyes; lake pigments; furnace method, channel method or thermal carbon black obtained by a method, or carbon black such as acetylene black, Ketjen black, or lamp black; carbon black prepared by adjusting or coating the above carbon black with an epoxy resin, dispersing the above carbon black in a resin in a solvent in advance, ~200mg/g of resin adsorbed, carbon black with acidic or alkaline surface treatment, average particle size of 8 nm or more and DBP oil absorption of 90ml/100g or less, CO in volatile matter at 950°C and those whose total oxygen amount calculated from CO ₂ is 9 mg or more per 100 m ² of surface area of carbon black; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene ;Aniline black, pigment black 7, titanium black, perylene black, lactam black, cyanine black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine, navy blue, ultramarine, cerulean Organic or inorganic pigments such as blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, synthetic iron black, and amber can be used. These pigments can be used alone or in combination.

As the pigment, commercially available pigments can also be used, such as 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, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185, 211, 215, 231; Pigment Green 7, 10, 36, 58, 59, 62, 63; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50; Pigment Violet 19, 23, 29, and the like.

The above dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, and phthalocyanine dyes. , cyanine dye, etc., and a plurality of these may be used in combination.

The content of the above-mentioned coloring agent may be any content as long as it can obtain a cured product with desired coloration, and for example, it is preferably 1 part by mass or more and 80 parts by mass or less in 100 parts by mass of solid content of the above-mentioned composition. Among them, it is preferably 5 parts by mass or more and 60 parts by mass or less, and particularly preferably 10 parts by mass or more and 50 parts by mass or less.
Further, the content of the colorant may be any content as long as it can obtain a cured product with a desired color, and for example, it may be 1 part by mass or more and 350 parts by mass or less based on 100 parts by mass of the polymerizable component B. The content is preferably 10 parts by mass or more and 250 parts by mass or less, particularly preferably 20 parts by mass or more and 200 parts by mass or less.

(5) Additives Other ingredients mentioned above include colorants, inorganic compounds, dispersants for dispersing colorants and inorganic compounds, chain transfer agents, sensitizers, surfactants, silane coupling agents, melamine, etc. Additives may be mentioned.
For the additive, known materials can be used, and for example, those described in International Publication No. 2014/021023 can be used.
As the above-mentioned additives, ultraviolet absorbers, antioxidants, etc. can also be used.
As the above-mentioned ultraviolet absorber, a latent ultraviolet absorber or a latent antioxidant that exhibits ultraviolet absorbing ability or antioxidant function by heat treatment or the like can also be used.
As such latent ultraviolet absorbers and latent antioxidants, those described as latent additives described in International Publication No. 2014/021023 can be used, for example.

The total content of the above additives can be 30 parts by mass or less in 100 parts by mass of solid content of the composition.

6. Manufacturing method The method for manufacturing the above-mentioned composition may be any method as long as it is possible to mix each of the above-mentioned components in a desired content, and it may be a method of adding and mixing each of the above-mentioned components at the same time, or a method of adding each component in sequence. It may also be a method of mixing while

The uses of the above composition can be the same as those of the composition to which the thiol generator described in the section "A. Compound" is added.

D. Cured Product Next, the cured product of the present invention will be explained.
The cured product of the present invention is characterized by being a cured product of the above-mentioned composition.

According to the present invention, the cured product has excellent patterning accuracy and heat resistance by using the above-mentioned composition.

The cured product of the present invention uses the above-mentioned composition.
The contents of the composition can be the same as those described in the section "C. Composition" above, so the explanation here will be omitted.

The cured product has a polymer in which the polymerizable components B are polymerized with each other.

The residual rate of unreacted polymerizable component B contained in the cured product is appropriately set depending on the use of the cured product, etc., but for example, it is not more than 10 parts by mass in 100 parts by mass of the cured product. The content is preferably 1 part by mass or less. This is because the cured product has excellent heat resistance.

Compound A contained in the cured product has a thiol group protected by a protecting group ^R1 , a compound in which a thiol group is generated by removing the protecting group ^R1 , and a compound in which the polymerizable components B are cross-linked. It may be something.
Here, the term "compound A crosslinking the polymerizable components B" refers to a state in which the compound A after R ¹ is eliminated crosslinks the polymerizable components B together.
Further, crosslinking refers to a state in which a thiol group generated from compound A due to ^R1 elimination forms a covalent bond with a thiol-reactive group of polymerizable component B through a thiol-ene reaction, etc. .
In the present invention, it is preferable that the compound A is one in which the polymerizable components B are crosslinked with each other. This is because the cured product has excellent heat resistance.
The polymerizable component B to which the compound A is crosslinked contains at least one of the following (1) and (2).
(1) Unreacted polymerizable component B remaining without polymerizing with polymerizable component B
(2) Among polymers in which polymerizable components B are polymerized, those having a thiol-reactive group

The planar shape of the cured product can be appropriately set depending on the use of the cured product, and is preferably in a pattern such as a dot shape or a line shape. This is because the effect of being able to form a composition with excellent patterning accuracy and heat resistance of the present invention can be more effectively exhibited.

The use of the cured product can be the same as described in the section "A. Compound" above.

The method for producing the cured product is not particularly limited as long as it is a method that can form the cured product of the composition into a desired shape.
As such a manufacturing method, for example, the manufacturing method described in the section "E. Manufacturing method of cured product" described later can be used.

E. Method for producing a cured product Next, a method for producing a cured product of the present invention will be described.
The manufacturing method of the present invention includes a step of crosslinking.
Each step of the manufacturing method of the present invention will be explained in detail below.

1. Crosslinking step The crosslinking step in the production method of the present invention is a step of crosslinking the polymerizable components B together using the compound represented by the general formula (A).
The crosslinking method in this step may be any method that can remove the protective group R ¹ from compound A and crosslink the polymerizable components B with each other using the generated thiol group, for example, a method of heat treating the above compound A. can be mentioned.
The heating temperature for heating the compound A may be any temperature condition that allows R ¹ to be desorbed from the compound A, and for example, it may be the same as described in the section "A. Compound" above. .
As a method for heat-treating the compound A, a method can be used in which the composition or a cured product thereof (the composition after the polymerization step described below) is heated using a known heating means such as an oven.
Moreover, the step of crosslinking may be performed simultaneously with the post-bake step described below.
Note that the polymerizable component B to be crosslinked in this step contains at least one of the following (1) and (2) when this step is performed after the polymerization step described below.
(1) Unreacted polymerizable component B remaining without polymerizing with polymerizable component B
(2) Among polymers in which polymerizable components B are polymerized, those having a thiol-reactive group

2. Step of Polymerizing The method for producing the cured product preferably includes a step of polymerizing the polymerizable components B together. This is because the patterning accuracy and heat resistance are excellent.
The method of polymerizing the polymerizable components B in this step may be any method as long as the polymerizable components B can be polymerized with each other. For example, the composition may contain a polymerization initiator together with the polymerizable component B. Here are some methods.
The above polymerization method differs depending on the type of radical polymerization initiator.
For example, when the above composition contains a photopolymerization initiator such as a photoradical polymerization initiator or a photocationic polymerization initiator, the composition is irradiated with light to separate the polymerizable components B from each other. A method of polymerization can be used.
The light irradiated onto the composition may include light with a wavelength of 300 nm to 450 nm.
Examples of the light source for the light irradiation include ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, and the like.
Laser light may be used as the irradiated light. As the laser light, one containing light with a wavelength of 340 to 430 nm can be used.
As the laser light source, those that emit light in the visible to infrared region, such as argon ion laser, helium neon laser, YAG laser, and semiconductor laser, can also be used.
In addition, when using these lasers, the said composition can contain the sensitizing dye which absorbs the said range from visible to infrared.

In the above polymerization method, for example, when the composition contains a thermal polymerization initiator such as a thermal radical polymerization initiator or a thermal cationic polymerization initiator, the composition is heat-treated and polymerizable. A method of polymerizing components B together can be used.
The heating temperature may be any temperature as long as it can stably cure the composition, 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 types of polymerization methods described above may include only one type, or may include two or more types.

The timing of performing the polymerization step may be before or after the crosslinking step, but from the viewpoint of producing a patterned cured product with good patterning accuracy, the crosslinking step Preferably before.

3. Other Steps The method for producing the cured product may include other steps as necessary in addition to the crosslinking and polymerization steps.
The other steps include, after the polymerization step, a development step in which the unpolymerized portion of the coating film of the composition is removed to obtain a patterned cured product, and a post-bake step in which the cured product is heat-treated after the polymerization step. A pre-baking step of heating the composition to remove the solvent in the composition before the polymerization step, a step of forming a coating film of the composition before the polymerization step, etc. can.

An example of a method for removing the unpolymerized portion in the development step is a method of applying an alkaline developer to the unpolymerized portion.
As the alkaline developer, those commonly used as alkaline developers such as a tetramethylammonium hydroxide (TMAH) aqueous solution and a potassium hydroxide aqueous solution can be used.
The development step may be performed after the polymerization step, but from the viewpoint of producing a patterned cured product with good patterning accuracy, it is preferably before the desorption step. .
The heating conditions in the post-baking step may be any conditions as long as they can improve the strength etc. of the cured product obtained in the polymerization step, and may be, for example, 100°C or higher and 300°C or lower, and 120°C or higher. The temperature is preferably 150°C or higher, and can be set at 200°C or higher and 250°C or lower for 20 minutes to 90 minutes. This is because, when the post-bake temperature is within the above-mentioned range, it becomes easy to carry out the post-bake step and the crosslinking step at the same time after the polymerization step.
The heating conditions in the prebaking step may be any condition as long as the solvent in the composition can be removed, and may be, for example, 70° C. or higher and 150° C. or lower for 30 seconds to 300 seconds.
Moreover, it is preferable that the heating conditions in the prebaking step be performed at a temperature below the desorption temperature of the compound A, from the viewpoint that, for example, the polymerization step and the crosslinking step can be easily performed in this order. From this point of view, the heating conditions in the pre-baking step are preferably lower than 150°C, particularly preferably lower than 120°C, particularly preferably lower than 100°C, and particularly preferably lower than 90°C. It is preferable that there be.
In the step of forming the coating film, known methods such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing methods, and dipping methods can be used to apply the composition.
The above coating film can be formed on a base material.
The above-mentioned base material can be appropriately selected depending on the intended use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, and the like.
Moreover, after the cured product is formed on a base material, it may be peeled off from the base material and used, or it may be used after being transferred from the base material to another adherend.

4. Others The cured product produced by the above production method and its uses can be the same as those described in the above "D. Composition" section.

The present invention is not limited to the above embodiments. The above-mentioned embodiments are illustrative, and any embodiment that has substantially the same configuration as the technical idea stated in the claims of the present invention and has similar effects is the present invention. within the technical scope of the invention.

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Example 1]
0.01 mol of a polyfunctional thiol represented by the following formula (A6-1') (TS-G manufactured by Shikoku Kasei), 0.05 mol of di-tert-butyl dicarbonate, and 30 g of pyridine were mixed, and the mixture was heated 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, then 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.

[Examples 2 to 6]
Instead of the polyfunctional thiol represented by the above formula (A6-1'), the following formulas (A4-1'), (A3b-1'), (A2-1'), (A5-1') and ( The following formulas (A4-1), (A3b-1), (A2-1), (A5-1 ) and (A3a-1) were obtained. The obtained compounds are compounds represented by the following formulas (A4-1), ⁽ A3b-1), (A2-1), (A5-1) and (A3a-1), respectively. Confirmed by H-NMR. Among these, the results for (A4-1), (A2-1), (A5-1) and (A3a-1) are shown in Table 1 below.

[Example 7]
0.06 mol of a polyfunctional thiol represented by the following formula (A6-1') (TS-G manufactured by Shikoku Kasei) was charged into a 500 mL two-neck round bottom flask, dried under reduced pressure and replaced with nitrogen, and then anhydrous. 42 mL of DMF (manufactured by Kanto Kagaku) 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. After further stirring for 3 hours, 600 mL of ethyl acetate was added. The organic layer was washed with 300 mL of distilled water. After performing the above washing four times, the organic layer was dried with sodium sulfate, filtered, and the solvent was removed under reduced pressure. The reaction product thus obtained was dried under reduced pressure at 60° C. for 2 hours to obtain a compound represented by the following formula (A6-2). It was confirmed by ¹ H-NMR that the obtained compound was a compound represented by the following formula (A6-2).

[Examples 8 to 10]
Instead of the polyfunctional thiol represented by the above formula (A6-1'), polyfunctional thiols represented by the following formulas (A4-1'), (A2-1') and (A5-1') are used. Compounds represented by the following formulas (A4-2), (A2-2) and (A5-2) were obtained in the same manner as in Example 1, except that It was confirmed by ¹ H-NMR that the obtained compounds were represented by the following formulas (A4-2), (A2-2), and (A5-2), respectively.

[Manufacture example 1]
A flask equipped with a cooling tube and a stirrer was charged with 4 parts by mass of 2,2'-azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate, followed by 55 parts by mass of methacrylic acid, 45 parts by mass of benzyl methacrylate, In addition, 2 parts by mass of α-methylstyrene dimer as a molecular weight regulator was charged, and the temperature of the solution was raised to 80° C. while stirring gently. After maintaining the temperature at 80° C. for 4 hours, the temperature of the solution was raised to 100° C., and this temperature was maintained for 1 hour for polymerization to obtain a solution containing the copolymer. Next, 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 this copolymer, and after stirring at 90°C for 30 minutes in an air atmosphere, methacrylic Polymer U-1 was obtained by adding 74 parts by mass of glycidyl acid and reacting at 90° C. for 10 hours (solid content concentration = 35.0%). The weight average molecular weight Mw of the polymer U-1 was 9,000.
The polymer U-1 has the above-described structural unit (U1), structural unit (U2), and structural unit (U4). The polymer U1 is a radically polymerizable compound and has an acid group.

[Production Example 2] Production of blue pigment dispersion DISPERBYK-161 (8.4 parts by mass; manufactured by BYK Chemie Japan) as a dispersant and Pigment Blue 15:6 (14 parts by mass) as a colorant, PGMEA (77.6 parts by mass) parts by mass) using a bead mill to produce a blue pigment dispersion (solid content concentration 22.4% by mass, pigment concentration in solid content 62.5% by mass, solvent PGMEA).

[Production Example 3] Production of black pigment dispersion DISPERBYK-161 (11.25 parts by mass; manufactured by BYK Chemie Japan, solid content concentration 40% by mass) as a dispersant and MA100 (15 parts by mass; manufactured by Mitsubishi Chemical, manufactured by Mitsubishi Chemical) as a coloring agent. black pigment) was dispersed in PGMEA (73.75 parts by mass) using a bead mill to obtain a black pigment dispersion (solid content concentration 19.5 mass%, pigment concentration in solid content 76.92 mass%, solvent PGMEA) was manufactured.

[Examples 2-1 to 2-22 and Comparative Examples 2-1 to 2-9]
According to the formulations shown in Tables 2 to 4 below, compound A, thiol compound, polymerizable component B, polymerization initiator, pigment dispersion, coupling agent, and solvent were mixed and stirred at 25°C for 1 hour to form a composition. I got it.
In addition, the following materials were used for each component.
Note that the blending amounts in the table represent parts by mass of each component.

(Compound A)
A-1: Compound A-2 produced in Example 1 and represented by the above general formula (A6-1) A-2: Compound A- produced in Example 2 and represented by the above general formula (A4-1) 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 9: Manufactured compound A-10 represented by the above general formula (A2-2): Compound represented by the above general formula (A5-2) manufactured in Example 10

(thiol compound)
A-1': A compound represented by the above formula (A6-1') A-2': A compound represented by the above formula (A4-1') A-3': A compound represented by the above formula (A3b-1') Compound A-4' represented by the above formula (A2-1'): Compound A-5' represented by the above formula (A5-1'): Compound A-6' represented by the above formula (A5-1'): Compound A-6' represented by the above formula (A3a- Compound represented by 1')

(Polymerizable component B)
B-1: SPC-3000 (radical polymerizable compound, acid group-containing compound (acid group-containing epoxy acrylate), high molecular weight compound; manufactured by Showa Denko, solid content 42.7% by mass, propylene glycol monomethyl ether acetate solution)
B-2: Dipentaerythritol hexaacrylate (radical polymerizable compound, compound without acid group, low molecular weight compound, Kayalad DPHA manufactured by Nippon Kayaku)
B-3: Polymer obtained in Production Example 1 above (radical polymerizable compound, compound having an acid group, high molecular weight compound, solid content concentration 35.0% by mass, propylene glycol monomethyl ether acetate solution)

(Polymerization initiator)
C-1: 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 (photoradical polymerization initiator, acylphosphine oxides)
C-4: Compound represented by the following formula (C4) (photoradical polymerization initiator, acetophenones)

(Pigment dispersion)
D-1: Blue pigment dispersion produced in Production Example 2 (solid content concentration 22.4% by mass, pigment concentration in solid content 62.5% by mass, solvent PGMEA)
D-2: Black pigment dispersion produced in Production Example 3 (solid content concentration 19.5% by mass, pigment concentration in solid content 76.92% by mass, solvent PGMEA)

(Silane coupling agent)
E-1: KBE-403 (silane coupling agent, manufactured by Shin-Etsu Chemical)
(solvent)
F-1: Propylene glycol-1-monomethyl ether-2-acetate (solvent)

[evaluation]
The compounds obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Tables 2 to 4.

1. Patterning accuracy The compositions of Examples and Comparative Examples were spin-coated on a glass substrate so that the chromaticity coordinates (x, y) = (0.135, 0.098) after post-baking were applied using a hot plate. After pre-baking at 90°C for 120 seconds, it was cooled at 23°C for 60 seconds.
Thereafter, exposure was performed using an ultra-high pressure mercury lamp through a photomask (mask opening 30 μm) (exposure gap 300 μm, exposure amount 40 mJ/cm ² ).
After developing for 60 seconds using a 0.04% by mass KOH aqueous solution as a developer, it was thoroughly washed with water and post-baked at 230° C. for 20 minutes using a clean oven to fix the pattern and obtain a sample for evaluation.
The obtained pattern was observed with an optical microscope, and the line width of the portion corresponding to the mask opening was measured. When the obtained line width was within the range of ±5 μm with respect to the mask opening of 30 μm as a reference, it was marked as ○, when it exceeded ±5 and fell within the range of ±10 μm, it was marked as △, and when it exceeded ±10 μm was marked as ×. 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 judged that the patterning accuracy is good.

2. Heat Resistance A sample for evaluation was obtained using a method similar to the method described in the section "1. Patterning Accuracy" above.
The film thickness of the obtained pattern was measured, and the film reduction rate was calculated using the following formula.
Film reduction rate (%) = 100 - (film thickness after post-baking / film thickness after pre-baking) x 100
Note that the film thickness was measured using DEKTAKXT manufactured by Bruker.
A film reduction rate of less than 20% was marked as ○, a film reduction rate of 20% or more and less than 25% was marked as △, and a film reduction rate of 25% or more was marked as ×. The results are shown in Tables 2 and 3 below.
It can be judged that the smaller the film reduction rate is, the higher the crosslinking density of the resist film is, and the better the heat resistance is.

3. Wrinkles Using an evaluation sample obtained by the method described in "1. Patterning Accuracy" above, the presence or absence of wrinkles observed on the surface of a pattern formed with a mask opening of 30 μm was observed using an optical microscope. Evaluation was performed based on the criteria. Note that "wrinkles" are observed when the film thickness of the obtained pattern is not uniform and there is thickness unevenness. Examples of optical microscope observation images and SEM observation images when wrinkles occur in the pattern are shown in Figures 1 and 2, and examples of optical microscope observation images and SEM observation images when wrinkles occur in the pattern are shown in Figures 4 and 2. Shown in Figure 5. When wrinkles occur, a striped pattern is observed, which is assumed to be caused by uneven thickness, as shown in FIGS. 1 and 2.
○: No wrinkles were observed.
Δ: Wrinkles were observed.
If there are no wrinkles, it can be determined that the pattern form is good.

4. Storage stability The viscosity of the compositions of Examples and Comparative Examples immediately after production and after being left at 23°C for 7 days was measured using a viscometer (cone-plate viscometer (Toki Sangyo TVE-22H) in an atmosphere at 25°C). )), and the storage stability was evaluated based on the following criteria.
〇: The viscosity change rate after standing compared to the viscosity immediately after production is less than 10% ×: The viscosity change rate after standing compared to the viscosity immediately after production is more than 10% If the evaluation is 〇, the storage stability is excellent. I can confirm that.

From Tables 2 to 4, Compound A in which the thiol group is protected by R ¹ has higher patterning accuracy and heat resistance than, for example, examples in which a thiol compound is used instead of Compound A, and examples that do not contain a thiol compound. It was confirmed that it was possible to form a composition with excellent properties.
Compound A is a compound represented by the above general formula (A6) such as the above formula (A6-1) and (A6-2), or a compound represented by the above general formula (A4) such as (A4-1) and (A4-2). It was confirmed that by using the compound represented by the following, it is possible to form a composition particularly excellent in patterning accuracy and heat resistance.
Furthermore, a structure in which R ¹ has a methylene group at the terminal end on the sulfur atom side substituted with -CO-O- is more likely to cause wrinkles than a structure in which the methylene group at the terminal end on the sulfur atom side is substituted with -CO-NR-. It was confirmed that the occurrence of
The structure in which the terminal methylene group on the sulfur atom side is substituted with -CO-NR- allows the elimination reaction of R ¹ to proceed more easily than the structure in which the terminal methylene group on the sulfur atom side is substituted with -CO-O-. As a result, there is a difference in the progress of the desorption reaction between areas where the temperature rise is easy during heat treatment, such as the front side of the patterned cured product, and areas where the temperature rise is not easy, such as the back side. It is presumed that the difference in crosslinking density within the resulting patterned cured product increases, causing wrinkles.

[Examples 2-23 to 2-28 and Comparative Examples 2-10 to 2-15]
According to the formulations shown in Tables 5 and 6 below, compound A, thiol compound, polymerizable component B, polymerization initiator, pigment dispersion, coupling agent, and solvent were mixed and stirred at 25°C for 1 hour to form a composition. I got it.
Moreover, the above-mentioned materials were used for each component.
Note that the blending amounts in the table represent parts by mass of each component.

Regarding the compounds obtained in Examples and Comparative Examples, in addition to the evaluation of "1. Patterning accuracy" described above, the following evaluation was performed. The results are shown in Tables 5 and 6.

5. Heat resistance 2
The compositions of Examples and Comparative Examples were spin-coated onto a glass substrate so that the film thickness after post-baking was 2 μm, and after pre-baking at 90°C for 120 seconds using a hot plate, the compositions were coated at 23°C. Cooled for 60 seconds.
Thereafter, exposure was performed using an ultra-high pressure mercury lamp through a photomask (mask opening 30 μm) (exposure gap 300 μm, exposure amount 40 mJ/cm ² ).
After developing for 60 seconds using a 0.04% by mass KOH aqueous solution as a developer, it was thoroughly washed with water, and post-baked for 20 minutes at 230°C using a clean oven to fix the pattern, and an evaluation sample with a film thickness of 2 μm was prepared. I got it.
Further, an evaluation sample with a film thickness of 10 μm was obtained in the same manner as described above, except that spin coating was performed so that the film thickness after post-baking was 10 μm.
Using these samples, the film reduction rate (%) was calculated in the same manner as in the evaluation of "2. Heat resistance" above. The table shows the numerical values of the film reduction rate (%).

6. Wrinkles Using the evaluation sample obtained by the method described in the above section "5. Heat resistance 2", the same evaluation as in the above "3. Wrinkles" was performed.

7. Development Margin The compositions of Examples and Comparative Examples were spin-coated onto a glass substrate so that the film thickness after post-baking was 3 μm, and after pre-baking at 90° C. for 120 seconds using a hot plate, Cooled for 60 seconds at °C.
Thereafter, exposure was performed using an ultra-high pressure mercury lamp through a photomask (mask opening 30 μm) (exposure gap 300 μm, exposure amount 40 mJ/cm ² ).
Using a 0.04% by mass KOH aqueous solution as a developer, spray development was performed at 23°C and a discharge pressure of 0.15 MPa, and the time until the cured part located at the opening of the mask peeled off from the base material was measured. , and evaluated based on the following criteria.
Good: The time until peeling was 100 seconds or more from the start of development.
Δ: The time until peeling was 80 seconds or more and less than 100 seconds from the start of development.
×: The time until peeling was more than 60 seconds and less than 80 seconds from the start of development.

From Tables 5 and 6, it can be seen that Compound A in which the thiol group is protected by R ¹ can form a composition with excellent patterning accuracy compared to an example in which a thiol compound is used instead of Compound A. It could be confirmed. Furthermore, it was confirmed that it was possible to form a composition that had excellent heat resistance and development margins and did not cause wrinkles, compared to examples that did not contain a thiol compound. The excellent development margin makes it possible to stably form a pattern with a predetermined shape even when the alkali development time fluctuates.
Compared to using A-6 (the compound represented by the above general formula (A3a-1)) as compound A, A-2 (the compound represented by the above general formula (A4-1)) was used. A composition with a better development margin was obtained when it was mixed. Since the equivalent weight of the protected thiol group in compound A is A-2>A-6, it is assumed that the crosslinking density will be higher when A-6 is used. However, since A-2, which is hexafunctional and has a large molecular weight, is highly hydrophobic, a cured product with higher resistance to alkaline developers can be obtained. It is presumed that a stable cured product was formed even when exposed to water for a long time.

8. Patterning accuracy 2
The compositions of Example 2-24, Comparative Examples 2-11 and 2-14 were spin-coated onto a glass substrate so that the thickness after prebaking was 4.0 μm to form a coating film. Next, using a hot plate, the mixture was prebaked at 90°C for 120 seconds, and then cooled at 23°C for 60 seconds. Thereafter, exposure was performed using an ultra-high pressure mercury lamp through a photomask with an exposure gap of 300 μm. After the exposed coating film was developed for 60 seconds using a 0.04% by mass KOH aqueous solution as a developer, it was thoroughly washed 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. Note that the evaluation sample was prepared by combining the following levels as the photomask opening width and exposure amount.
Mask opening width (5 levels): 2.0 μm, 10.0 μm, 30.0 μm, 50.0 μm, 100.0 μm
Exposure amount (3 levels): 50mJ/cm ² , 100mJ/cm ² , 300mJ/cm ²
The resulting 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 judged that the patterning accuracy is good.

9. Heat resistance 3
A sample for evaluation was obtained using the same method as described in "8. Patterning Accuracy 2" above.
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 better as there is no difference in the thickness after prebaking.

From Table 7, it was confirmed that by using Compound A, a patterned cured product having a width with a small difference from the mask opening width could be obtained regardless of the amount of exposure.
Further, from Table 7, it was confirmed that by using Compound A, a patterned cured product having a thickness with a small difference from the thickness after prebaking could be obtained regardless of the amount of exposure.
In this way, by using Compound A, a patterned cured product with a set width and thickness can be obtained regardless of the amount of exposure, and a patterned cured product with a high aspect ratio can be stably obtained. This was confirmed.

Claims (9)

A compound represented by the following general formula (A1), (A2), (A4) or (A6) .
(In the formula, 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 from 1 to 20,
R ²¹ , R ²² and R ²³ each independently represent 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 ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent the following general formula (101),
L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ and L ⁴⁶ represent an alkylene group having 1 to 10 carbon atoms,
R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent the following general formula (101),
L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ represent an alkylene group having 1 to 10 carbon atoms,
R ⁶⁵ and R ⁶⁶ each independently represent a hydrogen atom or a monovalent aliphatic group having 1 to 40 carbon atoms,
One or more methylene groups in the aliphatic group excluding R ²⁴ 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'-, -S-S-, or -SO ₂ -, or these may be substituted with a group selected from It may be replaced by a combination of groups,
One or more methylene groups in the aliphatic group represented by R ²⁴ are groups selected from -O-, -S-, -NR'-, -S-S-, or -SO ₂ - It may have been replaced by . )
(In the formula, R ¹ is a monovalent aliphatic group having 1 to 40 carbon atoms or a monovalent aliphatic group having 7 to 35 carbon atoms, in which the terminal methylene group on the sulfur atom side is substituted with -CO-O-. represents an arylalkyl group,
* represents the joint location,
One or more methylene groups in the aliphatic group and arylalkyl group 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'-, -S-S-, or -SO ₂ -, or these may be substituted with a group selected from It may be replaced by a combination of groups. ) The compound according to claim 1 , represented by the general formula (A4) or (A6). A thiol generator comprising the compound according to claim 1 or 2 . The thiol generator according to claim 3 , which is used for pattern formation. A compound according to claim 1 or 2 ,
a polymerizable component having thiol reactivity;
A polymerizable composition comprising: The polymerizable composition according to claim 5 , wherein the polymerizable component having thiol reactivity includes a radically polymerizable compound. A patterned cured product of the polymerizable composition according to claim 5 or 6 . The method for producing a patterned cured product according to claim 7 ,
A method for producing a patterned cured product, comprising a step of crosslinking the thiol-reactive polymerizable components with each other using a compound represented by the general formula (A). The method for producing a patterned cured product according to claim 8 , comprising a step of polymerizing the polymerizable components having thiol reactivity.