TWI660937B - Thiol compound, method for producing thiol compound, polymer, composition, curable composition, coloring composition, cured film, and color filter - Google Patents

Abstract

A thiol compound represented by formula (1); (HS-R ¹ -M ^1- ) _n L ¹ (1) In formula (1), L ¹ represents an n-valent organic linking group, and n represents 3 Integer to 15, M ¹ represents -O-, -S-, -N (R ² )-, -C (= O)-, -C (= O) -O-, -OC (= O) -O -, -C (= O) -NH-, -OC (= O) -NH-, -S (= O)-, -S (= O) -O-, -S (= O) ₂ -,- S (= O) ₂ -O- or -CH = N-, R ¹ represents an alkylene group or a group containing a combination of an alkylene group and an etheric oxygen atom, SH represents a thiol group, SH sulfur atom, The atom bonded to R ¹ with M ¹ is separated by 5 or more atoms of R ¹ .

Description

Thiol compound, method for producing thiol compound, polymer, composition, curable composition, coloring composition, cured film, and color filter

The present invention relates to a novel thiol compound. The present invention also relates to a method for producing a thiol compound, a polymer, a composition, a curable composition, and a coloring composition. The present invention further relates to a cured film using a curable composition or a colored composition, and a color filter using the colored composition.

Multifunctional thiol compounds have been used since before. For example, Patent Document 1 discloses the following compounds. [Chemical 1] In the above description, R is a hydrogen atom or an alkyl group, a is an integer of 1 to 4, and b is an integer of 1 to 4.

Further, Patent Documents 2 and 3 describe synthetic raw materials using a polyfunctional thiol compound as a dispersant. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication WO2009 / 129221 [Patent Document 2] Japanese Patent Laid-Open No. 2007-277514 [Patent Document 3] Japanese Patent Laid-Open No. 2013-79380

[Problems to be Solved by the Invention]

However, the present inventors have conducted studies, and as a result, it has been found that all of the polyfunctional thiol compounds described in Patent Documents 1 to 3 are inferior in heat resistance. The present invention aims to solve this problem, and an object thereof is to provide a thiol compound excellent in heat resistance. Furthermore, it aims at providing the manufacturing method of a thiol compound, a composition, a curable composition, a coloring composition, a cured film, and a color filter. [Means for solving problems]

Based on the above-mentioned problem, the present inventors conducted earnest research, and as a result, it was found that a predetermined linking group and a thiol group (SH) were separated by 5 or more atoms by a group such as an alkylene group, thereby suppressing the predetermined linking group Decomposition due to heat with a thiol group improves heat resistance and completes the present invention. Specifically, the problem can be solved by the following means <1>, preferably <2> to <17>. <1> A thiol compound represented by the following formula (1); (HS-R ¹ -M ^1- ) _n L ¹ (1) In the formula (1), L ¹ represents an n-valent organic linking group , N represents an integer from 3 to 15, M ¹ represents -O-, -S-, -N (R ² )-, -C (= O)-, -C (= O) -O-, -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -S (= O)-, -S (= O) -O-, -S (= O) _2- , -S (= O) ₂ -O-, or -CH = N-, R ¹ represents an alkylene group or a group containing a combination of an alkylene group and an etheric oxygen atom, R ² represents a hydrogen atom, or It may contain an alkyl group having 1 to 10 carbon atoms of an etheric oxygen atom, or an aromatic hydrocarbon group which may also contain an etheric oxygen atom, SH represents a thiol group, a sulfur atom of SH, and M ¹ is bonded to R ¹ The atom of is separated by 5 or more atoms of R ¹ . <2> The thiol compound according to <1>, wherein R ¹ represents a linear alkylene group having 5 to 30 carbon atoms, a branched alkylene group having 6 to 30 carbon atoms, and a straight alkylene group containing 3 to 27 carbon atoms. A group containing a combination of an alkylene group and an etheric oxygen atom, or a group containing a combination of a branched alkylene group having 4 to 28 carbon atoms and an etheric oxygen atom. <3> The thiol compound according to <1>, wherein R ¹ represents a linear alkylene group having 5 to 20 carbon atoms, an alkylene group having 5 to 20 carbon atoms including an ethyloxy group, or An alkylene group having 5 to 20 carbon atoms including an isopropyloxy group. <4> The thiol compound according to any one of <1> to <3>, wherein L ¹ is a linking group derived from a polyhydric alcohol. <5> The thiol compound according to any one of <1> to <4>, wherein L ¹ contains 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, and 0 to 50 oxygen atoms. Atom, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. <6> The thiol compound according to any one of <1> to <4>, wherein L ^{1 is} selected from a structure represented by any one of the following (L-1) to (L-21); [化 2] [Chemical 3] In the description, r is an integer of 0 to 10, R ³¹ to R ⁴¹ each independently represent an alkyl group, R ⁴² represents a hydrogen atom, an alkyl group, or an alkoxy group, and R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, or The alkyl group having 1 to 6 carbon atoms, s is an integer of 0 to 9, and L ⁴ represents -O- or -C (= O)-. <7> The thiol compound according to any one of <1> to <4>, wherein L ^{1 is} selected from a structure represented by any one of the following; In the above description, r is an integer of 0 to 10, and R ⁴² , R ⁴³ and R ⁴⁴ are ethyl groups. <8> A method for producing a thiol compound, which is a method for producing a thiol compound according to any one of <1> to <7>, comprising the step of: making a compound represented by the following formula (3) After reacting with a compound represented by the following formula (4), reacting the obtained product with a sulfur-containing compound having a protective group Z, the protective group Z is removed to generate a thiol group; L ^1- (R ^H ) _n (3) XM ^a -R ¹ -Y (4) In the formula, L ¹ represents an n-valent organic linking group, and R ^H represents at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, and includes an oxygen atom and a nitrogen atom. A group of a hydrogen atom connected to any of sulfur atoms, n represents an integer of 3 to 15, Y represents a group that is released by reaction with a sulfur-containing compound having a protective group Z, and R ¹ represents an alkylene group or a group containing combination of an alkyl group, an ether group oxygen atom, Y is bonded to R ¹ atoms, and R and M ^a junction atom via ^a bond R 5 is ¹ or more atoms, M ^a represents a single bond or two A valent linking group, X represents a group containing at least one of a halogen atom or a sulfonate. <9> A method for producing a thiol compound, comprising the steps of reacting a 3- to 15-membered polyhydric alcohol with a compound represented by the following formula (4-1), and causing the obtained product to react with a protective group Z After the sulfur-containing compound is reacted, the protective group Z is detached to generate a thiol group; XM ^a1 -R ¹ -Y (4-1) In the formula, Y represents that it is detached by reaction with a sulfur-containing compound having a protective group Z. R ¹ represents an alkylene group or a group containing a combination of an alkylene group and an etheric oxygen atom, an atom of Y bonded to R ¹ , and an atom of M ^a1 bonded to R ¹ are separated by R ¹ 5 or more atoms, M ^a1 represents -C (= O)-, and X represents a group containing at least one of a halogen atom or a sulfonate. <10> A method for producing a thiol compound, comprising the steps of reacting a 3- to 15-membered polyhydric alcohol with a compound represented by the following formula (4-2), and reacting the obtained product with a protective group Z After the reaction of the sulfur-containing compound, the protective group Z is detached to generate a thiol group; XR ¹ -Y (4-2) In the formula, Y represents a group that is detached by reaction with a sulfur-containing compound having a protective group Z, R ¹ represents an alkylene group, or a group comprising a combination of an alkylene group and an ether oxygen atom, Y is bonded to R ¹ atoms, and R and X bond via ^a junction atom R ¹ is 5 or more Atom, X represents a group containing at least one of a halogen atom or a sulfonate. <11> The method for producing a thiol compound according to any one of <8> to <10>, wherein the protective group Z is a group represented by the following formula (5) and is represented by the following formula (6) Or a salt of a group represented by the following formula (6); In the formula (5), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms. <12> A polymer represented by the following formula (7); In formula (7), L ¹ represents a (n1 + n2) valent organic linking group, n1 represents 1 to 15, n2 represents 0 to 14, the total of n1 and n2 is 3 to 15, and M ¹ represents -O-, -S-, -N (R ² )-, -C (= O)-, -C (= O) -O-, -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -S (= O)-, -S (= O) -O-, -S (= O) _2- , -S (= O) ₂ -O-, or- CH = N-, R ¹ represents an alkylene group or a group containing a combination of an alkylene group and an etheric oxygen atom, R ² represents a hydrogen atom, and an alkyl group having 1 to 10 carbon atoms which may also contain an etheric oxygen atom, Or an aromatic hydrocarbon group which may also contain an etheric oxygen atom, SH represents a thiol group, the sulfur atom of SH, and the atom bonded to R ^{1 of} M ¹ are separated by 5 or more atoms of R ¹ , and S represents a sulfur atom This sulfur atom and the atom bonded to R ^{1 of} M ¹ are separated by 5 or more atoms of R ¹ , and P ¹ represents a monovalent substituent having a repeating unit derived from a compound having an ethylenically unsaturated bond. <13> A composition comprising a thiol compound produced by the production method according to any one of <8> to <11>, and 50% by mass or more of the composition is represented by formula (1 A specific one of the thiol compounds represented by). <14> A composition comprising the thiol compound according to any one of <1> to <7>, and 50% by mass or more of the composition is a thiol compound represented by formula (1) A specific one. <15> A composition containing the polymer according to <12>. <16> A curable composition containing the thiol compound according to any one of <1> to <7>, and produced by the production method according to any one of <8> to <11> At least one of the obtained thiol compound, the polymer according to <12>, and the composition according to any one of <13> to <15>, and a polymerizable compound. <17> A coloring composition comprising the thiol compound according to any one of <1> to <7> and obtained by the production method according to any one of <8> to <11> At least one of the thiol compound, the polymer according to <12>, and the composition according to any one of <13> to <15>, a polymerizable compound, and a coloring agent. <18> A cured film obtained by curing a curable composition according to <16> or a colored composition according to <17>. <19> A color filter obtained by using the coloring composition according to <17>. [Effect of the invention]

According to the present invention, a thiol compound excellent in heat resistance can be provided. Further, a method for producing a thiol compound, a polymer, a composition, a curable composition, and a colored composition can be provided. Further, a cured film and a color filter having excellent heat resistance can be provided.

Hereinafter, the content of this invention is explained in full detail. In the description of the group (atomic group) in the present specification, the descriptions of the substituted and unsubstituted expressions include the case where there is no substituent and the case where there is a substituent. For example, the term "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent.

The "actinic rays" or "radiation" in this specification means, for example, a bright line spectrum of a mercury lamp, extreme ultraviolet rays (EUV light) represented by an excimer laser, X-rays, electron beams, and the like. In the present invention, the term "light" means actinic rays or radiation. Unless otherwise specified, the "exposure" in this manual is not limited to exposure using the bright line spectrum of a mercury lamp, far-ultraviolet rays, X-rays, and EUV light typified by an excimer laser, and electron beams, ion beams, etc. The depiction of the particle beam is also included in the exposure.

The numerical range shown using "~" in this specification means the range which includes the numerical value described before and after "~" as a lower limit and an upper limit. As used herein, the term "all solids" refers to the total mass of components from which the solvent is removed from all the components of the coloring composition.

In this specification, "(meth) acrylate" means both acrylate and methacrylate, or any one, and "(meth) acrylate" means both acrylate and methacrylate, or Either "(meth) acrylfluorenyl" means both acrylfluorenyl and methacrylfluorenyl, or any one.

In this specification, "single body" is synonymous with "monomer". The singular body in this specification is distinguished from an oligomer and a polymer, and means a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound refers to a compound having a polymerizable functional group, and may be a singular body or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.

In the present specification, Me in the chemical formula represents methyl, Et represents ethyl, Pr represents propyl, Bu represents butyl, and Ph and PH represent phenyl. In this specification, NMR stands for nuclear magnetic resonance analysis, DMSO stands for dimethyl sulfonium, MALDI stands for Matrix Assisted Laser Desorption / Ionization, and MS stands for Mass Spectrum ), HPLC stands for High performance liquid chromatography, and PGMEA stands for propylene glycol-1-methyl ether acetate.

In this specification, the term "step" is not merely an independent step. Even if it cannot be clearly distinguished from other steps, if the desired effect of the step can be achieved, it is also included in this term.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values measured by gel permeation chromatography (GPC). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by Tosoh Corporation) and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm (inner diameter)). ) × 15.0 cm) was determined as a column using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidone) solution as the eluent.

Thiol compound The thiol compound of the present invention is represented by the following formula (1). (HS-R ¹ -M ^1- ) _n L ¹ In formula (1), L ¹ represents an n-valent organic linking group, n represents an integer of 3 to 15, and M ¹ represents -O-, -S-,- N (R ² )-, -C (= O)-, -C (= O) -O-, -OC (= O) -O-, -C (= O) -NH-, -OC (= O ) -NH-, -S (= O)-, -S (= O) -O-, -S (= O) _2- , -S (= O) ₂ -O-, or -CH = N-, R ¹ represents an alkylene group or a group containing a combination of an alkylene group and an etheric oxygen atom, SH represents a thiol group, R ² represents a hydrogen atom, and an alkyl group having 1 to 10 carbon atoms which may also contain an etheric oxygen atom or an aromatic hydrocarbon group may contain an etheric oxygen atom, SH sulfur atom, and the atom M ¹ and R junction bond therebetween atoms or more R 5 ^{1 1.} By adopting such a structure, a thiol compound excellent in heat resistance is obtained. That is, a polyfunctional thiol compound having a plurality of SH groups functions as a chain transfer agent in the presence of a polymerizable compound, for example. Here, it is presumed that, when the composition containing the polymerizable compound and the polyfunctional thiol compound is hardened, the polyfunctional thiol compound in the hardened product is three-dimensionally crowded because it is polyfunctional, and as the hardening progresses, the nearby Since the amount of the polymerizable compound is reduced, an average of about 1 to 5 thiol groups of the polyfunctional thiol compound remain unreacted after the hardening treatment. Here, as described above, a polyfunctional thiol compound having a plurality of SH groups is known. However, in the aforementioned Patent Document 1 (International Publication WO2009 / 129221), since the SH group and the ester group are short, they are easily broken by heat. In Patent Document 2 (Japanese Patent Laid-Open No. 2007-277514) and Patent Document 3 (Japanese Patent Laid-Open No. 2013-79380), a polyfunctional group is reacted between a SH group and a predetermined linking group such as an ester group. Decomposition of thiol compounds. On the other hand, in the present invention, heat resistance is improved by providing an alkylene group or a group containing a combination of an alkylene group and an etheric oxygen atom between a predetermined linking group represented by M ¹ and an SH group. This is because the presence of an alkylene group having a carbon number of 5 or more between the predetermined linking group and the SH group makes it difficult to perform the reaction between them even if heating is performed.

In formula (1), L ¹ represents an n-valent organic linking group, which contains 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, The group having 0 to 20 sulfur atoms may be unsubstituted or substituted.

Specific examples of L ¹ include a group consisting of the following structural units or a combination of two or more of the following structural units (which may also form a cyclic structure).

[Chemical 7]

L ^{1 is} preferably a group containing 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and 0 to 10 sulfur atoms. More preferred are radicals containing 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 sulfur atoms. Still more preferred are radicals containing 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms. It is particularly preferred that, in the aspect, a state including a carbon atom and a hydrogen atom, a state including a carbon atom and a hydrogen atom and an oxygen atom, or in the aspect, it is further preferred that the carbon atom and the A state in which more than one -NH- and / or -S- is contained between carbon atoms.

L ¹ may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amine group, a carboxyl group, a sulfonamido group, and N-sulfonic acid. Fluorenyl fluorenylamino, fluorenyl ethoxyl and other alkoxyl groups having 1 to 6 carbon atoms, methoxyl and ethoxyl alkoxyl groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, methoxycarbonyl , Alkoxycarbonyl groups having 2 to 7 carbon atoms such as ethoxycarbonyl and cyclohexyloxycarbonyl, carbonate groups such as cyano and tertiary butyl carbonate, and the like. However, it is preferable not to have a substituent.

L ¹ as described above is derived from, for example, a polyhydric alcohol. The valence of the polyhydric alcohol is preferably from 3 to 15 yuan. In addition, L ^{1 is} preferably expressed by any one of the following (L-1) to (L-21). * Indicates a bonding site with M ¹ . [Chemical 8]

In the above description, r is an integer of 0 to 10, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5. In particular, r = 1, r = 2, r = 3, r = 4, r = 5, r = 6, and r = 7 are better, and more preferably r = 1, r = 2, r = 3. , R = 4, r = 5, r = 6. R ³¹ to R ⁴¹ each independently represent an alkyl group, preferably a branched alkyl group having 3 to 10 carbon atoms, and more preferably a third butyl group. R ³¹ to R ⁴¹ may be different from each other, but the same groups are preferred. R ⁴² represents a hydrogen atom, an alkyl group, or an alkoxy group, preferably a hydrogen atom, a methyl group, an ethyl group, and a methoxy group, and more preferably an ethyl group. R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an ethyl group. s is an integer from 0 to 9, preferably an integer from 1 to 5, and more preferably an integer from 1 to 3.

[Chemical 9]

L ⁴ represents -O- or -C (= O)-.

Among the (L-1) to (L-21), (L-1), (L-4) to (L-7), (L-13) to (L-15), More preferred are (L-1), (L-5) to (L-6), (L-13) to (L-14), and even more preferred are (L-1) and (L-13) .

n represents an integer from 3 to 15. The lower limit of n is preferably 4 or more, and more preferably 5 or more. The upper limit of n is preferably 10 or less, and more preferably 8 or less. M ¹ represents -O-, -S-, -N (R ² )-, -C (= O)-, -C (= O) -O-, -OC (= O) -O-, -C ( = O) -NH-, -OC (= O) -NH-, -S (= O)-, -S (= O) -O-, -S (= O) _2- , -S (= O) ₂ -O-, or -CH = N-, preferably -O-, -S-, -C (= O)-, -C (= O) -O-, -OC (= O) -O -, -C (= O) -NH-, -OC (= O) -NH-, more preferably -O-, -S-, -C (= O)-, -C (= O) -O -, Further more preferably -O- or -C (= O) -O-, and particularly preferably -C (= O) -O-. The n M ¹ may be the same or different. Preferably, the n M ¹ are all the same. One end of the linking group represented by M ¹ is bonded to R ¹ and the other end is bonded to L ¹ , but any end may be bonded to any base. For example, in the case of -C (= O) -O-, a carbon atom may be bonded to R ¹ , and an oxygen atom may be bonded to R ¹ . R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may contain an etheric oxygen atom, or an aromatic hydrocarbon group which may also contain an etheric oxygen atom, and is preferably a hydrogen atom or a methyl group, and more preferably Is a hydrogen atom.

R ¹ represents an alkylene group, or a group comprising a combination of an alkylene group and an etheric oxygen atom, SH represents a thiol group, SH sulfur atom, and the atom M ¹ and R junction bond therebetween. 5 ^{1 1} R More than atoms. The so-called etheric oxygen atom refers to the oxygen atom contained between the alkylene group and the alkylene group. The etheric oxygen atom indicates that there are not two consecutive oxygen atoms. The n R ¹ may be the same or different. Preferably, all n R ¹ are the same. The alkylene group as R ¹ is a linear, branched, or cyclic alkylene group, preferably a linear or branched alkylene group, and more preferably a linear alkylene group or a methyl chain as a branch The branches of the chain are alkylated. Regarding the group containing a combination of an alkylene group and an etheric oxygen atom, a group containing a combination of a linear or branched alkylene group and an etheric oxygen atom is also preferable, and a group containing a linear alkylene group is more preferable. Or a group having a combination of a branched alkylene group having a methyl chain as a branched chain and an etheric oxygen atom. The alkylene group may have a substituent, and preferably does not have a substituent. When the alkylene group has a substituent, examples of the substituent which the above-mentioned L ¹ may have are exemplified. When R ¹ is a linear alkylene group, the lower limit of the carbon number may be 5 or more, 6 or more, or 7 or more. The upper limit value is preferably 50 or less, more preferably 40 or less, even more preferably 30 or less, and particularly preferably 20 or less. The upper limit value may be 12 or less, 10 or less, or 8 or less. When R ¹ is a branched alkylene group, the lower limit of the carbon number may be set to 6 or more, 7 or more, or 8 or more. The upper limit value is preferably 50 or less, more preferably 40 or less, even more preferably 30 or less, and particularly preferably 20 or less. The upper limit value may be 12 or less, and may also be set to 10 or less. When R ¹ is a cyclic alkylene group, it is usually a group including a combination of the linear or branched alkylene group and a cyclic alkylene group. The number of carbon atoms of the ring constituting the cyclic alkylene group is preferably 3 to 8, and more preferably 6. When R ¹ is a group containing a combination of a linear alkylene group and an etheric oxygen atom, the lower limit of the number of carbon atoms may be 3 or more, preferably 4 or more, and more preferably 5 or more. The upper limit value is preferably 50 or less, more preferably 40 or less, even more preferably 27 or less, and particularly preferably 20 or less. The upper limit value can be set to 10 or less, 8 or less, or 6 or less. As a preferred embodiment in a case where R ¹ is a group containing a combination of a linear alkylene group and an etheric oxygen atom, a sulfur atom including SH and a sulfur atom of M ¹ and A group having 5 to 20 atoms separated by an R ¹ bonded atom, preferably 2 to 5 ethylenoxy chains are repeated. When R ¹ is a group including a combination of a branched alkylene group and an etheric oxygen atom, the lower limit value of the carbon number may be set to 4 or more, 5 or more, or 6 or more. The upper limit value is preferably 50 or less, more preferably 40 or less, even more preferably 28 or less, particularly preferably 20 or less, or 10 or less, or 8 or less. As a preferred embodiment in a case where R ¹ is a group containing a combination of a branched alkylene group and an etheric oxygen atom, a sulfur atom including SH and a sulfur atom of M ¹ including an isopropyloxy group and M ¹ may be exemplified. A group having 5 to 20 atoms separated by the atom to which R ^{1 is} bonded can list a form including a structure in which 2 to 5 isopropylideneoxy chains are repeated. When R ¹ is a group containing a combination of a cyclic alkylene group and an etheric oxygen atom, it usually becomes a group containing a combination of a group including a linear or branched alkylene group A combination of an alkyl group and an ethereal oxygen atom. R ¹ in the present invention is particularly preferably a straight-chain alkylene group having 5 to 20 carbon atoms, an alkylene group having 5 to 20 carbon atoms containing an ethyloxy group, or an isopropyloxy group containing The alkylene group having 5 to 20 carbon atoms is more preferably a linear alkylene group having 5 to 20 carbon atoms or an alkylene group having 5 to 20 carbon atoms including an ethylenoxy chain. It is a linear alkylene group having 5 to 20 carbon atoms.

The sulfur atom of SH and the atom bonded to R ^{1 of} M ¹ are separated by 5 or more atoms of R ¹ , which means that the shortest atom number of R ¹ connecting SH and M ¹ is 5 or more, that is, connecting SH The shortest number of atoms between the sulfur atom and the atom bonded to R ^{1 of} M ¹ is 5 or more. This atom is a carbon atom or contains a carbon atom and an oxygen atom, and the total number is 5 or more. For example, in the case of the following compound (A), the number of atoms separated by SH and M ¹ becomes 6 atoms, and in the case of the following compound (B), the number of atoms separated by SH and M ¹ also becomes 6 atoms. [Chemical 10]

The molecular weight of the thiol compound of the present invention is preferably 300 to 3000, and more preferably 500 to 2500. It is preferable that the thiol compound of the present invention does not have the following groups. By not having the following groups, the heat resistance tends to be further improved. Anhydride group (-C (= O) -OC (= O)-, -S (= O) ₂ -OS (= O) _2- , -P (= O) (OH) -OP (= O) (OH )-, -S (= O) ₂ -OC (= O)-), phosphate group (-P (= O) (OH) -O-), dioxy group (-OO-), dithio group ( -SS-), methylenedioxy (-OCH ₂ O-), ethylenedifluorenyl (-C (= O) C (= O)-), malondifluoride (-C (= O) CH ₂ C (= O)-), ureido group (-NH-C (= O) -NH-), hydrazine group (-NHNH-), -C (= O) -S-, -OC (= O ) -S-, -C (= S) -O-, -OC (= S) -O-, -C (= S) -S-, -OC (= S) -S-, -SC (= S ) -S-

Hereinafter, preferred examples of the thiol compound of the present invention are shown, but the present invention is not limited to these examples.

[Chemical 11] In said (S-15), n is an integer of 1-13.

[Chemical 12] In said (S-16), n is an integer of 1-13.

[Chemical 13] In said (S-29), n is an integer of 1-13. In said (S-32), n is an integer of 1-13.

[Chemical 14]

[Chemical 15]

In addition, the compounds shown below are also preferable. (HS-R ¹ -M ^1- ) _n L ¹ [Table 1] [Table 2] [table 3] [Table 4] [table 5] [TABLE 6]

[TABLE 7] [TABLE 8]

[TABLE 9] [TABLE 10]

[TABLE 11] [TABLE 12]

[TABLE 13] [TABLE 14]

[Table 15] [TABLE 16]

[TABLE 17] [TABLE 18]

[TABLE 19]

Among the compounds, (S-1) to (S-48) and (S-51) are preferable, and (S-1) to (S-3), (S-4) to (S) are more preferable. -16), (S-22) to (S-38), (S-41) to (S-48), and (S-51), and more preferably (S-2) to (S-3) ), (S-5) to (S-8), (S-13), (S-22) to (S-24), (S-26) to (S-28), (S-31), (S-37) to (S-38), (S-41), and (S-44).

A method for producing a thiol compound Next, a method for producing a thiol compound according to the present invention will be described. The thiol compound of the present invention can be produced by reacting a compound represented by the following formula (3) with a compound represented by the following formula (4), and reacting the obtained product with a protective group Z After the sulfur-containing compound is reacted, the protective group Z is detached, thereby generating a thiol group. L ^1- (R ^H ) _n (3) XM ^a -R ¹ -Y (4) wherein L ¹ represents an n-valent organic linking group, and R ^H represents at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, And a group containing a hydrogen atom bonded to any of an oxygen atom, a nitrogen atom, and a sulfur atom, n represents an integer of 3 to 15, Y represents a group that is released by reaction with a sulfur-containing compound having a protective group Z, and R ¹ represents alkylene, or a group comprising a combination of an alkylene group and an ether oxygen atom, Y is bonded to R ¹ atoms, and M ^a is bonded to R ¹ through R 5 atoms or more atoms of ¹ M ^a represents a single bond or a divalent linking group, and X represents a group containing at least one of a halogen atom or a sulfonate.

N, L ^{1 in} Formula (3) and R ^{1 in} Formula (4) have the same meanings as n, L ¹ and R ¹ in Formula (1), and the preferred ranges are also the same. R ^H is a group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, and a hydrogen atom connected to any of an oxygen atom, a nitrogen atom, and a sulfur atom, and preferably a hydroxyl group, a thiol group, and a substituted group. Or unsubstituted amine, carboxyl.

X represents a group containing at least one of a halogen atom or a sulfonate, and is preferably a halogen atom. The halogen atom is preferably a fluorine atom, a chlorine atom, or a bromine atom, more preferably a chlorine atom or a bromine atom, and even more preferably a chlorine atom. Specific examples of X include trifluoromethanesulfonate, p-toluenesulfonate, benzenesulfonate, methanesulfonate, Cl-C (= O)-, Br-C (= O)-, and p-toluenesulfonate. Ethoxycarbonyl, methanesulfonyloxycarbonyl. M ^{a is} preferably a single bond, -C (= O)-, -O-, -C (= O) -O-, -NH-, or -S (= O)-, more preferably a single bond or -C (= O)-.

Y represents a group detached by a reaction with a sulfur-containing compound having a protective group Z, and more preferably a group detached by a reaction with a fluorenyl group or a methylamyl group. Specific examples thereof include a halogen atom, a trifluoromethanesulfonate, a p-toluenesulfonate, a benzenesulfonate, and a methanesulfonate. The halogen atom is preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a bromine atom.

The sulfur-containing compound containing a protective group Z is not particularly limited as long as it contains a sulfur atom and a protective group Z, and a sulfur atom and a protective group Z are preferred. Examples of the protecting group include a fluorenyl group, a methacryl group, and a methacyl group salt, and a group represented by the following formula (5), a group represented by the following formula (6), or the following formula (6) is preferred. Represented base salt. [Chemical 16] In the formula (5), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms. R ^{4 is} preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and more preferably an alkyl group or phenyl group having 1 to 5 carbon atoms. Examples of the formamyl salt include sodium salt, potassium salt, calcium salt, and magnesium salt.

Preferred examples of the sulfur-containing compound containing the protective group Z used in the present invention are shown below, but the present invention is not limited to the following compounds. [Chemical 17]

A preferred first embodiment of the method for producing a thiol compound of the present invention is exemplified by reacting a 3- to 15-membered polyhydric alcohol with a compound represented by the following formula (4-1) so that the obtained product is protected with A method in which the sulfur-containing compound of the group Z is reacted, and the protective group Z is removed to generate a thiol group. XM ^a1 -R ¹ -Y (4-1) R ¹ represents an alkylene group or a group containing a combination of an alkylene group and an etheric oxygen atom, an atom of Y bonded to R ¹ , and an atom of M ^a1 and R ^One bonded atom has 5 or more atoms of R ¹ interposed, M ^a1 represents -C (= O)-, and X represents a group containing at least one of a halogen atom or a sulfonate.

A preferred second embodiment of the method for producing a thiol compound of the present invention is exemplified by reacting a 3- to 15-membered polyhydric alcohol with a compound represented by the following formula (4-2), and protecting the obtained product with a protective compound. A method in which the sulfur-containing compound of the group Z is reacted, and the protective group Z is removed to generate a thiol group. XR ¹ -Y (4-2) In the formula, Y represents a group that is released by reaction with a sulfur-containing compound having a protective group Z, and R ¹ represents an alkylene group or a combination containing an alkylene group and an etheric oxygen atom. A group of Y, an atom bonded to R ¹ , and an atom of X bonded to R ¹ are separated by 5 or more atoms of R ¹ , and X represents a group containing at least one of a halogen atom or a sulfonate.

In the first embodiment and the second embodiment, the polyol can be exemplified in the structures represented by the above (L-1) to (L-21), and the polyol having an OH group bonded to a part of * . A preferable range is also the same as the description of the structures represented by the above (L-1) to (L-21). The polyvalent alcohol has the same meaning as n in Formula (1), and the preferred range is also the same. X and Y in the formulae (4-1) and (4-2) have the same meaning as X and Y in the formula (4), and the preferred ranges are also the same. R ^{1 in} Formula (4-1) and Formula (4-2) has the same meaning as R ¹ in Formula (1), and the preferred ranges are also the same. The sulfur-containing compound having a protective group Z is synonymous with the sulfur-containing compound having a protective group Z, and a preferred range is also the same.

Other embodiments of the method for producing the thiol compound of the present invention may be exemplified polyol with a compound HS-R ¹ -COOH represented by the direct condensation method of manufacturing. The polyol in the present embodiment can also be exemplified by a polyol represented by (L-1) to (L-21) in which the OH is bonded to a part of *. A preferable range is also the same as the description of the structures represented by the above (L-1) to (L-21). The polyvalent alcohol has the same meaning as n in Formula (1), and the preferred range is also the same. The polyvalent alcohol has the same meaning as n in Formula (1), and the preferred range is also the same. R ¹ in this embodiment has the same meaning as R ¹ in Formula (1), and the preferred ranges are also the same. In the present embodiment, it is obtained by dehydration condensation, and therefore has the advantage of fewer manufacturing steps. However, from the viewpoint of suppressing the generation of impurities such as thioester adducts, it is more preferable to use the sulfur-containing group having the protective group Z. Method of manufacturing compounds.

As the use of the thiol compound of the present invention, raw materials for pigments, raw materials for resins (polymers) such as dispersants, hardeners or crosslinking agents, stabilizers for resins, curing agents for gums, raw materials for adhesives, mercury Or raw materials of heavy metal elements / ion removing agents such as lead, raw materials of functionalizing agents for metal surfaces such as sensors, and the like. Specifically, the thiol compound of the present invention may be used in place of the aforementioned Patent Document 1 (International Publication WO2009 / 129221), Patent Document 2 (Japanese Patent Laid-Open No. 2007-277514), and Patent Document 3 (Japanese Patent The polyfunctional thiol compound in Japanese Patent Application Laid-Open No. 2013-79380).

Examples of uses of the hardener or the cross-linking agent (the two are collectively referred to as hardeners) include hardeners of compounds having an epoxy group or compounds having an isocyanate group.

The compound having an epoxy group (also referred to as an epoxy compound) is preferably a compound having two or more epoxy groups in one molecule. Specific examples of the epoxy compound include compounds having an epoxy group described in the curable composition described later. When the thiol compound of the present invention is used as a curing agent for an epoxy compound, it is preferable that the SH group is 70 mol to 120 mol relative to 100 mol earring oxygen of the epoxy compound. It is more preferable to perform the preparation in such a manner that the SH group becomes 80 mol to 110 mol relative to 100 mol earring oxygen of the epoxy compound. When a hardener other than a thiol compound such as an acid anhydride is used in combination (also referred to as other hardeners), it is preferable to subtract the epoxy group consumed by the other hardeners in order to make the earrings less than the remaining 100 moles. In terms of oxygen, the SH group is prepared in such a manner that it is 70 mol to 120 mol (preferably 80 mol to 110 mol).

The compound having an isocyanate group (also referred to as an isocyanate compound) is preferably a compound having two or more isocyanate groups in one molecule. The isocyanate compound may be any of an aromatic compound and an aliphatic compound. Specific examples of the isocyanate compound include, for example, 2,4-toluene diisocyanate, 2,4-toluene diisocyanate dimer, 2,6-toluene diisocyanate, p-xylylene diisocyanate, and m-xylylene diisocyanate. Methyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4 ' -Aromatic diisocyanate compounds such as diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and dimer acid diisocyanate; isophor Ketone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanate methyl) cyclohexane, etc. Cycloaliphatic diisocyanate compounds; adducts of 1 mol 1,3-butanediol and 2 mol toluene diisocyanate, etc .; diisocyanate compounds that are reactants of diol and diisocyanate; hexamethylene diisocyanate Biuretization reaction product; hexamethylene diisocyanate and trihydroxy Propane adduct reaction products. When the thiol compound of the present invention is used as a curing agent for a compound having an isocyanate group, it is preferable that the SH group is 50 to 300 mol relative to 100 mol isocyanate group. It is more preferable to mix | blend so that SH group may become 50-150 mol with respect to 100 mol isocyanate group. When a hardener other than a thiol compound such as an acid anhydride is used in combination (also referred to as other hardeners), it is preferable to subtract the isocyanate group consumed by the other hardeners, so that the remaining isocyanate is 100 mol. Basically, the SH group is prepared in a manner of 50 mol to 300 mol (preferably 50 mol to 150 mol).

The thiol compound of the present invention can be preferably used as a raw material of a resin (polymer). In particular, it can be preferably used as a raw material of an alkali-soluble resin. The polymer obtained by using the thiol compound of the present invention is excellent in heat resistance. In addition, this polymer has a lower viscosity than a linear polymer and is excellent in homogenization. Therefore, when a color filter is formed using a coloring composition containing the polymer, it is possible to make it difficult to generate a step (sag suppression) in one pixel. Further, the thiol compound of the present invention can be used as a raw material of a pigment.

Polymer Next, the polymer of the present invention will be described. The polymer of the present invention is represented by the following formula (7). [Chemical 18] In formula (7), L ¹ represents a (n1 + n2) valent organic linking group, n1 represents 1 to 15, n2 represents 0 to 14, the total of n1 and n2 is 3 to 15, and M ¹ represents -O-, -S-, -N (R ² )-, -C (= O)-, -C (= O) -O-, -OC (= O) -O-, -C (= O) -NH-, -OC (= O) -NH-, -S (= O)-, -S (= O) -O-, -S (= O) _2- , -S (= O) ₂ -O-, or- CH = N-, R ¹ represents an alkylene group or a group containing a combination of an alkylene group and an etheric oxygen atom, R ² represents a hydrogen atom, and an alkyl group having 1 to 10 carbon atoms which may also contain an etheric oxygen atom, Or an aromatic hydrocarbon group which may also contain an etheric oxygen atom, SH represents a thiol group, SH and M ^{1 are} separated by 5 or more atoms of R ¹ , S represents a sulfur atom, and the sulfur atom, and M ¹ and R ¹ The bonded atom is separated by 5 or more atoms of R ¹ , and P ¹ represents a monovalent substituent having a repeating unit derived from a compound having an ethylenically unsaturated bond.

L ¹ , M ¹ , R ^1, and R ² in formula (7) have the same meanings as L ¹ , M ¹ , R ^1, and R ² described in formula (1), and preferred ranges are also the same. n1 represents 1 to 15, n2 represents 0 to 14, and the total of n1 and n2 is 3 to 15. N1 and n2 in one polymer are integers, respectively, but the polymer of the present invention may include a plurality of polymers in which n1 and n2 in formula (7) are different. n1 is preferably 2 or more, and more preferably 3 or more. P ^{1 in} Formula (7) represents a monovalent substituent having a repeating unit derived from a compound having an ethylenically unsaturated bond. The n P ¹ may be the same or different from each other. P ¹ preferably has 2 or more repeating units derived from a compound having an ethylenically unsaturated bond, more preferably has 2 to 10,000 repeating units, and even more preferably has 2 to 1,000 repeating units. .

Examples of the compound having an ethylenically unsaturated bond include (meth) acrylates, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (formaldehyde) Group) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl compounds having an acidic group, and the like. These compounds may be used singly or in combination of two or more kinds. Examples of the vinyl compound having an acid group include a vinyl compound having a carboxyl group, a vinyl compound having a sulfo group, and a vinyl compound having a phosphate group. For details of the compound having an ethylenically unsaturated bond, reference may be made to the description of paragraph number 0089 to paragraph number 0098 in Japanese Patent Application Laid-Open No. 2007-277514, and the contents thereof are incorporated herein. In addition, as the compound having an ethylenically unsaturated bond, a monomer described in an alkali-soluble resin described later can also be used. Specific examples include methacrylic acid and benzyl methacrylate.

The weight average molecular weight of the polymer of the present invention is preferably 3,000 to 1,000,000, more preferably 4,000 to 500,000, and still more preferably 5,000 to 300,000.

The acid value of the polymer of the present invention is not particularly limited. When the polymer of the present invention is used as an alkali-soluble resin, it is preferably 10 mgKOH / g to 200 mgKOH / g, and more preferably 20 mgKOH / g ～ 160 mgKOH / g, particularly preferably 30 mgKOH / g ～ 140 mgKOH / g. When the acid value is 10 mgKOH / g or more, the alkali developability is good. When the acid value is less than 200 mgKOH / g, the dispersion stability of the composition is good.

The polymer of the present invention can be obtained, for example, by radically polymerizing a compound having an ethylenically unsaturated bond in the presence of a thiol compound represented by the formula (1). The compound having an ethylenically unsaturated bond is not particularly limited, and a compound containing one or more acid groups is preferred. Examples of the compound having an ethylenically unsaturated bond include (meth) acrylates, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (formaldehyde) Based) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having acidic groups, etc., preferred (Meth) acrylic acid ester, (meth) acrylamidonium, styrene, vinyl ether, maleimide, vinyl monomer having an acidic group, more preferably (meth) Acrylates, styrenes, vinyl monomers with acidic groups. In addition, as the compound having an ethylenically unsaturated bond, a monomer described in an alkali-soluble resin described later can also be used.

The manufacturing conditions of the polymer are not particularly limited, and examples thereof include dissolving a thiol compound and a compound having an ethylenically unsaturated bond in an appropriate solvent, adding a polymerization initiator thereto, and at about 50 ° C to 220 ° C. A method of performing polymerization in a solution (a solution polymerization method) and the like. The solvent used in the solution polymerization method can be arbitrarily selected depending on the solubility of the raw material compound used and the solubility of the produced polymer. Examples include methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl acetate. Oxypropyl ester, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene. These solvents may be used in combination of two or more. In addition, as the polymerization initiator, 2,2'-azobis (isobutyronitrile) (AIBN), 2,2'-azobis- (2,4'-dimethylvaleronitrile), 2,2 Azo compounds such as' -azobis (2-methylpropionate) dimethyl, peroxides such as benzamidine peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

Composition The composition of the present invention is a composition containing the thiol compound of the present invention, and preferably 50% by mass or more of the composition is a specific one of the thiol compounds. The composition of the present invention is a composition containing a thiol compound produced by a method using the sulfur-containing compound having a protective group Z, and preferably 50% by mass or more of the composition is the A specific one of the thiol compounds. The compound having a thioester structure is liable to cause thioester structure decomposition due to heating. However, the composition of the present invention has few such impurities, and thus a molded article having higher heat resistance is obtained. The specific one is any one of the compounds represented by formula (1). In the composition containing the thiol compound of the present invention, the upper limit of the amount of a specific one of the thiol compounds is not particularly limited, and is preferably 100% by mass, but even if it is, for example, 80% by mass or less, A composition having sufficient practicality. The composition of the present invention includes the polymer represented by the above (7). Since the polymer of the present invention is excellent in heat resistance, a molded article having higher heat resistance can be obtained. In addition, the polymer of the present invention has low viscosity and excellent homogenization. Therefore, when a color filter is formed using a colored composition containing the composition of the present invention, it is difficult to generate a step difference in one pixel. (Inhibit depression).

<Curable composition> Hereinafter, the curable composition and the coloring composition of this invention are demonstrated. The curable composition of the present invention includes at least one of the thiol compound of the present invention, the thiol compound obtained by the production method of the present invention, and the composition of the present invention, and a polymerizable compound. As described above, the polyfunctional thiol compound functions as a chain transfer agent when the polymerizable compound is cured, but an unreacted thiol group remains in the obtained cured product. If it is a well-known thiol compound, an unreacted thiol group reacts with other groups and causes thermal decomposition. However, according to the present invention, it is difficult to cause this thermal decomposition, which is advantageous. The content of the thiol compound of the present invention in the curable composition of the present invention is preferably 0.1% by mass to 20% by mass of the solid content, more preferably 0.5% by mass to 10% by mass, and even more preferably 1 Mass% to 5 mass%.

The curable composition of the present invention can be used in dental and orthopedic materials such as a coloring composition, a composition for forming an antireflection film, a composition for forming an antifouling layer, and a glass ionomer cement. As an example, it can be used as a polymerizable composition including at least one of the thiol compound of the present invention, the thiol compound obtained by the production method of the present invention, and the composition of the present invention, and having a repeating unit. A compound having 4 or more polymerizable groups, a photopolymerization initiator, and a solvent, and the repeating unit has a polyether structure containing a fluorine atom. Such a polymerizable composition can be used as a composition for forming a low refractive index layer. The polymerizable composition is more preferably exemplified by a composition containing a perfluoroolefin copolymer, hollow silica particles, a polymerizable compound (preferably a polymerizable monomer), a photopolymerization initiator, and a fluorine-containing monomer. For details, refer to paragraphs 0024 to 0060 of Japanese Patent Laid-Open No. 2014-167596, paragraphs 0027 to 0126 of Japanese Patent Laid-Open No. 2014-070165, and paragraphs of Japanese Patent Laid-Open No. 2003-228741. The descriptions of 0018 to paragraph 0167 (especially the descriptions of paragraphs 0043 to 0048) are incorporated into this specification. Examples of the perfluoroolefin copolymer include a structure represented by the following formula (1). In the structural formula, 50:50 represents the molar ratio. [Chemical 19] Examples of the hollow silica particles include isopropanol silica sol. Commercially available products include "CS60-IPA" (manufactured by Catalytic Chemical Industries). Specific examples of the fluorine-containing monomer include the structures shown below. [Chemical 20] When the thiol compound of the present invention is used as a curing agent for an epoxy compound, the curable composition of the present invention includes, for example, at least a thiol compound and an epoxy compound of the present invention, and further includes 3- Composition of hardening accelerators such as aminomethyl-3,5,5-trimethylcyclohexylamine. When the thiol compound of the present invention is used as a curing agent for an isocyanate compound, examples of the curable composition of the present invention include at least the thiol compound and the isocyanate compound of the present invention, and further include dibutyl di A composition of a hardening accelerator such as tin chloride.

<Coloring composition> The colored composition of this invention contains the thiol compound of this invention, the thiol compound obtained by the manufacturing method of this invention, and at least one of the composition of this invention, a polymerizable compound, and a coloring agent. The content of the thiol compound of the present invention in the coloring composition of the present invention is preferably 0.1% to 20% by mass of the solid content, more preferably 0.5% to 10% by mass, and even more preferably 1% by mass. % To 5 mass%.

<< Polymerizable Compound >> The colored composition of the present invention contains a polymerizable compound. As the polymerizable compound, a known polymerizable compound that can be crosslinked by radicals, acids, and heat can be used. Examples of the polymerizable compound include an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane), and a methylol group. From the viewpoint of self-sensitivity, the polymerizable compound can be appropriately selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Among them, a polyfunctional polymerizable compound having 4 or more functions is preferable, and a polyfunctional polymerizable compound having 5 or more functions is more preferable.

Such a group of compounds is widely known, and these can be used without particular limitation in the present invention. These may be, for example, any of chemical forms such as monomers, prepolymers, that is, dimers, trimers, and oligomers, or mixtures thereof, and multimers thereof. The polymerizable compound in the present invention may be used alone or in combination of two or more.

Examples of monomers and prepolymers include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters, amidines, and these As the polymer, esters of an unsaturated carboxylic acid and an aliphatic polyalcohol compound, amidines of an unsaturated carboxylic acid and an aliphatic polyamine compound, and these multimers are preferable. In addition, it is also possible to suitably use a reactant: an addition reaction product of an unsaturated carboxylic acid ester or amidoamine having a nucleophilic substituent such as a hydroxyl group, an amine group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy. Or dehydration condensation reactants with monofunctional or polyfunctional carboxylic acids. Furthermore, the following reactants are also suitable: reactants of unsaturated carboxylic acid esters or amidines having an electrophilic substituent such as isocyanate group and epoxy group, and monofunctional or polyfunctional alcohols, amines, and thiols Reactants of unsaturated carboxylic acid esters or amidines having a detachable substituent such as a halogen group or tosylsulfonyloxy group, and monofunctional or polyfunctional alcohols, amines, or thiols. Further, instead of the unsaturated carboxylic acid, a group of compounds such as vinyl benzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether, and allyl ether may be used. As these specific compounds, the compounds described in paragraph number [0095] to paragraph number [0108] of Japanese Patent Laid-Open No. 2009-288705 can also be suitably used in the present invention.

Furthermore, the polymerizable compound is also preferably a compound having an ethylenically unsaturated group having at least one addition polymerizable ethylene group and having a boiling point of 100 ° C. or higher under normal pressure. As an example, reference can be made to paragraph 0227 of Japanese Patent Laid-Open No. 2013-29760, the content of which is incorporated in this specification.

Moreover, as a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group, refer to paragraph number 0254 to paragraph number 0257 of Japanese Patent Laid-Open No. 2008-292970. The compounds described in the above are incorporated into this specification.

Among them, the polymerizable compound is preferably dipentaerythritol triacrylate (commercial product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (commercial product is Kayalar (KAYARAD) D-320; manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol penta (meth) acrylate (commercially available product is Kayarad D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (Meth) acrylic acid ester (commercial product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), ethoxylated modified dipentaerythritol hexaacrylate (commercial product is A-DPH-12E; (Manufactured by Shin Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acrylfluorene groups have ethylene glycol and propylene glycol residues interposed therebetween (for example, SR454 and SR499 marketed by Sadobene Corporation). These oligomer types can also be used. The aspect of a preferable polymerizable compound is shown below.

The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphate group. If the polymerizable compound has an unreacted carboxyl group or the like, it can be used as it is, but if necessary, a hydroxyl group of the polymerizable compound can be reacted with a non-aromatic carboxylic anhydride to introduce an acid group. Specific examples of the non-aromatic carboxylic anhydride include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, and succinic anhydride , Maleic anhydride, etc.

The polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably one obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The acid-based polymerizable compound is particularly preferably an ester of which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available products include, for example, M-510 and M-520, which are polyacid-modified acrylic oligomers manufactured by Toa Kosei.

The polymerizable compound having an acid group may be used singly, but it is difficult to use a single compound in production, and therefore, two or more kinds may be used in combination. The preferable acid value of the polymerizable compound having an acid group is 0.1 mgKOH / g to 40 mgKOH / g, and particularly preferred is 5 mgKOH / g to 30 mgKOH / g. If the polyvalent monomer has an acid value of 0.1 mgKOH / g or more, the developing and dissolving characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in terms of manufacturing or operation. Furthermore, the photopolymerizable ability is good, and the hardening properties such as the surface smoothness of the pixels are excellent. Therefore, when two or more polymerizable compounds having different acid groups are used in combination, or when a polymerizable compound having no acid group and a polymerizable compound having an acid group are used in combination, it is preferred that The adjustment is performed so that the acidic group of the polymerizable compound as a whole falls within the above range.

In addition, as the polymerizable compound, a polymerizable compound having a caprolactone structure is also preferable. The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. Examples thereof include trimethylolethane, di-trimethylolethane, and trimethylolethane. Polyols such as methylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, trimethylolmelamine, etc. with (meth) acrylic acid and ε-caprolactone The ε-caprolactone obtained by esterification of the ester is a modified polyfunctional (meth) acrylate. Among these, a polymerizable compound having a caprolactone structure represented by the following general formula (Z-1) is preferred.

[Chemical 21]

In the general formula (Z-1), six Rs are all groups represented by the following general formula (Z-2), or one to five of the six Rs are represented by the following general formula (Z-2) The remaining groups are the groups represented by the following general formula (Z-3).

[Chemical 22]

In the general formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bonding bond.

[Chemical 23]

In the general formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bonding bond.

As the polymerizable compound having a caprolactone structure, for example, DPCA-20 (in the above-mentioned formula (Z-1) to formula (Z-3), which is commercially available as a KAYARAD DPCA series by Nippon Kayaku Co., Ltd.) ), M = 1, the number of groups represented by the formula (Z-2) = 2, and compounds in which R ¹ is a hydrogen atom), DPCA-30 (in the formulas (Z-1) to (Z-) In 3), m = 1, the number of groups represented by the formula (Z-2) = 3, and R ¹ is a hydrogen atom compound), DPCA-60 (in the formulas (Z-1) to (Z-1) -3), m = 1, the number of groups represented by the formula (Z-2) = 6, and R ¹ is a hydrogen atom compound), DPCA-120 (in the formula (Z-1) to formula (Z-1) In Z-3), m = 2, the number of groups represented by formula (Z-2) = 6, and compounds in which R ¹ is a hydrogen atom) and the like. In the present invention, the polymerizable compound having a caprolactone structure may be used alone or as a mixture of two or more.

The polymerizable compound may be a compound represented by the following general formula (Z-4) or (Z-5).

[Chemical 24]

In the general formula (Z-4) and the general formula (Z-5), E each independently represents-((CH ₂ ) _y CH ₂ O)-, or-((CH ₂ ) _y CH (CH ₃ ) O) -, Y each independently represent an integer of 0 to 10, and X each independently represents an acrylfluorenyl group, a methacrylfluorenyl group, a hydrogen atom, or a carboxyl group. In the general formula (Z-4), the total of acrylfluorenyl and methacrylfluorenyl is 3 or 4, m each independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. However, when the total of each m is 0, any one of X is a carboxyl group. In the general formula (Z-5), the total of acrylfluorenyl and methacrylfluorenyl is five or six, n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8. In the general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12. Moreover,-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-in the general formula (Z-4) or (Z-5) is preferred This is a form in which the terminal on the oxygen atom side is bonded to X.

The compound represented by the general formula (Z-4) or the general formula (Z-5) may be used singly or in combination of two or more kinds. It is particularly preferred that in the general formula (Z-5), all six X's are acrylfluorenyl groups.

The total content of the compound represented by the general formula (Z-4) or the general formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

The compound represented by the general formula (Z-4) or the general formula (Z-5) can be synthesized by a conventionally known procedure in which a ring-opening skeleton of ethylene oxide or propylene oxide is bonded by a ring-opening addition reaction. A step on pentaerythritol or dipentaerythritol; a step of introducing a (meth) acrylfluorenyl group by reacting a terminal hydroxyl group of the ring-opening skeleton with, for example, (meth) acrylfluorene. Each step is a sufficiently known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or the general formula (Z-5).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferred. Specific examples include compounds represented by the following formulae (a) to (f) (hereinafter also referred to as "exemplified compounds (a) to (f)"), and among them, exemplary compounds (a) are preferred. Exemplified compound (b), Exemplified compound (e), Exemplified compound (f).

[Chemical 25]

[Chemical 26]

Commercially available products of the polymerizable compound represented by the general formula (Z-4) and the general formula (Z-5) include, for example, a tetrafunctional acrylate SR- 494, a 6-functional acrylate DPCA-60 with 6 pentyloxy chains, a trifunctional acrylate TPA-330 with 3 isobutyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., etc.

In the present invention, a polymerizable compound may be a compound having an epoxy group. The compound having an epoxy group is preferably a compound having two or more epoxy groups in one molecule. By using a compound having two or more epoxy groups in one molecule, the effect of the present invention can be achieved more effectively. The number of epoxy groups in the molecule is preferably 2 to 10, more preferably 2 to 5, and particularly preferably 3. For details, refer to the descriptions of paragraphs 0034 to 0036 in Japanese Patent Laid-Open No. 2013-011869, the descriptions of paragraphs 0091 to 0103 in Japanese Patent Laid-Open No. 2014-153554, and Japanese Patent Laid-Open No. 2014-089408. The descriptions of paragraphs 0084 to 0095 of the No. 1 publication are incorporated into the present specification.

Specific examples of the compound having an epoxy group are exemplified below, but the present invention is not limited to these.

[Chemical 27]

The compound having an epoxy group may also preferably be an oligomer or a polymer having an epoxy group in a side chain. Examples of such compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and aliphatic epoxy resin. These compounds can be a commercially available product or can be obtained by introducing an epoxy group into the side chain of the polymer.

As commercially available products, for example, bisphenol A type epoxy resins include jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (the above are manufactured by Japan Epoxy Resin Co., Ltd.), Ai EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (above manufactured by Dickson Co., Ltd.), etc., bisphenol F-type epoxy resin can be List jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (above manufactured by Di Edison Co., Ltd.) , LCE-21, RE-602S (above manufactured by Nippon Kayaku Co., Ltd.), etc. Examples of phenol novolac epoxy resins include jER152, jER154, jER157S70, jER157S65 (above manufactured by Japan Epoxy Resin Co., Ltd.) , EPICLON N-740, EPICLON N-770, EPICLON N-775 (the above is provided by Di Aisheng shares (Manufactured by the company), etc., cresol novolac-type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, and EPICLON ) N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above manufactured by Di Edison Co., Ltd.), EOCN-1020 (above (Manufactured by Nippon Kayaku Co., Ltd.), etc., aliphatic epoxy resins include ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, and ADEKA RESIN ) EP-4088S (above manufactured by Aidco Co., Ltd.), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (above manufactured by Daicel Chemical Industry Co., Ltd.), DANACOL EX-212L, DANACAL ( DENACOL) EX-214L, DENACOL EX-2 16L, DENACOL EX-321L, DENACOL EX-850L (above manufactured by Nagase Kasei Co., Ltd.), etc. Other examples include ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, and ADEKA RESIN EP- 4011S (above manufactured by Aidike Co., Ltd.), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above manufactured by Aidike Co., Ltd.), jER1031S ( Japan Epoxy Resin Co., Ltd.) and so on. In addition, as the commercial product of the compound having an epoxy group, jER1031S (manufactured by Mitsubishi Chemical Co., Ltd.), jER1032H60 (manufactured by Mitsubishi Chemical Co., Ltd.), EPICLON HP-4700 (Diesen) Co., Ltd.), EPICLON N-695 (manufactured by Dickson Co., Ltd.), Epiclon 840 (manufactured by Dickson Co., Ltd.), Epiclon (EPICLON) N660 (Dickson) Co., Ltd.), EPICLON HP7200 (manufactured by Di Edison Co., Ltd.), etc.

[Chemical 28]

In the present invention, the compound having an epoxy group may be used alone or in combination of two or more kinds.

Further, in the present invention, as the polymerizable compound, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Acrylic urethanes described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39417. The urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent No. 39418 are also suitable. In addition, the polymerizable compound may have an amine group in the molecule as described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. 1-105238. Addition of a polymerizable compound having a structure or a thioether structure to obtain a coloring composition having an excellent light-sensing speed. In the present invention, a compound having an oxetanyl group may be used as the polymerizable compound. Examples of the compound having an oxetanyl group include those described in paragraphs 0134 to 0145 of Japanese Patent Laid-Open No. 2008-224970, and the contents are incorporated herein. For specific examples, ARON OXETANE OXT-121, ARON OXETANE OXT-221, ARON OXETANE OX-SQ, ARON OXETANE PNOX (above manufactured by Toa Synthesis Co., Ltd.). Examples of commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusei Pulp Co., Ltd.), UA-7200 (manufactured by Shin Nakamura Chemical Co., Ltd.), and DPHA-40H (Nippon Kayaku) (Manufactured by the company), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha).

The blending amount of the polymerizable compound in the curable composition or the coloring composition of the present invention is preferably 5% to 50% by mass relative to the solid content, and more preferably 10% to 30% by mass.

<< Colorant >> The colorant used in the coloring composition of the present invention is not particularly limited, and may be a pigment, a dye, or a combination of a pigment and a dye. The colorant may be used alone or in combination of two or more. The amount of the colorant is preferably 10% by mass to 90% by mass of the solid content of the coloring composition of the present invention, more preferably 30% by mass to 85% by mass, and still more preferably 60% by mass to 80% by mass. .

<<< Dye >> There is no restriction | limiting in particular in the dye which can be used as a coloring agent contained in a coloring composition, The conventionally well-known dye used as a color filter can be used. For example, pyrazole azo-based, aniline azo-based, triphenylmethane-based, anthraquinone-based, anthrapyridone-based, benzylidene-based, oxacyanine-based, pyrazolotriazole azo-based, Pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolo-pyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based, pyrrole methylene-based and other dyes. Furthermore, multimers of these dyes can also be used.

Furthermore, when developing with water or alkali, from the viewpoint of completely removing the adhesive and / or dye from the light-irradiated portion by development, there may be cases where an acid dye and / or a derivative thereof can be suitably used. In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azo dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.

Specific examples of the acid dye are listed below, but they are not limited to these. Examples include: acid alizarin purple N; acid black 1, acid black 2, acid black 24, acid black 48; acid blue 1, acid blue 7, acid blue 9, acid blue 15, acid blue 18, acid blue 23, Acid blue 25, acid blue 27, acid blue 29, acid blue 40 to acid blue 45, acid blue 62, acid blue 70, acid blue 74, acid blue 80, acid blue 83, acid blue 86, acid blue 87, acid blue 90, acid blue 92, acid blue 103, acid blue 112, acid blue 113, acid blue 120, acid blue 129, acid blue 138, acid blue 147, acid blue 158, acid blue 171, acid blue 182, acid blue 192, Acid Blue 243, Acid Blue 324: 1; Acid Chrome Violet K; Acid Magenta; Acid Green 1, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 16, Acid Green 25, Acid Green 27, Acid Green 50 ; Acid orange 6, acid orange 7, acid orange 8, acid orange 10, acid orange 12, acid orange 50, acid orange 51, acid orange 52, acid orange 56, acid orange 63, acid orange 74, acid orange 95; acid Red 1, Acid Red 4, Acid Red 8, Acid Red 14, Acid Red 17, Acid Red 18, Acid Red 26, Acid Red 27, Acid Red 29, Acid Red 31, Acid Red 34, Acid Red 35, Acid Red 37, Acid Red 42, Acid Red 44, Acid Red 50, Acid Red 51, Acid Red 52, Acid Red 57, Acid Red 66, Acid Red 73, Acid Red 80 , Acid red 87, acid red 88, acid red 91, acid red 92, acid red 94, acid red 97, acid red 103, acid red 111, acid red 114, acid red 129, acid red 133, acid red 134, acid Red 138, Acid Red 143, Acid Red 145, Acid Red 150, Acid Red 151, Acid Red 158, Acid Red 176, Acid Red 183, Acid Red 198, Acid Red 211, Acid Red 215, Acid Red 216, Acid Red 217 Acid Red 249, Acid Red 252, Acid Red 257, Acid Red 260, Acid Red 266, Acid Red 274; Acid Violet 6B, Acid Violet 7, Acid Violet 9, Acid Violet 17, Acid Violet 19; Acid Yellow 1, Acid Yellow 3, Acid Yellow 7, Acid Yellow 9, Acid Yellow 11, Acid Yellow 17, Acid Yellow 23, Acid Yellow 25, Acid Yellow 29, Acid Yellow 34, Acid Yellow 36, Acid Yellow 42, Acid Yellow 54, Acid Yellow 72 , Acid Yellow 73, Acid Yellow 76, Acid Yellow 79, Acid Yellow 98, Acid Yellow 99, Acid Yellow 111, Acid Yellow 112, Acid Yellow 114, Acid Yellow 116, Acid Yellow 184, Acid Yellow 243; Food Yellow 3; and the plurality of dye derivatives.

In addition, azo-based, xanthene-based, and phthalocyanine-based acid dyes other than those mentioned above are also preferable, and CI (colorimetric index) solvent blue 44 and CI solvent blue 38 may be preferably used; CI solvent orange 45; Acid dyes such as rose red B and rose red 110 and derivatives of these dyes.

Among them, the colorant is preferably selected from the group consisting of triarylmethane-based, anthraquinone-based, azomethine-based, benzylidene-based, oxacyanine-based, cyanine-based, phenothiazine-based, and pyrrolopyrazole-based Azoline-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based, pyrazole-azo-based, aniline-azo-based, pyrazolotriazole-azo-based, pyridone-azo-based, anthracene Pyridone-based and pyrrole methylene-based colorants.

More specifically, in terms of light resistance and heat resistance, a dipyrromethene-based dye in which a compound represented by the following general formula (1) is coordinated to a metal atom or a metal compound can be suitably used.

[Chemical 29] Formula (1)

In the general formula (1), R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.

For details of the compound represented by the general formula (1), reference may be made to the descriptions of paragraphs 0035 to 0075 of Japanese Patent Application Laid-Open No. 2011-095732, which are incorporated into the present specification. In addition, as a specific example of a pyrrole methylene dye that is preferably used in the present invention, the dye unit and its raw material monomers described in paragraphs 0118 to 0130 of Japanese Patent Laid-Open No. 2011-095732 can be exemplified. These are incorporated into this specification. As an example, the dye (A-1) used in the Example mentioned later is illustrated. As well-known dyes other than the said pigment (A), for example, Japanese Patent Laid-Open No. Sho 64-90403, Japanese Patent Laid-Open No. Sho 64-91102, Japanese Patent Laid-Open No. 1-94301, and Japan Patent Publication No. 6-11614, Japanese Patent Publication No. 2592207, U.S. Patent No. 4850501, U.S. Patent No. 5,667,920, U.S. Patent No. 505950, U.S. Patent No. 5667920, Japanese Patent No. 5-333207, The pigments disclosed in Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6-51115, Japanese Patent Laid-Open No. 6-194828, and the like. As the chemical structure, a pyrazole azo system, a pyrrole methylene system, an aniline azo system, a triarylmethane system, an anthraquinone system, a benzimine system, an oxacyanine system, and a pyrazolotriazole couple can be used. Dyes such as nitrogen, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, and the like. Moreover, a dye multimer can be used for a dye. Examples of the pigment multimer include compounds described in Japanese Patent Laid-Open No. 2011-213925 and Japanese Patent Laid-Open No. 2013-041097. The compound A-1 used in the examples described later also corresponds to an example of a preferable pyrrole methylene dye used in the present invention.

<< Pigment >> The pigment used in the present invention may be an organic pigment or an inorganic pigment. Examples of the inorganic pigment include metal compounds represented by metal oxides and metal salts, and specific examples include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and the like. And black pigments such as composite oxides of the metal, carbon black, titanium black.

Examples of the organic pigment include CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 53, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 99, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 167, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 199; CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 71; CI Pigment Red 81, CI Pigment Red 105, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 155, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 179, CI Pigment Red 209, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270; CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 32, CI Pigment Violet 39, CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 15, CI Pigment Blue 15: 1 CI Pigment Blue 15: 3, CI Pigment Blue 15: 6, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 66; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58; CI Pigment Brown 25, CI Pigment Brown 28; CI Pigment Black 1 and the like.

The pigments which can be preferably used in the present invention include the following. However, the present invention is not limited to these. CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 167, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Orange 36, CI Pigment Orange 71, CI Pigment Red 122, CI Pigment Red 150, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 32, CI Pigment Blue 15: 1. CI Pigment Blue 15: 3, CI Pigment Blue 15: 6, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 66, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37 , CI Pigment Green 58; CI Pigment Black 1, CI Pigment Black 7

These organic pigments can be used alone or in various combinations to adjust the spectral range or improve the color purity. A specific example of the combination is shown below. For example, an anthraquinone-based pigment, a perylene-based pigment, or a diketopyrrolopyrrole-based pigment may be used alone for the red pigment, or at least one of these and a bisazo-based yellow pigment, an isoindoline-based yellow pigment, and a quinoline yellow may be used. It is a mixture of yellow pigments and red pigments. For example, anthraquinone-based pigments include CI Pigment Red 177, fluorene-based pigments include CI Pigment Red 155, CI Pigment Red 224, and diketopyrrolopyrrole-based pigments include CI Pigment Red 254. In terms of color separation, It is preferably mixed with CI Pigment Yellow 139. The quality of the red pigment and the yellow pigment is preferably in the range of 100: 5 to 100: 50, and more preferably in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, adjustment can be made so as to match the obtained spectroscopic spectrum.

The green pigment may be a halogenated phthalocyanine-based pigment alone or mixed with a bisazo-based yellow pigment, a quinoline yellow-based yellow pigment, an azomethine-based yellow pigment, or an isoindoline-based yellow pigment. For example, this example is preferably CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, or CI. Mixture of Pigment Yellow 185. The quality of the green pigment and the yellow pigment is better in the range of 100: 5 to 100: 150, and more preferably in the range of 100: 30 to 100: 120.

As the blue pigment, a phthalocyanine-based pigment may be used alone, or a mixture thereof with a dioxazine-based purple pigment may be used. For example, a mixture of C.I. Pigment Blue 15: 6 and C.I. Pigment Violet 23 is preferred. The quality of the blue pigment and the purple pigment is 100: 0 to 100: 100.

The black matrix pigment may be used alone or in combination of carbon, titanium black, iron oxide, and titanium oxide, and a combination of carbon and titanium black is preferred. In addition, the quality of carbon and titanium black is preferably in the range of 100: 0 to 100: 60.

As for the primary particle diameter of the pigment, when a coloring composition is used as a color filter, from the viewpoint of color unevenness and contrast, it is preferably 100 nm or less, and from the viewpoint of self-dispersion stability, Preferably it is above 5 nm. The average primary particle diameter of the pigment is more preferably 5 nm to 75 nm, even more preferably 5 nm to 55 nm, and particularly preferably 5 nm to 35 nm. The average primary particle diameter of the pigment can be measured by a known method such as an electron microscope.

<< Pigment Dispersant >> When the coloring composition of the present invention contains a pigment, a pigment dispersant may be used in combination as necessary. Examples of the pigment dispersant usable in the present invention include polymer dispersants [for example, polyamidoamine and its salts, polycarboxylic acids and their salts, high molecular weight unsaturated esters, modified polyurethanes, modified Polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, formalin naphthalenesulfonate], and polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkyl Surfactants such as alcohol amines, and pigment derivatives. Macromolecular dispersants can be further classified into linear polymers, terminally modified polymers, graft polymers, and block polymers based on their structure. For details of the dispersant, refer to the descriptions in paragraphs 0098 to 0102 of Japanese Patent Laid-Open No. 2014-130344, which are incorporated into this specification.

These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a pigment derivative in combination with a polymer dispersant. In addition, the pigment dispersant may be used in combination with an alkali-soluble resin, together with a terminally modified polymer, a graft polymer, and a block polymer having a fixing portion fixed on the surface of the pigment. Examples of the alkali-soluble resin include (meth) acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like, and acidic fibers having a carboxylic acid in a side chain. It is particularly preferred that it is a (meth) acrylic acid copolymer. Furthermore, the N-substituted maleimide imide monomer copolymer described in Japanese Patent Laid-Open No. 10-300922, the ether dimer copolymer described in Japanese Patent Laid-Open No. 2004-300204, and Japanese Patent The alkali-soluble resin containing a polymerizable group described in Japanese Patent Application Laid-Open No. 7-319161 is also preferable. Specific examples of the alkali-soluble resin include benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer. Examples of commercially available products include BY-161 (manufactured by BYK).

When a pigment dispersant is contained in the coloring composition, the total content of the pigment dispersant is preferably 1 to 80 parts by mass, and more preferably 5 to 70 parts by mass based on 100 parts by mass of the pigment. Parts, more preferably 10 to 60 parts by mass. The specific dispersion resin is preferably 50% by mass or more of the dispersant component contained in the coloring composition, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The coloring composition of the present invention may include only one pigment dispersant, or may include two or more pigment dispersants. When two or more kinds are included, it is preferable that the total amount thereof is within the range.

<< Alkali-soluble resin> The curable composition or colored composition of the present invention may further contain an alkali-soluble resin. The alkali-soluble resin can also be used as a pigment dispersant. The alkali-soluble resin can be alkali-soluble from a linear organic polymer having at least one group that promotes alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). The resin is appropriately selected. From the viewpoint of heat resistance, polyhydroxystyrene resin, polysiloxane resin, acrylic resin, acrylamide resin, and acrylic / acrylamide copolymer resin are preferred. From a viewpoint, acrylic resin, acrylamide resin, and acrylic / acrylamide copolymer resin are preferable.

Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphate group, a sulfonic acid group, and a phenolic hydroxyl group. Preferred are those that are soluble in a solvent and can be developed by a weak alkaline aqueous solution. Particularly preferred is (meth) acrylic acid. These acid groups may be only one kind, or two or more kinds.

Examples of the monomer capable of imparting an acid group after polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, monomers having an epoxy group such as glycidyl (meth) acrylate, and the like. A monomer having an isocyanate group, such as (meth) acrylic acid-2-isocyanatoethyl. The monomer for introducing these acid groups may be only one kind, or two or more kinds. In order to introduce an acid group into an alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization can be polymerized as a monomer component.

For the production of the alkali-soluble resin, for example, a method using a known radical polymerization method can be applied. The polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, and the like when an alkali-soluble resin is produced by a radical polymerization method can be easily set by those skilled in the art, and can also be experimental. To determine conditions.

The linear organic polymer used as the alkali-soluble resin is preferably a polymer having a carboxylic acid in a side chain, and examples thereof include a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenol resins such as novolac resins, etc., acidic cellulose derivatives with carboxylic acids in side chains, and additions to polymers with hydroxyl groups Made from acid anhydride. In particular, a copolymer of (meth) acrylic acid and other monomers copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. , Isobutyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, Toluene (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Examples of vinyl compounds include styrene, α-methylstyrene, vinyl toluene, and glycidyl methacrylate Ester, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc. Examples of the N-position substituted maleimide imide monomer described in Japanese Unexamined Patent Application No. 10-300922 include N-phenylmaleimide, N-cyclohexylmaleimide, and the like. In addition, the other monomers copolymerizable with (meth) acrylic acid may be only one kind, or two or more kinds thereof.

The alkali-soluble resin also preferably contains a compound represented by the following general formula (ED) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds are also referred to as "ether dimers" ) Is a polymer (a) obtained by polymerizing a monomer component of an essential component.

[Chemical 30] General formula (ED)

In the general formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. [Chemical 31] In the general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For a specific example of the general formula (ED2), refer to the description in Japanese Patent Laid-Open No. 2010-168539.

Thereby, the curable composition or colored composition of the present invention can form a cured film having extremely excellent heat resistance and transparency. In the general formula (ED), the hydrocarbon group having 1 to 25 carbon atoms which may also have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, Linear or branched alkyl groups such as n-butyl, isobutyl, third butyl, third pentyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, Tertiary butyl cyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and other alicyclic groups; 1-methoxyethyl Alkoxy-substituted alkyl groups such as 1,1-ethoxyethyl; alkyl groups substituted with aryl groups such as benzyl. Among these, substitution of a primary or secondary carbon, such as methyl, ethyl, cyclohexyl, benzyl, and the like, which is difficult to be removed by acid or heat, is particularly preferred from the viewpoint of heat resistance.

As specific examples of the ether dimer, for example, reference can be made to the description in paragraph 0041 of Japanese Patent Laid-Open No. 2014-041301, which is incorporated into the present specification. These ether dimers may be only one kind, or two or more kinds. The structure derived from the compound represented by the general formula (ED) may copolymerize other monomers.

The alkali-soluble resin may include a structural unit derived from an ethylenically unsaturated compound represented by the following formula (X). General formula (X) (In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may also include a benzene ring. n represents an integer from 1 to 15)

In the formula (X), the carbon number of the alkylene group of R ₂ is preferably 2 to 3. The carbon number of the alkyl group of R ₃ is 1 to 20, more preferably 1 to 10, and the alkyl group of R ₃ may include a benzene ring. Examples of the benzene ring-containing alkyl group represented by R ₃ include benzyl and 2-phenyl (iso) propyl.

Further, in order to improve the crosslinking efficiency of the colored composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acrylic group, an allyloxyalkyl group or the like in a side chain is useful. Examples of the alkali-soluble resin containing the polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon), Photomer 6173 (COOH-containing acrylic urethane oligomer) (Polyurethane acrylic oligomer), manufactured by Diamond Shamrock Co. Ltd., Viscoat R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), SEC Rome (Cyclomer) P series, Placcel (CF200 series) (all manufactured by Daicel Chemical Industries), Ebecryl 3800 (made by Daicel UCB), etc. As these polymerizable group-containing alkali-soluble resins, preferred are those in which an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group, and a compound containing a (meth) acrylfluorene group and a compound containing Reaction of urethane modified polymerizable double bond-containing acrylic resin obtained by reaction of carboxyl acrylic resin, reaction of acrylic resin containing carboxyl group and compound having both epoxy group and polymerizable double bond in the molecule The obtained unsaturated resin containing acrylic resin, acid pendant epoxy acrylate resin, and polymerizable double bond-containing acrylic resin obtained by reacting an OH group-containing acrylic resin with a dibasic acid anhydride having a polymerizable double bond. A resin obtained by reacting an OH group-containing acrylic resin, an isocyanate, and a compound having a polymerizable group, as described in Japanese Patent Laid-Open No. 2002-229207 and Japanese Patent Laid-Open No. 2003-335814. A resin or the like obtained by subjecting a resin having a leaving group such as a halogen atom or a sulfonate group at the α-position or the β-position and having an ester group at a side chain to an alkaline treatment. Furthermore, ACRYCURE RD-F8 (manufactured by Japan Catalyst Corporation) is also preferable.

As the alkali-soluble resin, a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a multi-component copolymer containing benzyl (meth) acrylate / (meth) acrylic acid / other monomers is particularly suitable. Other examples include a copolymer of benzyl (meth) acrylate / (meth) acrylic acid / -2-hydroxyethyl (meth) acrylate copolymerized with 2-hydroxyethyl methacrylate, Japanese Patent Laid-Open No. 7 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxyacrylic acid, as described in JP-140654 Propyl ester / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / Methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc., particularly, benzyl methacrylate / Copolymers of methacrylic acid and the like.

The alkali-soluble resin can refer to paragraphs 0558 to 0571 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to US Patent Application Publication No. 2012/0235099, <0685> to <0700>), and these contents are combined. Into this manual. In addition, it is preferable to use the copolymer (B) described in paragraph number 0029 to paragraph number 0063 described in Japanese Patent Laid-Open No. 2012-32767 and the alkali-soluble resin used in the examples and Japanese patent special The adhesive resins described in paragraph numbers 0088 to 0098 of Japanese Patent Publication No. 2012-208474 and the adhesive resins used in the examples are described in paragraph numbers 0022 to 0032 of Japanese Patent Application Laid-Open No. 2012-137531. Adhesive resin used in Examples, the adhesive resin used in Examples, the adhesive resin described in paragraph number 0132 to paragraph number 0143 of Japanese Patent Laid-Open No. 2013-024934, and the adhesive resin used in the examples, Japanese Patent Laid-Open Adhesive resins described in paragraph numbers 092 to 0098 of the 2011-242752 and the adhesive resins used in the examples, and adhesives described in paragraph numbers 0030 to 0072 of the Japanese Patent Laid-Open No. 2012-032770 Resin. These contents are incorporated into this specification. More specifically, the following resins are preferred. In the following, n is an integer of 1-10.

[Chemical 33]

The polymers shown below can also be used. [Chem 34]

The alkali-soluble resin is also preferably a polymer of the present invention. Since the polymer of the present invention is excellent in heat resistance, a cured film having more excellent heat resistance can be formed. The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and particularly preferably 70 mgKOH / g to 120 mgKOH / g. The weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.

When an alkali-soluble resin is contained in the curable composition or coloring composition of the present invention, the content of the alkali-soluble resin is preferably 1% to 15% by mass relative to all solid components of the coloring composition. More preferred is 2% to 12% by mass, and particularly preferred is 3% to 10% by mass. When the polymer of the present invention is used as the alkali-soluble resin, it is preferable that the solid polymer of the alkali-soluble resin contains 5% to 100% by mass of the polymer of the present invention. The lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 50% by mass or more. The upper limit may be, for example, 95% by mass or less, or 90% by mass or less. The curable composition or colored composition of the present invention may contain only one kind of alkali-soluble resin, or may contain two or more kinds. When two or more kinds are included, it is preferable that the total amount thereof is within the range.

<< Photopolymerization initiator >> It is preferable that the curable composition or colored composition of the present invention further contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of a polymerizable compound, and it can be appropriately selected from known photopolymerization initiators. For example, those having a sensitivity from the ultraviolet region to visible light are preferred. In addition, it may be an active agent that generates some action with a photo-excited sensitizer and generates an active radical, or an initiator that initiates cationic polymerization according to the type of monomer. Further, the photopolymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and those having an oxadiazole skeleton), fluorenyl phosphine compounds such as fluorenylphosphine oxide, oximes such as hexaaryldiimidazole, and oxime derivatives Compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like.

Furthermore, from the viewpoint of exposure sensitivity, it is preferably selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a fluorenylphosphine compound, Phosphine oxide compound, metallocene compound, oxime compound, triallyl imidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene- Compounds consisting of iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

Even more preferred are trihalomethyltriazine compounds, α-aminoketone compounds, fluorenylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, The acetophenone compound is particularly preferably at least one selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triallyl imidazole dimer, and a benzophenone compound. A compound. Commercially available products include TAZ-107 (manufactured by Green Chemical Co., Ltd.).

In particular, when the colored composition of the present invention is used in the production of a color filter for a solid-state imaging element, it is necessary to form a fine pattern with a sharp shape. Therefore, it is important that the hardening property is applied to the unexposed portion. Development was carried out without residue. From such a viewpoint, it is particularly preferable to use an oxime compound as a photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging element, stepwise exposure is used for curing exposure. However, the exposure machine may be damaged due to halogen, and it is necessary to also suppress the addition amount of the photopolymerization initiator. Since it is low, considering these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator in order to form a fine pattern such as a solid-state imaging element. In addition, by using an oxime compound, the color shift property can be further improved. As a specific example of the photopolymerization initiator used in the present invention, for example, paragraphs 0265 to 0268 of Japanese Patent Laid-Open No. 2013-29760 can be referred to, and the contents thereof are incorporated into the present specification.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a fluorenylphosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and a fluorenylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used. . As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IGACURE (1 IRGACURE) -127 (trade name; all manufactured by BASF). Aminoacetophenone-based initiators can be commercially available as IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names; all manufactured by BASF) Company). As the aminoacetophenone-based initiator, a compound described in Japanese Patent Laid-Open No. 2009-191179 can be used in which the absorption wavelength matches a long-wave light source such as 365 nm or 405 nm. As the fluorenylphosphine-based initiator, commercially available products such as IRGACURE-819 or DAROCUR-TPO (trade names; all manufactured by BASF) can be used.

The photopolymerization initiator is more preferably an oxime compound. Specific examples of the oxime initiator include compounds described in Japanese Patent Laid-Open No. 2001-233842, compounds described in Japanese Patent Laid-Open No. 2000-80068, and compounds described in Japanese Patent Laid-Open No. 2006-342166. .

Examples of the oxime compound such as an oxime derivative suitably used as the photopolymerization initiator in the present invention include 3-benzyloxyiminobutane-2-one, and 3-acetamidooxyimine Butane-2-one, 3-propionyloxyiminobutane-2-one, 2-ethoxymethyliminopentane-3-one, 2-ethoxymethylimino- 1-phenylpropane-1-one, 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- Ketones, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, and the like.

Examples of oxime compounds include the Journal of the British Chemical Society, JCS Perkin II (1979), pages 1653 to 1660, the Journal of the British Chemical Society, JJ Perkin II (1979) Pages 156 to 162, Journal of Photopolymer Science and Technology (1995) pages 202 to 232, compounds described in Japanese Patent Laid-Open No. 2000-66385, Japanese patents The compounds described in each publication of JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166. For commercial products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can also be suitably used. In addition, you can also use TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO. , LTD), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (made by Adiko).

In addition, oxime compounds other than those described above can also be used: compounds described in Japanese Patent Publication No. 2009-519904, in which an oxime is linked to the N position of carbazole, and a heterogeneous substituent is introduced into a benzophenone moiety. Compounds described in U.S. Patent No. 7626957, Japanese Patent Laid-Open No. 2010-15025 in which a nitro group is introduced into a pigment portion, and compounds described in U.S. Patent Publication No. 2009-292039, and International Publication No. 2009-131189 The ketoxime compound described in the above, the compound described in U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule, and a Japanese patent having an absorption maximum at 405 nm and a good sensitivity to a g-ray light source Compounds described in Japanese Patent Application Laid-Open No. 2009-221114. For example, paragraphs 0274 to 0275 of Japanese Patent Laid-Open No. 2013-29760 can be referred to, and the contents are incorporated into the present specification. Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). In addition, the oxime can be an oxime compound whose NO bond is (E) form, an oxime compound whose NO bond is (Z) form, or an oxime NO bond (E) form and (Z) form. mixture.

[Chemical 35]

In the general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetal atomic group. Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, a fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, an arylthiocarbonyl group, and the like. These groups may have one or more substituents. Moreover, the substituent may be further substituted with another substituent. Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a fluorenyloxy group, a fluorenyl group, an alkyl group, and an aryl group. In the general formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have more than one substituent. Examples of the substituent include those described above. In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, a cycloalkylene group, or an alkynyl group having 1 to 12 carbon atoms. These groups may have more than one substituent. Examples of the substituent include those described above.

Specific examples (C-4) to (C-13) of the compound represented by the general formula (OX-1) are shown below, but the present invention is not limited to these.

[Chemical 36]

The present invention may also use an oxime compound having a fluorine atom as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in Japanese Patent Laid-Open No. 2010-262028, compounds 24, Compound 36 to Compound 40 described in Japanese Patent Laid-Open No. 2014-500852, and Japanese Patent Laid-Open Compound (C-3) and the like described in 2013-164471. The contents are incorporated into this specification.

The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, and preferably has a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm. Particularly preferred are high absorbances at 365 nm and 455 nm.

From the viewpoint of self-sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The Molar absorption coefficient of the compound can be measured by a known method. Specifically, for example, a UV-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian) is preferably used, and ethyl acetate is preferably used. The ester solvent was measured at a concentration of 0.01 g / L. The photopolymerization initiator used in the present invention may also be used in combination of two or more kinds as necessary.

When the curable composition or colored composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1% by mass to 50% with respect to all the solid components of the colored composition. Mass%, more preferably 0.5% to 30% by mass, and still more preferably 1% to 20% by mass. If it is this range, more favorable sensitivity and pattern formation property can be obtained. The composition of the present invention may include only one photopolymerization initiator, or may include two or more. When two or more kinds are included, it is preferable that the total amount thereof is within the range.

<< Other components> In addition to the above components, the curable composition or colored composition of the present invention may further include a solvent, a polymerization inhibitor, a surfactant, and an organic compound within a range that does not impair the effects of the present invention. Other components such as carboxylic acid and organic carboxylic anhydride.

<<< Solvent >> The curable composition or coloring composition of this invention may contain a solvent. The solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coatability of the colored composition. It is preferred to consider the solubility, coatability, and safety of the pigment (A), the hardening compound, and the like. select. Moreover, when preparing the coloring composition of the present invention, it is preferable to include at least two solvents.

Examples of the solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and butyric acid. Ethyl acetate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg, methyl oxyacetate, ethyl ethoxylate, butyl oxyacetate (eg methyl methoxyacetate) , Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionates (for example: 3-oxypropyl Methyl ester, ethyl 3-oxypropionate, etc. (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc.)), alkyl 2-oxypropionates (e.g., methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (e.g. Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate) ), Methyl 2-oxy-2-methylpropionate, and ethyl 2-oxy-2-methylpropionate (e.g. 2- Methyloxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methylpyruvate, ethylpyruvate, propylpyruvate, methylacetate, Ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like; and ethers include, for example, diethylene glycol dimethyl ether, tetrahydrofuran, and ethylene glycol monomethyl ether. , Ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol mono Methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and the like; and ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and the like. 3-heptanone and the like; and examples of the aromatic hydrocarbons include toluene and xylene.

These solvents are also preferably mixed with two or more kinds from the viewpoints of the solubility of the pigment (A), the hardening compound, and the like, and the improvement of the coating surface. In this case, it is particularly preferable to include a material selected from the group consisting of the methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethyl Dimethyl glycol ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether And two or more mixed liquids of propylene glycol methyl ether acetate. In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

From the viewpoint of coatability, the content of the solvent in the coloring composition is preferably an amount in which all solid content concentrations of the coloring composition become 5 to 80% by mass, and more preferably 5 to 60% by mass. Particularly preferred is 10% to 50% by mass. The curable composition or colored composition of the present invention may contain only one kind of solvent, or may contain two or more kinds. When two or more kinds are included, it is preferable that the total amount thereof is within the range.

<<< Polymerization inhibitor >> In order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored composition, it is desirable to add it to the curable composition or the colored composition of the present invention. Small amount of polymerization inhibitor. Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-third-butyl-p-cresol, catechol, third-butylcatechol, and benzene. Quinone, 4,4'-thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6-third butylphenol), N -Nitrosylphenylhydroxylamine cerium salts and the like. When the curable composition or the colored composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably about 0.01 to 5 mass% based on the mass of the colored composition. The curable composition or colored composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more kinds are included, it is preferable that the total amount thereof is within the range.

<Surfactant> From the viewpoint of further improving coatability, various surfactants may be added to the composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

In particular, the composition of the present invention further improves the liquid characteristics (especially fluidity) when the coating liquid is prepared by containing a fluorine-based surfactant, and thus can further improve the uniformity of coating thickness or liquid-saving properties. That is, when a film is formed using a coating liquid to which a composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, thereby improving the effect on the surface to be coated. Wettability improves coating properties on the surface to be coated. Therefore, it is effective in forming a thin film having a uniform thickness with small thickness unevenness even when a thin film having a thickness of several μm is formed with a small amount of liquid.

The fluorine content in the fluorine-based surfactant is preferably 3% to 40% by mass, more preferably 5% to 30% by mass, and particularly preferably 7% to 25% by mass. A fluorine-based surfactant having a fluorine content ratio within this range is effective in terms of thickness uniformity or liquid saving of the coating film, and also has good solubility in the composition.

Examples of the fluorine-based interface activity include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, and Mega (Megafac) F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac (Megafac) F482, Megafac F554, Megafac F780, Megafac F781 (above manufactured by Dickson), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above manufactured by Sumitomo 3M), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above Manufactured by Asahi Glass Company), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like. In addition, the following compounds may be exemplified as the fluorine-based surfactant used in the present invention. [Chemical 37]

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate, Glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene ole alkenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, poly Ethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters (Pluronic L10, Pluronic L31, Pluronic L61 manufactured by BASF) , Pluronic L62, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tetronic 701, Tetronic ) 704, Tetronic 901, Tetronic 904, Tetronic 150R1), Solsperse 20000 (Lubrizol Corporation of Japan), etc.

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Industries, Ltd.), an organosiloxane polymer (manufactured by Shin-Etsu Chemical Co., Ltd.), (methyl ) Acrylic (co) polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (Manufactured by Yushang Corporation), etc.

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yushang Corporation).

Examples of the silicone-based surfactant include "Toray Silicone DC3PA", "Toray Silicone SH7PA", and "Toray Silicone DC11PA" manufactured by Toray Dow Corning Corporation. , "Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray Silicone SH30PA", " Toray Silicone SH8400 "," TSF-4440 "," TSF-4300 "," TSF-4445 "," TSF-4460 "," TSF-4452 ", Shin-Etsu Silicon manufactured by Momentive Advanced Materials Co., Ltd. "KP341", "KF6001", "KF6002" manufactured by Liko Corporation, "BYK307", "BYK323", "BYK330", etc. manufactured by BYK Corporation. When a surfactant is contained in the composition of the present invention, the added amount of the surfactant is preferably 0.001% to 2.0% by mass relative to the total mass of the composition, and more preferably 0.005% by mass. To 1.0% by mass. The composition of the present invention may contain only one kind of surfactant, or may contain two or more kinds. When two or more kinds are included, it is preferable that the total amount thereof is within the range.

<<< Organic carboxylic acid, organic carboxylic anhydride >> The curable composition or colored composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1,000 or less and / or an organic carboxylic anhydride. Specific examples of the organic carboxylic acid and the organic carboxylic acid anhydride can be referred to, for example, paragraphs 0338 to 0340 of Japanese Patent Laid-Open No. 2013-29760, the contents of which are incorporated herein. When an organic carboxylic acid and an organic carboxylic anhydride are contained in the curable composition or coloring composition of this invention, the addition amount of an organic carboxylic acid and / or an organic carboxylic anhydride is 0.01 to 10 mass% normally in all the solid content The mass% is preferably in the range of 0.03 mass% to 5 mass%, and more preferably in the range of 0.05 mass% to 3 mass%. The curable composition or the coloring composition of the present invention may contain only one kind of organic carboxylic acid and / or organic carboxylic anhydride, respectively, or may contain two or more kinds. When two or more kinds are included, it is preferable that the total amount thereof is within the range.

In addition to the above, various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation inhibitors can be blended into the curable composition or the colored composition of the present invention as necessary. Examples of such additives include those described in paragraphs 0155 to 0156 of Japanese Patent Laid-Open No. 2004-295116, and these contents are incorporated into the present specification. Furthermore, the following compounds may be contained. [Chemical 38] The curable composition or colored composition of the present invention may contain the sensitizer or light stabilizer described in paragraph 0078 of Japanese Patent Laid-Open No. 2004-295116, and the The thermal polymerization inhibitor described in paragraph 0081. Moreover, the binder may contain a resin containing a monomer represented by the general formula (1) as a copolymerization component in Japanese Patent Laid-Open No. 2006-215453. The coloring composition contains metal elements due to the raw materials used, but from the viewpoint of suppressing the occurrence of defects, the content of the Group 2 element (calcium, magnesium, etc.) in the coloring composition is preferably 50 ppm or less. It is preferable to control it to 0.01 ppm to 10 ppm. In addition, the total amount of the inorganic metal salt in the coloring composition is preferably 100 ppm or less, and more preferably controlled to 0.5 to 50 ppm.

<The manufacturing method of a curable composition and a coloring composition> The curable composition and the coloring composition of this invention can be prepared by mixing the said component. In the preparation of the curable composition or the coloring composition, the components constituting the curable composition or the coloring composition may be prepared at one time, or each component may be prepared by dissolving and dispersing the components in a solvent. In addition, the order of input and working conditions during deployment are not particularly restricted. For example, all components can be dissolved and dispersed in a solvent at the same time to prepare a composition. If necessary, each component can be appropriately prepared into two or more solutions / dispersions, and these can be mixed during use (during coating). Instead, a composition was prepared. The curable composition or the colored composition of the present invention is preferably filtered through a filter for the purpose of removing foreign matter or reducing defects. If it is a user currently used for filtration etc., it can use it without a restriction | limiting. Examples include the use of fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6, nylon-6,6, polyolefin resins such as polyethylene, polypropylene (PP) Density, ultra-high molecular weight polyolefin resin) and other filters. Among these raw materials, polypropylene (including high-density polypropylene) is preferred. The pore diameter of the filter is preferably about 0.01 μm to 7.0 μm, preferably about 0.01 μm to 3.0 μm, and more preferably about 0.05 μm to 0.5 μm. By setting it as this range, fine foreign matter can be reliably removed, and the fine foreign matter hinders the preparation of a uniform and smooth curable composition or a coloring composition in a subsequent step.

When using filters, different filters can also be combined. In this case, the filtration by the first filter may be performed only once, or may be performed twice or more. Furthermore, the first filters having different pore diameters within the above range may be combined. The pore size here can refer to the nominal value of the filter manufacturer. Commercially available filters can be obtained, for example, from PALL Corporation, Edubontech Toyo Co., Ltd., Intertek Corporation (formerly Japan Mykrolis Corporation), or Kitazawa Microfilter Corporation. Choose from a variety of filters provided. As the second filter, a filter made of the same material as the first filter can be used. For example, the filtration using the first filter may be performed only with the dispersion liquid, or the second filtration may be performed after mixing with other components.

<Curable Film> The cured film of the present invention is obtained by curing the curable composition of the present invention or the colored composition of the present invention. In particular, when the colored composition of the present invention is used, a cured film having good heat resistance and color shift properties can be formed. Therefore, it can be suitably used for forming a colored layer of a color filter. In addition, the coloring composition of the present invention can be used as a solid-state imaging device (such as a Charge Coupled Device (CCD), a Complementary Metal-Oxide Semiconductor (CMOS), or the like) or a liquid crystal display device (LCD). It is suitable for coloring pattern forming applications such as color filters used in image display devices. It can also be suitably used as a production application of printing ink, inkjet ink, paint, and the like. Among them, it can be suitably used in the manufacture of color filters for solid-state imaging elements such as CCDs and CMOS.

<Color filter> The color filter of this invention can be obtained using the coloring composition of this invention. The manufacturing method of the color filter is not particularly limited, and a photolithography method and a dry etching method can be preferably used. For details of the manufacturing method of the color filter, refer to the descriptions of paragraphs 0137 to 0145 of Japanese Patent Laid-Open No. 2014-080589, paragraphs 0215 to 0264 of Japanese Patent Laid-Open No. 2014-043556, and the like. The figures referred to in the article are incorporated into this specification.

<Solid-state imaging element> The color filter of the present invention can be used in a solid-state imaging element. For details of the solid-state imaging device, refer to the descriptions in paragraphs 0155 to 0156 of Japanese Patent Laid-Open No. 2014-080589, the descriptions of paragraphs 0291 to 0305 in Japanese Patent Laid-Open No. 2013-257543, and Japanese Patent Laid-Open The descriptions of paragraphs 0312 to 0314 of the 2013-257543 gazette are incorporated into this specification.

<Image display device> The color filter of the present invention can be used in an image display device such as a liquid crystal display device or an organic EL display device (organic light emitting display device), and is particularly suitable for use in a liquid crystal display device. For details of the image display device, refer to the descriptions of paragraphs 0150 to 0154 of Japanese Patent Laid-Open No. 2014-080589, and the descriptions of paragraphs 0307 to 0311 of Japanese Patent Laid-Open No. 2013-257543. Into this manual. [Example]

Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples as long as the present invention does not exceed the gist thereof. In addition, unless otherwise specified, "%" and "part" are quality standards.

<Synthesis Example 1> Synthesis of (S-27) (thiourea to potassium carbonate method) [Chem. 39]

Five parts of dipentaerythritol (DPE, manufactured by Tokyo Chemical Industry Co., Ltd.) and 80 parts of N, N-dimethylacetamide (DMAc) were added to a three-necked flask, and stirred in a water bath at 20 ° C. under a nitrogen atmosphere. After 31 parts of 6-bromohexamethylene chloride [manufactured by Tokyo Chemical Industry Co., Ltd.] was added dropwise thereto at a temperature not exceeding 30 ° C, stirring was performed at room temperature for 2 hours. The reaction solution was added to 350 parts of a 1 N aqueous hydrochloric acid solution in small portions at a time to stop the reaction, and then 500 parts of ethyl acetate was added to perform a liquid separation operation. Then, the organic layer was washed with 250 parts of a saturated sodium bicarbonate aqueous solution, 250 parts of water, and 150 parts of a saturated saline solution. After adding sodium sulfate to the obtained organic layer, filtration and separation were performed, and the filtrate was concentrated under reduced pressure, thereby obtaining 24 parts of an intermediate S-27-1 (yield: 93%). 20 parts of intermediate S-27-1, 9.5 parts of thiourea, 200 parts of ethanol, and 17.6 parts of potassium iodide were added to a three-necked flask, and the mixture was heated and refluxed under a nitrogen atmosphere to react for 18 hours. 81 parts of a 20% potassium carbonate aqueous solution was added to the solution after the reaction, and the reaction was carried out at 70 ° C for 3 hours, followed by cooling. Next, 150 parts of a 1N aqueous hydrochloric acid solution and 300 parts of chloroform were added thereto to carry out a liquid separation operation. Next, the organic layer was washed twice with 150 parts of saturated brine, sodium sulfate was added to the organic layer, and then filtered and separated. The filtrate was concentrated under reduced pressure to obtain 14.7 parts of S-27 (93% yield). ). ¹ H NMR (DMSO-d6) δ 4.05 (s, 12H), 3.40 (s, 4H), 2.47 (td, 12H), 2.30 (t, 12H), 2.17 (t, 6H), 1.54 (m, 24H) , 1.35 (m, 12H). MALDI-MS m / z count value: 1057 [M + Na], experimental value: 1057. The purity measured by HPLC was 53%.

<Synthesis Example 2> Synthesis of (S-27) (potassium thioacetate to hydrazine method) [Chem. 40]

4.3 parts of intermediate S-27-1, 43 parts of DMAc, and 2.2 parts of tetrabutylammonium bromide were added to a three-necked flask, and stirred in a water bath under a nitrogen atmosphere. To this, 2.63 parts of potassium thioacetate was added in 4 portions, and the reaction was carried out at 50 ° C for 4 hours. To the solution after the reaction, 129 parts of ethyl acetate, 65 parts of a saturated sodium bicarbonate aqueous solution, and 65 parts of water were added to perform a liquid separation operation. Next, the organic layer was washed twice with 129 parts of 1 N hydrochloric acid and 129 parts of saturated saline, and sodium sulfate was added, followed by filtration and separation. The filtrate was concentrated under reduced pressure to obtain 4.2 parts of intermediate S-27-2. (100% yield). 2.2 parts of intermediate S-27-2 and 22 parts of DMAc were added to a three-necked flask, and stirred at 15 ° C under a nitrogen atmosphere. 0.85 parts of hydrazine hydrochloride and 2.0 parts of sodium acetate were added thereto, and reacted at 15 ° C for 4 hours. 66 parts of ethyl acetate were added to the solution after the reaction, and the solution was washed twice with 66 parts of a 1 N aqueous hydrochloric acid solution, and then washed twice with 66 parts of saturated common salt. After adding magnesium sulfate to the obtained organic layer, filtration and separation were performed, and the filtrate was concentrated under reduced pressure to obtain 1.73 parts of S-27 (yield: 98%). The purity measured by HPLC was 80%.

<Synthesis Example 3> (S-27) Synthesis (dehydration shrinkage method) [Chem. 41]

2.3 parts of dipentaerythritol (DPE, manufactured by Tokyo Chemical Industry Co., Ltd.), 8.0 parts of 6-mercaptohexanoic acid, 50 parts of toluene, and 1 part of concentrated sulfuric acid were added to a flask, and heated under reflux in a nitrogen atmosphere. After 6 hours, the outflow of water stopped. Next, 100 parts of ethyl acetate was added to the refluxed solution, and the organic layer was washed once with 100 parts of water, washed twice with 100 parts of a 3% sodium hydrogen carbonate aqueous solution, and 50 parts with 1 N hydrochloric acid. The washing was performed twice, and further washed twice with 50 parts of saturated saline. After sodium sulfate was added to the obtained organic layer, it was separated by filtration, and the filtrate was concentrated under reduced pressure, thereby obtaining 7.3 parts of S-27 (yield: 78%). The purity measured by HPLC was 38%.

<Synthesis Example 4> Synthesis of (S-28) [Chem. 42]

In Synthesis Example 1 of (S-27), 38.2 parts of 10-bromodecanoyl chloride (synthesized by 10-bromodecanoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) according to a known method) was used in place of 6-bromohexano The same procedure as in Synthesis Example 1 of (S-27) was carried out except for the addition of chlorine, and 27.7 parts of an intermediate S-28-1 was obtained (yield: 85%). In Synthesis Example 1 of (S-27), 25 parts of Intermediate S-28-1 was used instead of Intermediate S-27-1, and synthesis was performed in the same manner as in Synthesis Example 1 to obtain 17.7 parts of S-28 ( The yield is 85%). ¹ H NMR (DMSO-d6) δ 4.05 (s, 12H), 3.42 (s, 4H), 2.48 (td, 12H), 2.32 (t, 12H), 2.18 (t, 6H), 1.53 (m, 24H) , 1.30 (m, 60H). MALDI-MS m / z count value: 1394 [M + Na], experimental value: 1394. The purity measured by HPLC was 51%.

<Synthesis Example 5> Synthesis of (S-3) [Chem. 43]

In Synthesis Example 1 of (S-27), except that 5.3 parts of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of dipentaerythritol, synthesis was performed in the same manner as in Synthesis Example 1 of (S-27) to obtain 23.1 parts of intermediate S-3-1 (88% yield). The synthesis example 1 of (S-27) was the same as the synthesis example 1 of (S-27), except that 20 parts of the intermediate S-3-1, 8.2 parts of thiourea, 200 parts of ethanol, and 18 parts of potassium iodide were used. Synthesis was carried out to obtain 11.8 parts of S-3 (75% yield). ¹ H NMR (DMSO-d6) δ 4.05 (s, 6H), 2.47 (td, 6H), 2.30 (t, 6H), 2.17 (t, 3H), 1.54 (m, 14H), 1.35 (m, 6H) , 0.96 (t, 3H). MALDI-MS m / z count: 547 [M + Na], experimental value: 547. The purity measured by HPLC was 85%.

<Synthesis Example 6> Synthesis of (S-8) [Chem. 44]

In Synthesis Example 1 of (S-27), 5.3 parts of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of dipentaerythritol, and 38.1 parts of 10-bromodecanoic acid chloride (using 10-bromodecanoic acid (Tokyo (Manufactured by Kasei Kagaku Kogyo Co., Ltd.) and synthesized in accordance with a known method), except that 6-bromohexamethylene chloride was used instead of 6-bromohexamidine chloride. The yield is 89%). In Synthesis Example 1 of (S-27), 25 parts of Intermediate S-8-1 was used instead of Intermediate S-27-1, and synthesis was performed in the same manner as in Synthesis Example 1 to obtain 16.4 parts of S-8 ( The yield is 79%). ¹ H NMR (DMSO-d6) δ 4.05 (s, 6H), 2.47 (td, 6H), 2.30 (t, 6H), 2.17 (t, 3H), 1.53 (m, 14H), 1.30 (m, 30H) , 0.94 (t, 3H). MALDI-MS m / z count: 715 [M + Na], experimental value: 715. The purity measured by HPLC was 79%.

<Synthesis Example 7> Synthesis of (S-24) [Chem. 45]

In Synthesis Example 1 of (S-27), 4 parts of pentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of dipentaerythritol, and synthesis was performed in the same manner as in Synthesis Example 1 of (S-27) to obtain 22.8 parts of an intermediate. S-24-1 (92% yield). The synthesis example 1 of (S-27) was the same as the synthesis example 1 of (S-27), except that 20 parts of the intermediate S-24-1, 12.3 parts of thiourea, 200 parts of ethanol, and 24 parts of potassium iodide were used. Synthesis was carried out to obtain 14.6 parts of S-24 (94% yield). ¹ H NMR (DMSO-d6) δ 4.03 (s, 8H), 2.46 (td, 8H), 2.29 (t, 8H), 2.16 (t, 4H), 1.54 (m, 16H), 1.35 (m, 8H) . MALDI-MS m / z count: 679 [M + Na], experimental value: 679. The purity measured by HPLC was 82%.

<Synthesis Example 8> Synthesis of (S-31)

In Synthesis Example 1 of (S-27), except that 3.6 parts of D-sorbitol (manufactured by Kanto Chemical Co., Ltd.) was used instead of dipentaerythritol, synthesis was performed in the same manner as in Synthesis Example 1 of (S-27), and 18.8 parts of intermediate was obtained. Compound S-31-1 (76% yield). The synthesis example 1 of (S-27) was the same as the synthesis example 1 of (S-27), except that 10 parts of the intermediate S-31-1, 4.4 parts of thiourea, 100 parts of ethanol, and 9 parts of potassium iodide were used. Synthesis was carried out to obtain 5.7 parts of S-31 (yield: 74%). ¹ H NMR (CDCl ₃ ) δ 5.42 (m, 2H), 5.24 (m, 1H), 5.05 (m, 1H), 4.3 (m, 2H), 4.1 (m, 2H), 2.46 (td, 12H), 2.30 (m, 12H), 2.19 (t, 6H), 1.55 (m, 24H), 1.36 (m, 12H). MALDI-MS m / z count value: 985 [M + Na], experimental value: 985. The purity measured by HPLC was 73%.

<Synthesis Example 9> Synthesis of (S-32) [Chem. 47]

5 parts of polypropylene glycol sorbitol ether (manufactured by Nippon Oil Corporation, trade name UNIOL HS-1600D, average molecular weight 1,600, n = 3 (average)), 80 parts of tetrahydrofuran, 3.2 parts of potassium hydroxide, 0.5 Tetraethylammonium bromide was added to the flask and stirred in a 70 ° C bath. After 6.8 parts of allyl bromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, the mixture was directly stirred for 12 hours. Next, 100 parts of ethyl acetate was added to the agitated solution, washed twice with 100 parts of water, washed once with 100 parts of a saturated aqueous sodium hydrogen carbonate solution, and then washed once with 100 parts of a saturated saline solution. Cleaning. After adding magnesium sulfate to the obtained organic layer, filtration and separation were performed, and the filtrate was concentrated under reduced pressure, thereby obtaining 4.9 parts of an intermediate S-32-1 (yield: 85%). 2 parts of intermediate S-32-1, 30 parts of cyclohexanone, and 1.5 parts of thioacetic acid were added to a flask, and stirred in a bath at 80 ° C. To this was added 1.5 parts of 2,2'-azobis (isobutyric acid) dimethyl ester (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-601), followed by heating and stirring at 80 ° C for 2 hours, and further adding 0.3 parts of V-601 was heated and stirred at 80 ° C for 2 hours, and heated and stirred at 90 ° C for 1.5 hours. Next, 100 parts of ethyl acetate was added, washing was performed twice with 50 parts of a 5% sodium carbonate aqueous solution, and 50 parts of saturated brine was added. After adding magnesium sulfate to the organic layer, filtration and separation were performed, and the filtrate was concentrated under reduced pressure. Thereby, 2.0 parts of intermediate S-32-2 was obtained (80% yield). Two parts of the intermediate S-32-2 and 22 parts of DMAc were added to the flask, and the mixture was stirred under a nitrogen atmosphere at 15 ° C. 0.43 parts of hydrazine hydrochloride and 1.1 parts of sodium acetate were added thereto, and the reaction was performed at 15 ° C for 4 hours. Next, 80 parts of ethyl acetate was added, and washing was performed twice with 50 parts of a 1 N aqueous hydrochloric acid solution, followed by washing twice with 50 parts of a saturated saline solution. After adding magnesium sulfate to the organic layer, the mixture was filtered and separated. It was concentrated under pressure to obtain 1.35 parts of S-32 (76% yield). The purity measured by HPLC was 90%.

<Synthesis Example 10> Synthesis of (S-38)

In Synthesis Example 1 of (S-27), 1.7 parts of hexahydroxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of dipentaerythritol, 40 parts of N, N-dimethylacetamide (DMAc), 19 parts of 6- Bromhexyl chloride was synthesized in the same manner as in Synthesis Example 1 of (S-27) except for stirring at room temperature for 18 hours, to obtain 9.6 parts of intermediate S-38-1 (yield: 80%). The synthesis example 1 of (S-27) was the same as the synthesis example 1 of (S-27), except that 8 parts of the intermediate S-38-1, 3.6 parts of thiourea, 80 parts of ethanol, and 7.7 parts of potassium iodide were used. Synthesis was carried out to obtain 4.4 parts of S-38 (71% yield). ¹ H NMR (DMSO-d6) δ 2.47 (td, 12H), 2.28 (t, 12H), 2.17 (t, 6H), 1.52 (m, 24H), 1.35 (m, 12H). MALDI-MS m / z count: 977 [M + Na], experimental value: 977. The purity measured by HPLC was 70%.

<Synthesis Example 11> Synthesis of (S-41) [Chem. 49]

The intermediate S-41-1 can be synthesized according to a known method (Synth. Commun., 1994, Vol. 24, pp. 2153 to 2158). In Synthesis Example 1 of (S-27), 3.8 parts of intermediate S-41-1 was used in place of dipentaerythritol, 40 parts of N, N-dimethylacetamide (DMAc), and 9.8 parts of 6-bromohexamidine were used. Except for chlorine, synthesis was carried out in the same manner as in Synthesis Example 1 of (S-27), and 7.4 parts of an intermediate S-41-2 was obtained (yield: 80%). In Synthesis Example 1 of (S-27), 7 parts of the intermediate S-41-2, 2.7 parts of thiourea, 60 parts of ethanol, and 5.8 parts of potassium iodide were used, and were the same as in Synthesis Example 1 of (S-27). Synthesis was carried out to obtain 4.3 parts of S-41 (yield 76%). MALDI-MS m / z count: 1179 [M + Na], experimental value: 1179. The purity measured by HPLC was 72%.

<Synthesis Example 12> Synthesis of (S-45)

In Synthesis Example 1 of (S-27), 3.5 parts of D (+)-glucose (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of dipentaerythritol, except that synthesis was performed in (S-27) Synthesis Example 1 , 16.1 parts of intermediate S-45-1 were obtained (77% yield). In Synthesis Example 1 of (S-27), 16.2 parts of Intermediate S-45-1 was used in place of Intermediate S-27-1, and synthesis was performed in the same manner as in Synthesis Example 1 of (S-27) to obtain 10.7 parts of S-45 (85% yield). MALDI-MS m / z count: 853 [M + Na], experimental value: 853. The purity measured by HPLC was 69%.

<Synthesis Example 13> Synthesis of (S-51) [Chem. 51]

In Synthesis Example 1 of (S-27), 7.4 parts of bis-trimethylolpropane (manufactured by Mitsubishi Gas Chemical) was used in place of dipentaerythritol, except that synthesis was performed in Synthesis Example 1 of (S-27). 22.9 parts of intermediate S-51-1 were obtained (81% yield). In Synthesis Example 1 of (S-27), 21.8 parts of Intermediate S-51-1 was used instead of Intermediate S-27-1, and synthesis was performed in the same manner as in Synthesis Example 1 of (S-27) to obtain 14.9 parts of S-51 (85% yield). MALDI-MS m / z count value: 793 [M + Na], experimental value: 793. The purity measured by HPLC was 73%.

<Synthesis Example 14> Synthesis of (T-1) [Chem. 52]

7.6 parts of dipentaerythritol (DPE, manufactured by Tokyo Chemical Industry Co., Ltd.), 16.6 parts of thioglycolic acid (manufactured by Wako Pure Chemical Industries, Ltd.), 75 parts of toluene, 0.29 parts of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) ) Add to the flask and heat to reflux under a nitrogen atmosphere. After 8 hours, the outflow of water stopped. Next, after the solvent was distilled off under reduced pressure, 200 parts of chloroform was added to the residue, and the washing was performed once with 100 parts of a saturated aqueous sodium hydrogen carbonate solution, and the washing was performed three times with 100 parts of a 3% sodium hydrogen carbonate aqueous solution. Wash once with 50 parts of 1 N hydrochloric acid, and wash twice with 50 parts of saturated saline. After adding sodium sulfate to the obtained organic layer, filtration and separation were performed, and the filtrate was concentrated under reduced pressure to obtain 16.8 parts of T-1 (yield: 80%). The purity measured by HPLC was 40%.

<Synthesis Example 15> Synthesis of (T-3) [Chem. 53]

In Synthesis Example 1 of (S-27), except that 34.1 parts of 4-bromobutyrium chloride was used instead of 6-bromohexamidine chloride, synthesis was performed in the same manner as in Synthesis Example 1 of (S-27), and 11.2 parts were obtained. T-3 (65% yield). ¹ H NMR (CDCl ₃ ) δ 4.02 (s, 12H), 3.40 (s, 4H), 2.48 (td, 12H), 2.36 (t, 12H), 1.84 (m, 12H), 1.27 (t, 6H). MALDI-MS m / z count value: 889 [M + Na], experimental value: 889. The purity measured by HPLC was 50%.

<Synthesis Example 16> Synthesis of (T-4)

The synthesis example 1 of (S-27) was the same as the synthesis example 1 of (S-27), except that 33.9 parts of 5-bromopentyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 6-bromohexamidine chloride. Synthesis was carried out to obtain 10.1 parts of T-4 (54% yield). ¹ H NMR (CDCl ₃ ) δ 4.02 (s, 12H), 3.40 (s, 4H), 2.52 (td, 12H), 2.34 (t, 12H), 1.70 (m, 24H), 1.26 (t, 6H). The purity measured by HPLC was 55%.

<Method for measuring purity> A 5 mg measurement sample was dissolved in 1 mL of methanol, and HPLC measurement was performed under the following conditions. Dissolution and separation condition column: Shim-pack CLC-ODS manufactured by Shimadzu Corporation, dimensions 6.0 mm ID x 15 cm. Mobile phase A: methanol. Mobile phase B: 1% phosphoric acid + 1% triethylamine aqueous solution. Conditions: Dissolution was performed with A50% and B50% at 0 minutes, and a gradient concentration gradient of A95% and B5% at 30 minutes. Flow rate: 1.0 mL / min. Column temperature: 40 ° C. Detection wavelength: 210 nm.

<Example 1> 1. Preparation of a resist solution The components having the following composition were mixed and dissolved to prepare a resist solution for an undercoat layer. Composition of resist solution for undercoat layer · Solvent: 19.20 parts of propylene glycol monomethyl ether acetate · Solvent: 36.67 parts of ethyl lactate · Alkali soluble resin: benzyl methacrylate / methacrylic acid / methacrylic acid-2 -30.51 parts of a 40% PGMEA solution of a hydroxyethyl ester copolymer (molar ratio = 60/22/18, weight average molecular weight 15,000, number average molecular weight 9,000) · Polymerizable compound: dipentaerythritol hexaacrylate (Japanese Chemicals) Manufactured by the company, KAYARAD (DPHA) 12.20 parts · Polymerization inhibitor: 0.0061 parts of p-methoxyphenol · Fluorine-based surfactant: F-475, 0.83 parts manufactured by Diaisen Co., Ltd. · Start of photopolymerization Agent: 0.586 parts of trihalomethyltriazine-based photopolymerization initiator (TAZ-107, manufactured by Green Chemical Co., Ltd.)

2. Fabrication of a silicon wafer substrate with an undercoat layer A 6-inch silicon wafer was heated in an oven at 200 ° C for 30 minutes. Next, on this silicon wafer, an undercoat layer resist solution was applied so that the dry film thickness became 1.5 μm, and further dried by heating in an oven at 220 ° C. for 1 hour to form an undercoat layer. Undercoat silicon wafer substrate.

3. Preparation of colored composition 3-1. Colored composition The following components were mixed and dissolved, and filtered through a nylon filter having a pore size of 0.45 μm to prepare a colored composition. · Organic solvent 1 (cyclohexanone) 17.12 parts · Alkali soluble resin 1 (benzyl methacrylate / methacrylic acid (47/53 [mass ratio]), 30% propylene glycol monomethyl ether solution, Mw = 11,000) 1.23 parts · Alkali soluble resin 2 (ACRYCURE) RD-F8 (manufactured by Nippon Catalytic Corporation) 0.23 parts · Polymerizable compound 1 (manufactured by Shin Nakamura Chemical Co., Ltd., NK ESTER A-DPH-12E) 1.96 parts · Polymerization inhibitor (p-methoxyphenol) 0.0007 parts Photoinitiator 1 (IRGACURE OXE-02) 0.975 parts Thiol compound (S-27 synthesized in Synthesis Example 1) 0.35 parts · Fluorine surfactant (manufactured by Deaison, trade name: Megafac F-475, 1% propylene glycol monomethyl ether acetate solution) 2.50 parts · Pigment dispersion P1 (CI Pigment Blue 15: 6 dispersion Liquid, propylene glycol monomethyl ether acetate solution, solid content concentration of 12.8% by mass 1 51.40 parts dye solution (dye solution prepared by following) 24.57 parts

3-2. Preparation of Dye Solution 1 Dye solution 1 was prepared by mixing and dissolving the following components. · Organic solvent 1 (cyclohexanone) 21.55 parts · Dye (A-1) 3.02 parts

[Chem 55]

3-3. Preparation of Pigment Dispersion Liquid P1 (CI Pigment Blue 15: 6 Dispersion Liquid) A pigment dispersion liquid P1 (CI Pigment Blue 15: 6 dispersion liquid) was prepared as described below. 19.4 parts by mass of CI Pigment Blue 15: 6 (blue pigment; hereinafter also referred to as "PB15: 6") (average primary particle diameter of 55 nm) and 2.95 parts by mass of pigment dispersant BY-161 (manufactured by BYK Corporation) ), 2.95 parts by mass (9.93 parts by mass of solution) of alkali-soluble resin 1 (benzyl methacrylate / methacrylic acid (47/53 [mass ratio])), 30% propylene glycol monomethyl ether in terms of solid content The solution, Mw = 11,000) and 165.3 parts by mass of propylene glycol monomethyl ether were mixed, and the resulting mixed solution was dispersed in a beads mill (zirconia particles having a diameter of 0.3 mm) for 3 hours and dispersed. Thereafter, a high-pressure disperser NANO-3000-10 (manufactured by BEE Co., Ltd.) with a decompression mechanism was further used, and the dispersion treatment was performed at a flow rate of 500 g / min at a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to prepare a pigment dispersion liquid to obtain a CI Pigment Blue 15: 6 dispersion liquid. The obtained CI Pigment Blue 15: 6 dispersion was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)). The average primary particle diameter of the pigment was 24 nm.

4. Production of colored cured film 4-1: Production of colored cured film using colored composition The prepared colored composition is applied to the bottom of the prepared silicon wafer substrate with an undercoat layer. A colored layer (coating film) is formed on the coating. Then, the coating film was subjected to a heat treatment (pre-baking) for 120 seconds using a 100 ° C. hot plate so that the dry film thickness of the coating film became 1 μm. Next, the pre-baked silicon wafer substrate was heated at 200 ° C. for 5 minutes, and the coating film was cured to produce a colored cured film.

5. Evaluation of heat resistance The silicon wafer substrate with a colored hardened film produced as described above was heated by a hot plate at 280 ° C for 30 minutes, followed by immersion in cyclohexanone for 10 minutes. A colorimeter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.) was used to measure the visible light transmittance difference (ΔT) between 400 nm and 700 nm of a silicon wafer substrate with a colored cured film before and after immersion in cyclohexanone. Based on the measured ΔT, heat resistance was evaluated in accordance with the following evaluation criteria.

A: ΔT is less than 5% B: ΔT is 5% or more and less than 10% C: ΔT is 10% or more and less than 20% D: ΔT is 20% or more

<Other Examples and Comparative Examples> A colored composition was prepared in the same manner as in Example 1 except that the thiol compound was changed to the thiol compound shown in the following table to prepare a colored composition. The cured film was evaluated for heat resistance.

As a comparative thiol compound, T-1, T-3, T-4, or a commercially available T-2 synthesized in the synthesis example was used. Compound T-2 is dipentaerythritol hexa (3-mercaptopropionate) (manufactured by SC Organic Chemical Industries, Inc., product name DPMP).

[TABLE 20]

From these results, it was found that the colored composition of the present invention is excellent in heat resistance. In the preparation of the coloring composition of the present example, the use of the same quality of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate) instead of NK ESTER A-DPH-12E as a polymerizable compound 1 The obtained colored hardened film also obtained the same result. Furthermore, in the preparation of the coloring composition of this example, it was considered to use the same quality IRGACURE OXE-01 (manufactured by BASF) instead of IRGACURE OXE-02 as the photopolymerization initiator 1 The obtained colored hardened film also obtained the same result.

<Example 14> 1. Preparation of coating liquid (synthesis of perfluoroolefin copolymer (1))

[Chemical 56]

In the structural formula, 50:50 represents a mole ratio.

In a 100 ml autoclave with a stainless steel stirrer, 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether, and 0.55 g of dilaurin peroxide were added, and the system was degassed by nitrogen. Perform the replacement. Further, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave, and the temperature was raised to 65 ° C. The pressure at the time when the temperature in the autoclave reached 65 ° C was 0.53 MPa (5.4 kg / cm ² ). The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 0.31 MPa (3.2 kg / cm ² ), heating was stopped and the mixture was left to cool. At the time when the internal temperature was lowered to room temperature, the unreacted monomer was expelled, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large amount of excess hexane, and the solvent was removed by decantation, whereby the precipitated polymer was taken out. This polymer was further dissolved in a small amount of ethyl acetate and reprecipitated twice with hexane, thereby completely removing the residual monomer. The obtained polymer was dried, thereby obtaining 28 g of a polymer. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of propylene chloride was added dropwise thereto under ice-cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the obtained reaction solution, and the mixture was washed with water. After the product was extracted, the organic layer was concentrated to obtain a polymer. The obtained polymer was reprecipitated with hexane, thereby obtaining 19 g of a perfluoroolefin copolymer (1). The obtained polymer had a refractive index of 1.422 and a weight average molecular weight of 50,000.

(Preparation of Hollow Silica Dioxide Particle Dispersion A) 500 parts by mass of hollow silica dioxide microparticle sol (isopropanol silica sol, manufactured by Catalytic Chemical Industries, CS60-IPA, average particle size 60 nm, shell thickness 10 nm, silicon dioxide concentration is 20% by mass, and silicon dioxide particles have a refractive index of 1.31) 30 parts by mass of acryloxypropyltrimethoxysilane and 1.51 parts by mass of diisopropoxyethyl After aluminum acetate was mixed, 9 parts by mass of ion-exchanged water was added thereto. After the mixed solution was reacted at 60 ° C. for 8 hours, it was cooled to room temperature, and 1.8 parts by mass of acetamidine and acetone were added thereto to obtain a dispersion liquid. Thereafter, cyclohexanone was added to the obtained dispersion so that the content of silicon dioxide became approximately constant, and the solvent was replaced by vacuum distillation at a pressure of 30 Torr. Finally, the concentration was adjusted to obtain Dispersion A having a solid content concentration of 18.2% by mass. The residual amount of isopropyl alcohol (IPA) of the obtained dispersion liquid A was analyzed by gas chromatography, and the result was 0.5% by mass or less.

(Preparation of Coating Liquid) Each of the following components was mixed and dissolved in methyl ethyl ketone to prepare a coating liquid having a solid content concentration of 5% by mass. · 15 parts of perfluoroolefin copolymer (1) · 50 parts of hollow silica dispersion A · Polyfunctional monomer 1 (the following compound (A-2)) 20 parts · Polyfunctional monomer 2 (dipentaerythritol pentaacrylic acid) Mixture of esters and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd. 7 parts. Photopolymerization initiator (manufactured by BASF, Irgacure 127) 2.5 parts. Thiol compound (synthesized in Synthesis Example 1) (S-27)) 0.5 parts · Fluorine-containing monomer (following compound (A-3)) 5 parts

[Chemical 57]

2. Production of colorless cured film The prepared coating solution was applied on a glass substrate having an area of 100 cm ² using a gravure coater to form a coating film. Next, this coating film was dried at 90 ° C for 30 seconds, and then the coating film was irradiated with ultraviolet rays. Nitrogen flushing was performed to create an environment with an oxygen concentration of 0.1% by volume or less, and ultraviolet irradiation was performed using a 240 W / cm air-cooled metal halide lamp (manufactured by EYE GRAPHICS). The ultraviolet rays to be irradiated were ultraviolet rays having an illuminance of 600 mW / cm ² and an irradiation amount of 600 mJ / cm ² . The coating film was cured by irradiating ultraviolet rays to form a cured film having a thickness of 150 nm, and a glass substrate with a colorless cured film was obtained. The film thickness was calculated using a reflection spectrometer "FE-3000" (manufactured by Otsuka Electronics Co., Ltd.).

3. Evaluation of heat resistance The glass substrate with a colorless cured film produced as described above was heated by a hot plate at 220 ° C. for 30 minutes, followed by immersion in cyclohexanone for 10 minutes. The solvent was distilled off from the cyclohexanone solution under reduced pressure, and the obtained residue was dissolved in CDCl ₃ , and ¹⁹ F-NMR was measured. In the measurement, trifluorotoluene (manufactured by Wako Pure Chemical Industries, Ltd.) was used as an internal standard. The peak area of trifluorotoluene was set to 1, and the area of the CF ₃ group derived from the fluorine-containing monomer (A-3) was calculated. Due to its ratio. Next, the mass of the fluorine-containing monomer (A-3) eluted into cyclohexanone (the amount of eluted A-3) was calculated according to the following (Formula 1). Using the amount of eluted A-3, heat resistance was evaluated based on the following evaluation criteria.

(Formula 1) Dissolved amount of fluorine-containing monomer (A-3) [μg] = mass of trifluorotoluene [μg] × [(area ratio of fluorine-containing monomer) / (molecular weight of fluorine-containing monomer)] × (trifluorotoluene Molecular weight). A: Less than 1 μg of dissolved A-3 B: More than 1 μg and less than 2 μg of dissolved A-3 C: More than 2 μg and less than 4 μg of dissolved A-3 D: 4 μg of dissolved A-3 the above

In Example 14, the coating liquid was prepared in the same manner as in Example 14 except that the thiol compound was changed to the thiol compound shown in the following table to prepare a cured film, and the heat resistance was evaluated.

[TABLE 21]

From these results, it was found that the colored composition of the present invention is excellent in heat resistance.

<Example 20> 1. 102 parts by mass of the thiol compound S-27 obtained in Synthesis Example 2 and 100 parts by mass of an epoxy compound (manufactured by Mitsubishi Chemical Corporation, epoxy resin jER825, and epoxy equivalent were 170 [g / eq ]), And 4 parts by mass of a hardening accelerator (manufactured by Wako Pure Chemical Industries, Ltd., 3-aminomethyl-3,5,5-trimethylcyclohexylamine (IPDA)) are mixed to obtain a hardening composition. The mechanical strength of the hardened | cured material obtained using the obtained hardenable composition was evaluated by the following evaluation method.

2. Measurement of mechanical strength According to JIS K-7113, the tensile strength of the cured product after the curable composition was heated at 80 ° C. for 4 hours at room temperature was measured.

3. Evaluation of heat resistance The hardened | cured material after hardening at 80 degreeC for 4 hours was heated with the 300 degreeC heating plate for 1 hour. The tensile strength TS of the cured product before and after heating at 300 ° C was measured at room temperature. Using the ratio ΔTS of the tensile strength before and after heating, heat resistance was evaluated based on the following evaluation criteria. ΔTS = tensile strength of hardened material after heating / tensile strength of hardened material before heating

A: ΔTS is 0.90 or more. B: ΔTS is 0.80 or more and less than 0.90. C: ΔTS is 0.60 or more and less than 0.80. D: ΔTS is less than 0.60.

<Example 21 to Example 24 and Comparative Example 9> Example 20 was the same as Example 20 except that the thiol compound was changed to the thiol compound shown in the following table to prepare a curable composition. A hardened product was produced and evaluated for heat resistance. [TABLE 22]

From the results, it is understood that the examples are excellent in heat resistance. In Example 20, 76.5 parts by mass of 3,4-epoxycyclohexanecarboxylic acid-3 ', 4'-epoxycyclohexyl methyl ester (manufactured by Daicel Chemical Industry Co., Ltd., Celloxide) 2021P, an epoxy equivalent of 130 [g / eq]) were obtained in place of 100 parts by mass of jER825 as an epoxy compound, and the same results were obtained.

<Example 25> 1. Preparation of hardenable composition 205 parts by mass of the thiol compound S-27 obtained in Synthesis Example 2 and 100 parts by mass of an isocyanate compound (manufactured by Wako Pure Chemical Industries, Ltd., hexamethylene diisocyanate ( HDI), an isocyanate equivalent weight of 84 [g / eq]) and 0.5 parts by mass of a hardening accelerator (manufactured by Wako Pure Chemical Industries, Ltd., dibutyltin dichloride) were mixed to obtain a hardenable composition. The mechanical strength of the hardened | cured material obtained using the obtained hardenable composition was evaluated by the following evaluation method.

2. Measurement of mechanical strength According to JIS K-7113, the tensile strength of the cured product after the curable composition was heated at 80 ° C. for 4 hours at room temperature was measured.

3. Evaluation of heat resistance The cured product after being cured at 80 ° C for 4 hours was heated for 1 hour by a 300 ° C heating plate. The tensile strength TS of the cured product before and after heating at 300 ° C was measured at room temperature. Using the ratio ΔTS of the tensile strength before and after heating, heat resistance was evaluated based on the following evaluation criteria. ΔTS = tensile strength of hardened material after heating / tensile strength of hardened material before heating

A: ΔTS is 0.80 or more. B: ΔTS is 0.60 or more and less than 0.80. C: ΔTS is less than 0.60.

<Example 26 to Example 29, Comparative Example 10> The same as Example 25 except that the thiol compound was changed to the thiol compound shown in the following table to prepare a curable composition. The hardened | cured material was produced similarly, and heat resistance was evaluated. [TABLE 23]

From the results, it is understood that the examples are excellent in heat resistance.

<Synthesis Example 17> 1. Synthesis of alkali-soluble resin 15.3 parts by mass of the thiol compound S-27 obtained in Synthesis Example 2, 30 parts by mass of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), and 70 parts by mass of methacrylic acid Benzyl ester (manufactured by Wako Pure Chemical Industries, Ltd.) and 117 parts by mass of propylene glycol monomethyl ether acetate were mixed, and 1.5 parts by mass of a polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., 2,2'-azobis (2-methylpropionic acid) dimethyl (product name: V-601) to obtain a monomer solution. In a flask, 117 parts by mass of propylene glycol monomethyl ether acetate was taken, and heated to 80 ° C. under a nitrogen stream. A monomer solution was added dropwise to the flask over 2.5 hours, and then heated at 80 ° C for 2.5 hours, and further heated at 90 ° C for 2 hours. This was cooled to room temperature to obtain an alkali-soluble resin solution. The polystyrene-equivalent molecular weight (weight average molecular weight) of the alkali-soluble resin measured by GPC was 10,800, and the acid value was 190 KOHmg / g.

<Synthesis Example 18, Synthesis Example 19, Synthesis Example 20> The synthesis example 17 was obtained in the same manner as in Synthesis Example 17 except that the thiol compound was changed to the thiol compound shown in the following table. Alkali-soluble resin solutions of Synthesis Examples 18 to 20.

[TABLE 24]

<Example 30> 2. Preparation of colored composition 2-1. Blue colored composition The following components were mixed and dissolved, and filtered through a nylon filter having a pore size of 0.45 μm to prepare a blue colored composition. . · Organic solvent 1 (cyclohexanone) 17.12 parts · Alkali soluble resin 1 (alkali soluble resin synthesized in Synthesis Example 17) 1.12 parts · Alkali soluble resin 2 (ACRYCURE) RD-F8 (Nippon Catalytic Corporation) (Manufactured)) 0.23 parts polymerizable compound 1 (manufactured by Shin Nakamura Chemical Co., Ltd., NK ESTER A-DPH-12E) 1.96 parts polymerization inhibitor (p-methoxyphenol) 0.0007 parts photoinitiator 1 ( IRGACURE OXE-02, manufactured by BASF) 0.975 parts · Fluorine surfactant (manufactured by Dickson, trade name: Megafac F-475, 1% propylene glycol monomethyl ether acetate solution 2.50 parts · Pigment Dispersion P1 (CI Pigment Blue 15: 6 Dispersion, Propylene Glycol Monomethyl Ether Acetate solution, solid content concentration%) 12.8 parts by mass 51.40 1 24.57 parts of dye solution and the dye solution a dye pigment dispersion P1 using the solution of the coloring composition as used in Example 1 and the pigment dispersion P1 1 embodiment.

2-2. Green coloring composition Using a bead mill, a 100/55 (mass ratio) mixture containing 12.6 parts of CI Pigment Green 58 and CI Pigment Yellow 139, and 5.2 parts of BYK2001 (Discopac ( Disperbyk); manufactured by BYK Corporation, with a solid content concentration of 45.1% by mass), a mixture of 2.7 parts of resin (P-1) as a dispersing resin, and 78.3 parts of propylene glycol monomethyl ether acetate as a solvent Mix and disperse for 15 hours to prepare a green pigment dispersion P2. Using the obtained green pigment dispersion liquid P2, the components were mixed so as to have the following composition to obtain a solution. The resulting solution was filtered through a nylon filter having a pore size of 0.45 μm to prepare a green colored composition. <Composition> • 83.3 parts of green pigment dispersion P2 • 1.0 part of alkali-soluble resin (resin (P-1)) • Photopolymerization initiator (IRGACURE OXE-01, manufactured by BASF) 1.2 parts • polymerization 1.4 parts of polymer compound 1 (M-1 below) Polymerizable compound 2 (M-305, manufactured by Toa Kosei Corporation) 1.4 parts of 80% solution of compound (A-8) (manufactured by Sigma-Aldrich) 1.3 Parts · 0.001 parts of p-methoxyphenol · 7.4 parts of polyethylene glycol methyl ether acetate · Surfactant (PGMEA 0.2% solution) 4.2 parts

Compound (A-8): The following structure [Chem. 58] Polymerizable compound 1: the following structure [Chem. 59] Polymerizable compound 2: the following structure [Chem. 60] · Surface active agent: the following mixture (Mw = 14000) [Chem 61] Resin P-1: The following structure (acid value = 54 mgKOH / g, Mw = 15000) [Chem. 62]

3-1: Production of colored hardened film using colored composition The blue colored composition prepared as described above was applied to a silicon wafer substrate with an undercoat layer manufactured by the same method as in Example 1. On the undercoat layer, a colored layer (coating film) is formed. Then, a heat treatment (pre-baking) was performed for 120 seconds using a 100 ° C. hot plate so that the dry film thickness of the coating film was 1 μm. Next, the pre-baked silicon wafer substrate was heated at 200 ° C. for 5 minutes, and the coating film was cured to produce a silicon wafer substrate with a colored cured film.

3-2. Production of color filter by photolithography method The prepared green coloring composition was coated on a 200 mm (8 inch) silicon wafer sprayed with hexamethyldisilazane in advance. Then, a photocurable coating film is formed. Then, a heat treatment (pre-baking) was performed for 180 seconds using a 100 ° C. hot plate so that the dry film thickness of the coating film was 1.0 μm. Next, an i-ray stepping exposure device FPA-3000i5 + (manufactured by Canon Co., Ltd.) was used to pass a 1.0 μm square Bayer pattern mask at a wavelength of 365 nm. Exposure amount (selected in advance from 50 mJ / cm ² to 1000 mJ / cm ² ) and irradiation was performed. Thereafter, the irradiated silicon wafer on which the coating film was formed was placed on a horizontal rotary table of a rotary shower developing machine (type DW-30; manufactured by Chemitronics Co., Ltd.), and a developing solution CD- A 40% dilution of 2000 (manufactured by Fujifilm Electronic Materials Co., Ltd.) was developed by immersion development at 23 ° C for 180 seconds to form a green colored pattern on a silicon wafer. The silicon wafer on which the green coloring pattern was formed was fixed on a horizontal rotary table by a vacuum chuck, and the silicon wafer was rotated at a speed of 50 rpm by a rotating device, and sprayed from above the center of rotation. Pure water was supplied from the spray nozzle to perform a rinsing treatment, and then spray-dried. Next, the silicon wafer on which the green colored pattern was formed was heated by a heating plate at 200 ° C. for 5 minutes to form a green pattern. Further, using the blue coloring composition, a 1.0 μm square island distribution pattern mask was used instead of the Bayer pattern mask for exposure, and the exposure was performed in the same manner as the formation of a green pattern to form a blue pattern to produce a color filter. Light film.

4. Evaluation of heat resistance The produced silicon wafer substrate with a colored hardened film was heated by a hot plate at 280 ° C for 30 minutes, followed by immersion in cyclohexanone for 10 minutes. A colorimeter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.) was used to measure a visible light transmittance difference (ΔT) between 400 nm and 700 nm of a silicon wafer substrate with a colored hardened film before and after solvent immersion. Using the measured ΔT, heat resistance was evaluated based on the following evaluation criteria.

A: ΔT is less than 5% B: ΔT is 5% or more and less than 10% C: ΔT is 10% or more and less than 20% D: ΔT is 20% or more

5. Evaluation of depression The atomic force microscope (AFM, manufactured by Seiko Instruments Inc., SPA-400AFM) was used to measure the height of the blue pixels of the produced color filter along the diagonal of the pixels. Based on the measured values, the depressions were evaluated based on the difference in height between the highest point and the central portion as the depression depth based on the following evaluation criteria. A: Depression depth is less than 75 nm B: Depression depth is more than 75 nm and less than 100 nm C: Depression depth is more than 100 nm

<Example 31, Comparative Example 11 to Comparative Example 12> In Example 30, as the alkali-soluble resin 1 used in the blue coloring composition, the alkali-soluble resin synthesized in Synthesis Examples 18 to 20 was used instead. A blue-colored composition was prepared in the same manner as in Example 30 except that the alkali-soluble resin synthesized in Synthesis Example 17 was used, and the depression was evaluated in the same manner as in Example 30.

[TABLE 25]

From the results, it was found that the examples containing the alkali-soluble resin produced using the thiol compound of the present invention are excellent in heat resistance. In addition, the dent reduction performance is also excellent. In the preparation of the blue coloring composition of Example 30, the same quality of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate) was used instead of NK ESTER A-DPH-12E for polymerization. The coloring composition obtained from the sexual compound 1 also obtained the same result. Moreover, the same result was obtained also about the coloring composition obtained by using IRGACURE OXE-01 (made by BASF) instead of IRGACURE OXE-02 as a photopolymerization initiator of the same quality.

no

no

Claims (25)

A thiol compound, which is represented by the following formula (1); (HS-R ¹ -M ¹ -) _n L ¹ (1) In the formula (1), L ¹ represents a member selected from the following (L-1) ~ Structures represented by any of (L-11), (L-14), (L-15), (L-17), (L-18), (L-20) and (L-21) Organic linking group, n represents an integer of 3 to 15, M ¹ represents -O-, -C(=O)-O-, -OC(=O)-O- or -OC(=O)-NH-, R ¹ represents an alkylene group, or a group containing a combination of an alkylene group and an etheric oxygen atom, R ² represents a hydrogen atom, a C 1-10 alkyl group which may also contain an etheric oxygen atom, or may contain an etheric property An aromatic hydrocarbon group of an oxygen atom, SH represents a thiol group, the sulfur atom of SH, and the atom bonded to R ^{1 of} M ¹ are separated by 5 or more atoms of R ¹ ;

In the above, r is an integer from 1 to 10, R ³¹ to R ⁴¹ each independently represent an alkyl group, R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and s is 0 to An integer of 9; * indicates a bonding site with M ¹ . The thiol compound according to item 1 of the patent application, wherein R ¹ represents a linear alkylene group having 5 to 30 carbon atoms, a branched alkylene group having 6 to 30 carbon atoms, and includes 3 to 27 carbon atoms A group consisting of a combination of a straight chain alkylene group and an etheric oxygen atom, or a group containing a combination of a branched alkylene group having 4 to 28 carbon atoms and an etheric oxygen atom. The thiol compound as described in item 1 of the patent application, wherein R ¹ represents a linear alkylene group having 5 to 20 carbon atoms and an alkylene group having 5 to 20 carbon atoms including an ethyloxy chain Or an alkylene group having 5 to 20 carbon atoms containing an isopropyl propyloxy chain. The thiol compound according to item 1 of the patent application scope, wherein L ¹ is a linking group derived from a polyhydric alcohol. The thiol compound according to any one of claims 1 to 4, wherein said L ^{1 is} selected from the group consisting of (L-1) to (L-11), (L-15), The structure represented by any of (L-17), (L-20) and (L-21). The thiol compound according to any one of claims 1 to 4, wherein said L ^{1 is} selected from the group consisting of (L-1), (L-3) to (L-5) and The structure represented by any of (L-17). The thiol compound according to any one of claims 1 to 4, wherein L ¹ is the structure represented by (L-1). A method for producing a thiol compound, which is a method for producing a thiol compound as described in item 1 of the patent application scope, which comprises: a compound represented by the following formula (3) and a formula (4) below After the reaction of the compound, the resulting product is reacted with a sulfur-containing compound having a protective group Z, and the thiol group is generated by detaching the protective group Z; L ¹ -(R ^H ) _n (3) XM ^a -R ^1- Y (4) In the formula, L ¹ represents selected from (L-1) to (L-11), (L-14), (L-15), (L-17), (L-18), An organic linking group of the structure represented by either (L-20) or (L-21), R ^H represents a group containing an oxygen atom and a hydrogen atom linked to the oxygen atom, n represents an integer of 3 to 15, Y represents a group that is detached due to a reaction with a sulfur-containing compound having a protecting group Z. The sulfur-containing compound having a protecting group Z is a compound containing a sulfur atom and the protecting group Z, and the protecting group Z is an acyl group , carbamimidoyl, formamidine salt group, R ¹ represents an alkylene group, or a group comprising a combination of an alkylene group and an ether oxygen atom, Y atoms bonded to R ^1, and the M ^a to R ¹ atoms bonded via R 5 is ¹ or more atoms, M ^a represents a single bond or a divalent linking group, X represents a halogen atom or sulphonate comprises at least one of the group;

In the above, r is an integer from 1 to 10, R ³¹ to R ⁴¹ each independently represent an alkyl group, R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and s is 0 to An integer of 9; * indicates a bonding site with M ¹ . The method for producing a thiol compound according to item 8 of the patent application scope, wherein the L ^{1 is} selected from the group consisting of (L-1) to (L-11), (L-15), and (L-17) , (L-20) and (L-21) any one of the structures represented. The method for producing a thiol compound according to item 8 of the patent application range, wherein the L ^{1 is} selected from the group consisting of (L-1), (L-3) to (L-5) and (L-17) The structure represented by any of The method for producing a thiol compound according to claim 8 of the patent application, wherein the L ¹ is the structure represented by the (L-1). A method for producing a thiol compound, which is a method for producing a thiol compound as described in item 1 of the patent application scope, which comprises: a polyhydric alcohol of 3 to 15 yuan and the following formula (4-1) After the reaction of the compound, the resulting product is reacted with a sulfur-containing compound having a protective group Z, the thiol group is generated by detaching the protective group Z; XM ^a1 -R ¹ -Y (4-1) where Y represents A group that is released due to a reaction with a sulfur-containing compound having a protective group Z, and the sulfur-containing compound having a protective group Z is a compound containing a sulfur atom and the protective group Z, and the protective group Z is an acyl group or a methyl group amidino, formamidine salt group, R represents ^an alkylene group, or alkylene group containing an etheric oxygen atom in combination with, Y and R ¹ junction atom bond, and M ^a1 and R ¹ are bonded The atoms of are separated by 5 or more atoms of R ¹ , M ^a1 represents -C(=O)-, and X represents a group containing at least one halogen atom or sulfonate. A method for producing a thiol compound, which is a method for producing a thiol compound as described in item 1 of the patent application scope, which comprises: a polyhydric alcohol of 3 to 15 yuan and the following formula (4-2) After reacting the resulting compound with the sulfur-containing compound having a protecting group Z, the thiol group is generated by detaching the protecting group Z. The polyol has the following (L-1) to (L-11 ), (L-14), (L-15), (L-17), (L-18), (L-20) and (L-21), any structure represented by XR ¹ -Y ( 4-2) In the formula, Y represents a group detached by reaction with a sulfur-containing compound having a protective group Z. The sulfur-containing compound having a protective group Z is a compound containing a sulfur atom and the protective group Z, so The protective group Z is a salt of an acyl group, amidino group, or amidino group, R ¹ represents an alkylene group or a group containing a combination of an alkylene group and an etheric oxygen atom, and the atom bonded to R ^{1 of} Y, The atoms bonded to R ¹ and X are separated by 5 or more atoms of R ¹ , X represents a group containing at least one halogen atom or sulfonate;

In the above, r is an integer from 1 to 10, R ³¹ to R ⁴¹ each independently represent an alkyl group, R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and s is 0 to An integer of 9; * represents an OH group. The method for producing a thiol compound according to any one of claims 8 to 13, wherein the protective group Z is a group represented by the following formula (5), and the following formula (6) A salt of the group represented by the group represented by the following formula (6);

In formula (5), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms. A polymer, which is represented by the following formula (7);

In formula (7), L ¹ represents selected from (L-1) to (L-11), (L-14), (L-15), (L-17), (L-18), The organic linking group of the structure represented by either (L-20) or (L-21), n1 represents 1 to 15, n2 represents 0 to 14, the total of n1 and n2 is 3 to 15, and M ¹ represents -O -, -C(=O)-O-, -OC(=O)-O- or -OC(=O)-NH-, R ¹ represents alkylene, or contains alkylene and etheric oxygen atoms Combined group, R ² represents a hydrogen atom, a C 1-10 alkyl group which may also contain an etheric oxygen atom, or an aromatic hydrocarbon group which may also contain an etheric oxygen atom, SH represents a thiol group, and sulfur of SH The atom, the atom bonded to R ^{1 of} M ¹ is separated by 5 or more atoms of R ¹ , S represents a sulfur atom, and the atom bonded to R ^{1 of} M ¹ is separated by 5 of R ¹ More than one atom, P ¹ represents a monovalent substituent having a repeating unit derived from a compound having an ethylenically unsaturated bond;

In the above, r is an integer from 1 to 10, R ³¹ to R ⁴¹ each independently represent an alkyl group, R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and s is 0 to An integer of 9; * indicates a bonding site with M ¹ . The polymer according to item 15 of the patent application scope, wherein the L ^{1 is} selected from the group consisting of (L-1) to (L-11), (L-15), (L-17), and (L- The structure represented by any of 20) and (L-21). The polymer according to item 15 of the patent application scope, wherein the L ^{1 is} selected from any of the (L-1), (L-3) to (L-5) and (L-17) Represented structure. The polymer according to item 15 of the patent application scope, wherein the L ¹ is the structure represented by the (L-1). A composition comprising a thiol compound produced by the method for producing a thiol compound according to any one of claims 8 to 14 of the patent application, 50 mass of the composition % Or more is a specific one of the thiol compounds represented by formula (1). A composition comprising the thiol compound according to any one of claims 1 to 7 of the patent application, wherein 50% or more of the composition is sulfur represented by formula (1) A specific one of alcohol compounds. A composition comprising the polymer according to any one of claims 15 to 18. A hardenable composition comprising the thiol compound according to any one of the patent application items 1 to 7, and according to any one of the patent application item 8 to item 14 A thiol compound obtained by a method for producing a thiol compound, a polymer as described in any one of items 15 to 18 of the patent application, and any one of any one of items 19 to 21 in the patent application At least one of the aforementioned compositions, and a polymerizable compound. A coloring composition comprising the thiol compound according to any one of the patent application items 1 to 7, and the sulfur according to any one of the patent application items 8 to 14 The thiol compound obtained by the method for producing an alcohol compound, the polymer as described in any one of items 15 to 18 of the patent application, and the compound as described in any one of items 19 to 21 of the patent application At least one of the aforementioned compositions, a polymerizable compound, and a coloring agent. A cured film obtained by curing a curable composition as described in item 22 of the patent application range or a coloring composition as described in item 23 of the patent application range. A color filter obtained by using the coloring composition as described in item 23 of the patent application.