KR101398503B1 - Compound, photosensitive composition, curable composition, curable composition for color filter, color filter, and producing method thereof - Google Patents

Abstract

The present invention provides a curable composition for a color filter, which comprises a sensitizer having a specific chemical structure, a photopolymerization initiator, a polymerizable compound, and a colorant. The present invention also provides a color filter characterized by having a coloring pattern formed by using the curable composition for a color filter. The present invention also provides a color filter comprising: a step of applying a curable composition for a color filter on a support to form a colored curable composition layer; a step of exposing the colored curable composition layer through a mask; a step of developing the colored curable composition layer after exposure And forming a coloring pattern on the surface of the color filter.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive composition, a photosensitive composition, a curable composition, a curable composition for a color filter, a color filter, and a method of manufacturing the same. TECHNICAL FIELD [0001]

1 is a ¹ H-NMR chart of Compound 2-1.

2 is a ¹ H-NMR chart of Compound 2-2.

3 is a ¹ H-NMR chart of Compound 2-3.

4 is a ¹ H-NMR chart of Compound 2-4.

5 is a ¹ H-NMR chart of Compound 2-5.

6 is a ¹ H-NMR chart of Compound 2-6.

The present invention relates to a curable composition for a color filter, a color filter, and a method for manufacturing the same, which are used for a liquid crystal display element (LCD) or a solid-state image pickup element (CCD, CMOS or the like).

Color filters are indispensable components of liquid crystal displays.

The liquid crystal display is a display device that is compact as compared with a CRT, and is equivalent to or more in terms of performance, and thus is being converted into a CRT as a television screen, a PC screen, and other display devices. In recent years, trends in the development of liquid crystal displays are directed toward the use of TVs, which are large in screen size and require high image quality, from conventional monitor applications where the screen is relatively small in area.

In the liquid crystal display for TV applications, higher image quality is demanded as compared with the conventional monitor. That is, the contrast and color purity are improved. For the purpose of improving the contrast, the curing composition for producing a color filter is required to have a smaller particle size as a colorant (organic pigment or the like) to be used.

Further, in order to improve the color purity, a higher content of the colorant (organic pigment) occupied in the solid content of the curable composition for producing a color filter is required.

On the other hand, in a color filter for a solid-state image pickup device, higher fineness is required. However, in the curable composition using the conventional pigment dispersion system, since the pigment is relatively coarse particles, there is a problem that a color deviation occurs, so that it is difficult to improve the resolution even more. In the case of a solid- Lt; / RTI > Thus, a technique of using an organic solvent-soluble dye instead of a pigment as a coloring agent has been proposed (see, for example, JP-A-2-127602).

In addition, for a color filter for use in a solid-state image sensor, it is required to make the coloring pattern thinner. In order to make the color filter thinner with the same color density as the conventional one, it is required to increase the content of the coloring agent in the curing composition for manufacturing a color filter.

As described above, in any of the liquid crystal display and the solid-state imaging device, the curable composition for the color filter production contains the colorant. Therefore, the content of the photopolymerization initiator and the photopolymerizable monomer, which are components necessary for curing the curable composition The strength becomes insufficient, or the curability is insufficient and the adhesion to the hard surface as the base material is not sufficiently obtained.

In addition, with the recent increase in the substrate size, there is a demand for a highly sensitive curable composition that maintains a pattern shape for a long time even in a developing solution in the developing process, and has no cracks or peelings in the pattern.

With respect to the curable composition for producing a color filter, development of a photopolymerization initiator having higher sensitivity capable of sufficiently achieving a curing reaction even in the vicinity of the bottom of the coating film when applying the composition onto a substrate and performing exposure curing has been attempted.

Conventionally, as a curable composition for producing a color filter, for example, a radiation sensitive composition comprising a binder polymer containing a carboxyl group and a polyfunctional acrylate such as pentaerythritol hexaacrylate and a photopolymerization initiator has been used, (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and the like have been proposed (see, for example, JP-A-6-75372 and JP-A-6-75373)

Examples of the photopolymerization initiator that can be applied to the curable composition include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5-dihydroxybenzophenone as a photopolymerization initiator applicable to a radiation- (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) imidazole, 2,2'-bis (See, for example, Japanese Patent Publication No. 48-38403 and Japanese Patent Laid-Open No. 62-174204). In order to improve the sensitivity of the curable composition (photopolymerizable composition) for a color filter, attempts have been made to incorporate a specific compound into a polymerization initiator-based composition comprising a polymerization initiator, a sensitizer, and the like Open No. 2002-221791).

However, with respect to any of the above-mentioned curable compositions, the sensitivity is not yet at a level that can satisfy them, and it is necessary to irradiate high-energy radiation for curing. When a coloring pattern of a color filter is formed using such a curable composition, insufficient irradiation dose causes a problem such as a pattern missing or a defect, a residual film ratio, or a decrease in pixel intensity. Furthermore, in the coloring pattern of the obtained color filter, there may arise a problem that the resolving power and the adhesion of the support are deteriorated.

As described above, there is a demand for a curable composition for a color filter that cures at a high sensitivity even in the case where a colorant is contained at a high concentration and has good pattern formability.

The present invention has been made in view of the above problems in the conventional art.

That is, the present invention relates to a novel compound useful for high sensitivity of a curable composition capable of forming a colored pattern excellent in adhesion to a support, having good pattern forming properties by curing with high sensitivity even when the colorant is contained at a high concentration, A curable composition, and a curable composition for a color filter.

The present invention also provides a color filter having a coloring pattern having excellent resolution and adhesion to a support obtained by using the curable composition for a color filter of the present invention and a manufacturing method capable of manufacturing the color filter with high productivity do.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a curable composition for a color filter because it contains a specific compound, and the present invention has been completed. Means for solving the above problems are as follows.

A compound represented by the following general formula (1-I), a compound represented by the general formula (1-II), a compound represented by the following general formula (2-1), and a compound represented by the general formula (3-1) At least one compound selected from the group consisting of:

A photopolymerization initiator;

Polymerizable compounds; And

A curable composition for a color filter, characterized by containing a colorant:

In the general formulas (1-I) and (1-II), R ¹¹ and R ¹² each independently represent a monovalent substituent; R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent; n represents an integer of 0 to 5; n 'represents an integer of 0 to 5; n and n 'are not both 0; When n is 2 or more, plural R ^{11 s} present may be the same or different; When n 'is 2 or more, plural R ^{12 s} may be the same or different,

In the general formula (2-I), A represents an aromatic ring or a heterocycle which may have a substituent; R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent nonmetal atomic group; A, R ²² , R ²³ and R ²⁴ may be bonded to each other to form an aliphatic or aromatic ring;

In the general formula (3-1), A represents an aromatic ring or a heterocycle which may have a substituent; X represents an oxygen atom, a sulfur atom or -N (R ³³ ) -; Y represents an oxygen atom, a sulfur atom or -N (R ³³ ) -; R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a monovalent nonmetal atomic group; A, R ³¹ , R ³² and R ³³ may be bonded to each other to form an aliphatic or aromatic ring.

Preferred embodiments of the present invention include the following embodiments <1> to <18>.

(1) A coloring agent which comprises at least one compound selected from the compounds represented by the general formula (1-I) or the general formula (1-II), a photopolymerization initiator, a polymerizable compound and a colorant Curable composition for a filter.

(2) In the general formula (1-I) or the general formula (1-II), n represents an integer of 1 to 5, and at least one of R ¹¹ is an alkyl group, an alkoxy group or a dialkylamino group The curable composition for a color filter according to < 1 >

<3> The curable composition for a color filter according to <1> or <2>, further comprising a thiol compound.

<4> The curable composition for a color filter according to any one of <1> to <3>, wherein the photopolymerization initiator contains a nonimidazole-based compound.

<5> A color filter having a coloring pattern formed on a support using the curable composition for a color filter according to any one of <1> to <4>.

<6> A method for manufacturing a color filter substrate, comprising the steps of: applying a curable composition for a color filter according to any one of <1> to <4> on a support to form a colored curable composition layer; And a step of developing the colored curable composition layer after exposure to form a colored pattern.

&Lt; 7 > A compound represented by the above general formula (2-I).

&Lt; 8 > A photosensitive composition comprising a compound represented by the general formula (2-I).

<9> A curable composition comprising a compound represented by the general formula (2-I), a photopolymerization initiator, a polymerizable compound, and a colorant.

<10> The curable composition according to <9>, which contains a nonimidazole-based compound as the photopolymerization initiator.

<11> A curable composition for a color filter, which comprises a compound represented by the general formula (2-I), a photopolymerization initiator, a polymerizable compound, and a colorant.

<12> The curable composition for a color filter according to <11>, which contains a nonimidazole-based compound as the photopolymerization initiator.

<13> The color filter according to <11> or <12>, which has a coloring pattern formed of a curable composition for a color filter on a support.

<14> A method for manufacturing a color filter substrate, comprising the steps of: applying a curable composition for a color filter described in <11> or <12> on a support to form a colored curable composition layer; exposing the colored curable composition layer through a mask; And a step of developing the colored curable composition layer to form a colored pattern.

<15> A curable composition for a color filter, which comprises a compound represented by the general formula (3-1), a photopolymerization initiator, a polymerizable compound, and a colorant.

<16> The curable composition for a color filter according to <15>, which contains a nonimidazole-based compound as the photopolymerization initiator.

<17> A color filter having a coloring pattern formed by using the curable composition for a color filter according to <15> or <16> above on a support.

A step of applying a curable composition for a color filter described in <15> or <16> on a support to form a colored curable composition layer; a step of exposing the colored curable composition layer through a mask; And a step of developing the colored curable composition layer to form a colored pattern.

Hereinafter, a compound, a photosensitive composition, a curable composition, a curable composition for a color filter, a color filter using the curable composition for a color filter, and a method for producing the same will be described in detail.

Curable composition for color filter

The curable composition for a color filter according to the present invention comprises (A) a compound represented by the general formula (1-I), the general formula (1-II), a compound represented by the general formula (B) a polymerization initiator, (C) a polymerization initiator, (D) a colorant, and (D) a colorant. .

Hereinafter, each component contained in the curable composition for a color filter of the present invention (hereinafter, simply referred to as &quot; curable composition &quot;) will be sequentially described.

<(A) Specific sensitizer>

The curable composition and the curable composition for a color filter of the present invention can be produced by reacting a compound represented by the following general formula (1-I), a compound represented by the general formula (1-II), a compound represented by the following general formula (2-1) And a compound represented by the general formula (3-1).

The compound represented by the general formula (1-I), the general formula (1-II), the general formula (2-I) or the general formula (3-1) is a compound which can act as a sensitizer. Although the action mechanism thereof is not yet clear, it is considered that, by containing these compounds in the curable composition of the present invention, the absorption efficiency of the irradiated active radiation is improved and the curing sensitivity of the composition is improved. Compounds represented by the above general formula (1-I), general formula (1-II), general formula (2-I) or general formula (3-1) are energetically absorbed by actinic radiation, It is considered that the curing reaction of the curable composition can be highly sensitized by generating an active polymerization initiator of the polymerization initiator by performing electron transfer or energy transfer efficiently with the polymerization initiator.

First, general formula (1-I) and general formula (1-II) will be described in detail.

In the general formula (1-I) or the general formula (1-II), R ¹¹ and R ¹² each independently represent a monovalent substituent, and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or Represents a monovalent substituent. n represents an integer of 0 to 5, n 'represents an integer of 0 to 5, and neither n nor n' is 0 in both cases. When n is 2 or more, plural R ^{11 s} present may be the same or different. When n 'is 2 or more, plural R ^{12 s} may be the same or different.

In the general formula (1-I) or the general formula (1-II), R ¹¹ and R ¹² each independently represent a monovalent substituent, and when n is 2 or more, plural R ^{11 s} present may be the same or different, When n 'is 2 or more, plural R ^{12 s} present may be the same or different.

When n is 2 or more, a plurality of R ^{11 s} present may combine with each other to form a ring. When n 'is 2 or more, plural R ^{12 s} may combine with each other to form a ring.

R ¹¹ and / or R ¹² may be bonded to at least one of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ to form a ring.

The monovalent substituent in R ¹¹ and R ¹² is not particularly limited and includes, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group An alkenyl group, an aryl group, a heterocyclic group (also referred to as a "heterocyclic group"), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group , An aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group (dialkylamino group, alkylamino group, diarylamino group, aryl An amino group, and an anilino group), an ammonia group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, A sulfonyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, A carbamoyl group, an aryl and a heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a phosphono group, a silyl group, a hydrazino group, a ureido group, OH) ₂ ), a phosphate group (-OPO (OH) ₂ ), and a sulfate group (-OSO ₃ H).

a plurality of R ^{11 s} present when n is 2 or more, or a plurality of R ^{12 s} present when n 'is 2 or more are bonded to each other to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring) A polycyclic fused ring) can be formed. Specific examples of the ring that can be formed include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a naphthacene ring, a biphenyl ring, a pyrrole ring, a furan ring, An imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazin ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophen ring, an isobenzofuran ring, A heterocyclic ring, a thianthrene ring, a cromene ring, a xanthylene ring, a phenanthrene ring, a phenanthrene ring, a thiophene ring, a thiophene ring, a thiophene ring, Thiazine ring, phenothiazine ring, and phenanthrene ring.

R ¹¹ and R ¹² are preferably a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, (Including a dialkylamino group, an alkylamino group, a diarylamino group, and an arylamino group), an acylamino group, an amino group, a carboxyl group, An alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, , A carbamoyl group, an imide group, a silyl group, or a ureido group is preferable.

R ¹¹ and R ¹² are more preferably a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, A dialkylamino group, an alkylamino group, a diarylamino group, and an arylamino group).

The monovalent substituent represented by R &lt; ¹¹ &gt; and R &lt; ¹² &gt; may further have a substituent when it can be introduced.

R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a monovalent substituent, and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be bonded to each other to form a ring. R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be bonded to R ¹¹ and / or R ¹² to form a ring.

Examples of the monovalent substituent in R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ include, but not limited to, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), an alkenyl group An aryl group, a heterocyclic group (which may be a heterocyclic group), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group (Including an anilino group), an ammonio group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an alkoxycarbonyloxy group, an alkoxycarbonyloxy group, A sulfonyl group, a sulfonyl group, an alkylsulfinyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, An acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl and a heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and the phosphono group, a silyl group, a hydrazino group, a ureido group, boronic acid group (-B (OH) _2), phosphate groups (-OPO (OH) _2), sulfate group (-OSO ₃ H) or the like as for example, .

R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may combine with each other to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring, which may also be combined to form a polycyclic condensed ring).

R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be bonded to each other to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring, which may also be combined to form a polycyclic fused ring) with R ¹¹ and / or R ¹² . Specific examples of the ring that can be formed include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a naphthacene ring, a biphenyl ring, a pyrrole ring, a furan ring, An imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazin ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophen ring, an isobenzofuran ring, A heterocyclic ring, a thianthrene ring, a cromene ring, a xanthylene ring, a phenanthrene ring, a phenanthrene ring, a thiophene ring, a thiophene ring, a thiophene ring, Thiamine, phenothiazine, phenanthrene), and the like.

R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are preferably a hydrogen atom, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), an alkenyl group (a cycloalkenyl group and a bicycloalkenyl group) An alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxy group, an aryloxy group, An aryl group, an aryl group, an aryl group, an aryl group, an aryl group, an aryl group, an alkoxycarbonyl group, a carbamoyl group, an imide group, a silyl group, an aryloxycarbonyl group, Or urea pottery.

R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are more preferably a hydrogen atom or an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group).

The monovalent substituent represented by R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may further have a substituent when it can be introduced.

Examples of the compound represented by the general formula (1-I) include a compound wherein R ¹¹ is an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), an alkoxy group, an amino group (a dialkylamino group, an alkylamino group, a diarylamino group, R ¹² represents an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), an alkoxy group, an amino group (a dialkylamino group, an alkylamino group, a diarylamino group, an aryl group includes an amino group), an alkylthio group, an arylthio group, R ^13, R ^14, R ¹⁵ and R ¹⁶ is a hydrogen, an alkyl group, n is 0 ~ 3, n 'is preferably from 1 to 3.

Examples of the compound represented by the general formula (1-II) include those wherein R ¹¹ is an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), an alkoxy group, an amino group (a dialkylamino group, R ¹² represents an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), an alkoxy group, an amino group (including a dialkylamino group, an alkylamino group, a diaryl group, It includes an amino group, an arylamino group), alkylthio group, arylthio group, and, R ^13, R ^14, that the R ¹⁵ and R ¹⁶ is a hydrogen, an alkyl group, n is is 0 ~ 3, n 'is 1-3 desirable.

In the present invention, when n represents an integer of 1 to 5, at least one of R &lt; ¹¹ &gt; in the formula (1-I) or the formula (1-II) An alkyl group, an alkoxy group, or a dialkylamino group.

Examples of the alkyl group represented by R ¹¹ in the case where n represents an integer of 1 to 5 include methyl, ethyl, propyl, s-butyl, t-butyl, , Octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, cyclohexyl group and 2-ethylhexyl group . Of these alkyl groups, preferred are methyl, ethyl, propyl, s-butyl, t-butyl, n-butyl, heptyl, hexyl and 2-ethylhexyl.

Examples of the alkoxy group represented by R ¹¹ in the case where n represents an integer of 1 to 5 include methoxy group, ethoxy group, propoxy group, isopropoxy group, s-butoxy group, t-butoxy group, Ethylhexyloxy group, a 2-ethylhexyloxy group, a 2-ethylhexyloxy group, a 2-ethylhexyloxy group, a 2-ethylhexyloxy group, a 2-ethylhexyloxy group, an isoamyloxy group, ₃ OC ₂ H ₄ O-, C ₂ H ₅ OC ₂ H ₄ O-, CH ₃ OC ₂ H ₄ OC ₂ H ₄ O-, CH ₃ OC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ O-, CH ₃ OC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ O-, CH ₃ OC ₃ H ₆ O-, C ₂ H ₅ OC ₃ H ₆ O-, CH ₃ OC ₃ H ₄ OC ₃ H ₆ O-, CH ₃ OC ₃ H ₆ OC ₃ H ₆ OC ₃ H ₆ O-. Of these alkoxy groups, preferably methoxy, ethoxy, isopropoxy, propoxy, s-butoxy, t-butoxy, n-butoxy, heptyloxy, hexyloxy, , CH ₃ OC ₂ H ₄ O-, C ₂ H ₅ OC ₂ H ₄ O-, and CH ₃ OC ₂ H ₄ OC ₂ H ₄ O-.

In the case where n represents an integer of 1 to 5, examples of the dialkylamino group represented by R ¹¹ include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a diheptylamino group, a dihexylamino group, An amino group, a dodecylamino group, a morpholine group, a piperidine group and a julolidine group. Of these dialkylamino groups, preferred are dimethylamino group, diethylamino group, dipropylamino group, morpholine group, piperidine group and julolidine group.

The compound represented by the general formula (1-I) is preferably a compound represented by the following general formula (1-III) from the viewpoint of color sensitivity in the case of containing sensitivity and coloring agent.

In the general formula (1-III), R ¹⁷ represents an alkyl group, an alkoxy group or a dialkylamino group. R ¹ and R ² each independently represent a monovalent substituent, and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. n represents an integer of 0 to 4, and n 'represents an integer of 0 to 5. When n is 2 or more, plural R ^{11 s} present may be the same or different. When n 'is 2 or more, plural R ^{12 s} may be the same or different. In the formula (1-III), the isomer formed by the double bond is not limited to either one.

In the formula (1-III), R monovalent substituent represented by ^11, and R ¹² is a monovalent substituent and agreement represented by R ¹¹ and R ¹² in the general formula (1-I), a preferred range is also same.

R ¹⁷ is an alkyl group, an alkoxy group, or a dialkylamino group. The compound represented by the general formula (1-III) is excellent in light absorption efficiency and solvent solubility because R ¹⁷ is one of these substituents.

Examples of the alkyl group represented by R ¹⁷ include a methyl group, an ethyl group, a propyl group, an s-butyl group, a t-butyl group, a n-butyl group, a heptyl group, a hexyl group, a heptyl group, A decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a cyclohexyl group and a 2-ethylhexyl group. Of these alkyl groups, preferred are methyl, ethyl, propyl, s-butyl, t-butyl, n-butyl, heptyl, hexyl and 2-ethylhexyl.

Examples of the alkoxy group represented by R ¹⁷ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an s-butoxy group, a t-butoxy group, A cyclohexyloxy group, a 2-ethylhexyloxy group, CH ₃ OC ₂ H ₄ O-, a C ₂ H ₅ OC group, a cyclohexyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, ₂ H ₄ O-, CH ₃ OC ₂ H ₄ OC ₂ H ₄ O-, CH ₃ OC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ O-, CH ₃ OC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ O-, CH ₃ OC ₃ H ₆ O-, C ₂ H ₅ OC ₃ H ₆ O-, CH ₃ OC ₃ H ₄ OC ₃ H ₆ O-, CH ₃ OC ₃ H ₆ OC ₃ H ₆ OC ₃ H ₆ O-. Of these alkoxy groups, preferably methoxy, ethoxy, isopropoxy, propoxy, s-butoxy, t-butoxy, n-butoxy, heptyloxy, hexyloxy, , CH ₃ OC ₂ H ₄ O-, C ₂ H ₅ OC ₂ H ₄ O-, and CH ₃ OC ₂ H ₄ OC ₂ H ₄ O-.

Examples of the dialkylamino group represented by R ¹⁷ include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a diheptylamino group, a dihexylamino group, a dioctylamino group, a dodecylamino group, a morpholinyl group, , And a julolidine group. Of these dialkylamino groups, preferred are dimethylamino group, diethylamino group, dipropylamino group, morpholine group, piperidine group and julolidine group.

As the compound represented by the general formula (1-III), it is preferable that n is 0, R ¹² is an alkyl group, a dialkylamino group, a diarylamino group or an alkoxy group, R ¹⁷ is alkoxy and n 'is an integer of 0 to 3 desirable.

As the compound represented by the general formula (1-I) or the general formula (1-II), the molar extinction coefficient (?) At a wavelength of 365 nm is preferably 500 mol ^-1 · L · cm ^-1 or more, ε is more preferably at least 3000mol ^-1 · L · ㎝ ^-1 in, and that the ε at a wavelength of not less than 365㎚ 20000mol ^-1 · L · ㎝ ^-1 is most preferred. When the value of the molar extinction coefficient? At each wavelength is within the above range, the effect of improving the sensitivity is high from the viewpoint of the light absorption efficiency.

As R ¹¹ and R ¹² , an alkyloxy group, an aryloxy group, an amino group, an alkylamino group, a dialkylamino group, an arylamino group and a diarylamino group are preferable among the above-mentioned monovalent substituents from the viewpoint of the absorption wavelength.

As R ¹¹ and R ¹² , an alkyloxy group (in this case, n and n 'are more preferably two or more), a dialkylamino group and a diarylamino group are preferable, and a diarylamino group is most preferable.

Specific preferred examples of the compound represented by formula (1-I) or formula (1-II) are illustrated below, but the present invention is not limited thereto.

In the present specification, the chemical formulas may be described by a simplified structural formula, and particularly, solid lines and the like which do not specify the atoms or substituents represent hydrocarbon groups. In the following specific examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, n-Bu represents an n-butyl group, and Ph represents a phenyl group.

In the curable composition of the present invention, the compounds represented by the general formula (1-I) or (1-II) may be used singly or in combination of two or more, ) May be used in combination with a compound selected from the compounds represented by the general formula (1-II).

Next, the compound represented by the general formula (2-I) will be described in detail.

In the general formula (2-I), A represents an aromatic ring or a heterocycle which may have a substituent. R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent nonmetal atomic group, and A, R ²² , R ²³ and R ²⁴ are each bonded to each other to form an aliphatic or aromatic ring May be formed.

It is considered that the compound represented by the general formula (2-I) of the present invention may have a stereoisomer which is a cause of axial fixation of a double bond between carbon atoms. The chemical structure of the compound is not limited to a particular stereoisomer, but may be any geometric structure.

The compound represented by the general formula (2-I) will be described in detail.

In the general formula (2-I), R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent nonmetal atomic group. ^{R 21, R 22, R 23} , R 24 and R ²⁵ that indicate a monovalent non-metal atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, summon a substituted or unsubstituted aromatic heterocyclic A substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

Preferable examples of R ²¹ , R ²² , R ²³ , R ²⁴ and R ^{25 in} the general formula (2-I) will be specifically described.

Preferable examples of the unsubstituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ , or R ²⁵ include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group , An ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a hexadecyl group, an octadecyl group, An isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclohexyl group, an isobutyl group, an isobutyl group, an isobutyl group, an isobutyl group, an isopentyl group, A cyclopentyl group, and a 2-norbornyl group. Of these, a straight chain, branched chain having 3 to 12 carbon atoms, and cyclic alkyl group having 5 to 10 carbon atoms are more preferable.

As the alkylene group (alkyl moiety) in the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ , or R ²⁵ , any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms, And an alkylene group having from 1 to 12 carbon atoms, a linear chain having from 3 to 12 carbon atoms, and a cyclic alkylene group having from 5 to 10 carbon atoms.

As the substituent of the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ , or R ²⁵ , a monovalent non-metal atom group other than hydrogen may be exemplified. Preferred examples thereof include a halogen atom (-F, -Br, Cl, -I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an alkyldithio group, an aryldithio group, An N-alkylcarbamoyloxy group, an N-arylcarbamoyloxy group, an N, N-diarylamino group, , N-dialkylcarbamoyloxy groups, N, N-diarylcarbamoyloxy groups, N-alkyl-N-arylcarbamoyloxy groups, alkylsulfoxy groups, arylsulfoxy groups, acyloxy groups, Amino group, N-alkyl acylamino group, N-aryl acylamino group, ureido group, N'-alkylureido group, N '

N'-arylureido groups, N ', N'-diarylureido groups, N'-alkyl-N'-arylureido groups, N-alkylureido groups, N-arylureido groups, N'-dialkyl-N-arylureido, N'-alkyl-N-arylureido, N'-N'-dialkyl-N-alkylureido, N'- Alkyl-ureido groups, N'-aryl-N-aryl ureido groups, N ', N'-diaryl-N-alkylureido groups, N'- Alkyl-N'-aryl-N-alkylureido groups, N'-alkyl-N'-aryl-N-arylureido groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, An N-aryl-N-aryloxycarbonylamino group, an N-aryl-N-aryloxycarbonylamino group, a formyl group, an acyl group,

Alkylcarbamoyl group, an N, N-dialkylcarbamoyl group, an N, arylcarbamoyl group, an N, N-diarylcarbamoyl group, an N-alkyl-N An arylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and a conjugated salt thereof (hereinafter referred to as a sulphonate group), an alkoxysulfonyl group, an alkylsulfonyl group, an arylsulfonyl group, Alkylsulfinylamino group, an N, N-dialkylsulfamoyl group, an N-arylsulfinamoyl group, an N, N-diarylsulfinamoyl group, an N-alkyl-N- An arylsulfamoyl group, an arylsulfamoyl group, a sulfamoyl group, an N-alkylsulfamoyl group, an N, N-dialkylsulfamoyl group, an N-arylsulfamoyl group, an N, N-diarylsulfamoyl group, A phospho group (-PO ₃ H ₂ ) and a conjugated salt thereof (hereinafter referred to as a phospho nitro group),

A dialkylphosphono group (-PO ₃ (alkyl) ₂ ), a diarylphosphono group (-PO ₃ (aryl) ₂ ), an alkylarylphosphono group (-PO ₃ (alkyl) phono group (-PO ₃ H (alkyl)) and its conjugated salts device (hereinafter referred to as phosphonic Ney earthenware), monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugated salts device (hereinafter referred to as (Hereinafter referred to as an arylphosphono group), a phosphonooxy group (-OPO ₃ H ₂ ) and a conjugated salt thereof (hereinafter referred to as a phosphonate tooxy group), a dialkylphosphonooxy group (-OPO ₃ ) _2), diaryl phosphono oxy group _{(-OPO 3 (aryl) 2)} , alkyl aryl phosphono oxy group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphono aryl oxy group (-OPO ₃ H (hereinafter referred to as alkyl phosphonate tooxy group), monoarylphosphonooxy group (-OPO ₃ H (aryl)), and conjugated salts thereof (hereinafter referred to as arylphosphonates) Quot;), an alkyl group, a cyano group, a nitro group, an aryl group, a heteroaryl The can be cited, an alkenyl group, an alkynyl group.

Specific examples of the alkyl group in the substituent of the substituted alkyl group include the above-mentioned alkyl group as the unsubstituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ , or R ²⁵ .

Specific examples of the aryl group in the substituent of the substituted alkyl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a chloromethylphenyl group, , A methoxyphenyl group, an ethoxyphenyl group, a phenoxyphenyl group, an acetoxyphenyl group, a benzoyloxyphenyl group, a methylthiophenyl group, a phenylthiophenyl group, a methylaminophenyl group, a dimethylaminophenyl group, an acetylaminophenyl group, a carboxyphenyl group, A phenoxycarbonylphenyl group, an N-phenylcarbamoylphenyl group, a phenyl group, a cyanophenyl group, a sulfophenyl group, a sulfonatophenyl group, a phosphonophenyl group, and a phosphonatophenyl group.

Examples of the heteroaryl group in the substituent of the substituted alkyl group include a monocyclic or polycyclic aromatic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Particularly preferred examples of heteroaryl rings in the heteroaryl group include, for example, thiophene, thiasrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole , Pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolyl, indazole, purine, quinolizine, isoquinoline, phthalazine, naphthyridine, quinazoline, , Carboline, phenanthrene, acridine, perimidine, phenanthroline, phenarazine, phenoxazine, furanaz and the like, which may also have a benzo ring and may further have a substituent.

Examples of the alkenyl group in the substituent of the substituted alkyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group and a 2-chloro-1-ethenyl group.

Examples of the alkynyl group in the substituent of the substituted alkyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a trimethylsilylethynyl group.

The substituted alkyl group as G ₁ in the acyl group (G ₁ CO-) in which the substituent may be a hydrogen atom and alkyl groups of the aryl group.

Among these substituents, still more preferred are a halogen atom (-F, -Br, -Cl, -I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, Alkylcarbamoyl group, an N-alkylcarbamoyloxy group, an acylamino group, a formyl group, an acyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an N-alkylcarbamoyl group, Alkylcarbamoyl group, a sulfo group, a sulfonato group, a sulfamoyl group, an N-alkylsulfamoyl group, an N, N-dialkylcarbamoyl group, Arylsulfamoyl group, an N-alkyl-N-arylsulfamoyl group, a phosphono group, a phosphonato group, a dialkylphosphono group, a diarylphosphono group, a monoalkylphosphoric group, A phosphono group, a phosphono group, a phosphono group, a phosphono group, a phosphono group, a phosphono group, a phosphono group, An aryl group, an alkenyl group, and an alkylidene group (e.g., a methylene group).

Examples of the substituted alkyl group which is preferable as R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include a combination of the aforementioned substituent and an alkylene group (alkyl moiety), and specific examples thereof include a chloromethyl group, a bromomethyl group, , A trifluoromethyl group, a methoxymethyl group, a methoxyethoxyethyl group, an allyloxymethyl group, a phenoxymethyl group, a methylthiomethyl group, a tolylthiomethyl group, an ethylaminoethyl group, a diethylaminopropyl group, a morpholino propyl group, And examples thereof include a methyl group, a benzoyloxymethyl group, an N-cyclohexylcarbamoyloxyethyl group, an N-phenylcarbamoyloxyethyl group, an acetylaminoethyl group, an N-methylbenzoylaminopropyl group, a 2-oxoethyl group, A carbamoylmethyl group, an N-methylcarbamoylethyl group, an N, N-dipropylcarbamoylmethyl group, a N- (methoxycarbonylmethyl group), a methoxycarbonylethyl group, an allyloxycarbonylbutyl group, a chlorophenoxycarbonylmethyl group, Phenyl) carbamoyl group, N- methyl -N- (sulfophenyl) carbamoyl methyl group,

A sulfonamido group, a sulfamoyl group, a sulfamoyl group, a sulfamoyl group, a sulfamoyl group, a sulfamoyl group, a sulfobutyl group, a sulfonato propyl group, a sulfonato butyl group, a sulfamoyl butyl group, An alkylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, , Phosphonatooxybutyl group, benzyl group, phenethyl group,? -Methylbenzyl group, 1-methyl-1-phenyl Methylphenyl group, 2-propynyl group, 2-butynyl group, 3-methylphenyl group, 3-methylphenyl group, Butynyl group and the like.

Specific examples of the unsubstituted aryl group as R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include those in which 1 to 3 benzene rings form condensed rings, those in which the benzene rings and 5-membered unsaturated rings form condensed rings Specific examples thereof include phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, and fluorenyl groups.

Specific examples of the substituted aryl group preferable as R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include those having a monovalent nonmetal atomic group as a substituent on the ring forming carbon atom of the unsubstituted aryl group. Examples of the preferable substituent include the above-mentioned alkyl group and substituted alkyl group, and those shown as substituents in the above-mentioned substituted alkyl group. Specific preferred examples of the substituted aryl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ , or R ²⁵ include biphenyl, tolyl, xylyl, mesityl, cumenyl, Examples of the aryl group include phenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, , A morpholinophenyl group, an acetyloxyphenyl group, a benzoyloxyphenyl group, an N-cyclohexylcarbamoyloxyphenyl group, an N-phenylcarbamoyloxyphenyl group,

N-methylcarbamoylphenyl, N-methylcarbamoylphenyl, N-methylcarbamoylphenyl, N-methylcarbamoylphenyl, N-methylcarbamoylphenyl, N-methylcarbamoylphenyl, N-methylcarbamoylphenyl, (Methoxyphenyl) carbamoylphenyl, N-methyl-N- (sulfophenyl) carbamoylphenyl, sulfophenyl, sulfonatophenyl, sulfamoylphenyl, N-ethylsulfamoyl An N, N-dipropylsulfamoylphenyl group, an N-tolylsulfamoylphenyl group, an N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, a phosphonophenyl group, a phosphonatophenyl group, a diethylphosphonophenyl group , A phenylphosphonophenyl group, a diphenylphosphonophenyl group, a methylphosphonophenyl group, a methylphosphonatophenyl group, a tolylphosphonophenyl group, a tolylphosphonatophenyl group, an allylphenyl group, a 1-propenylmethylphenyl group, Allylphenyl group, 2-methylpropenylphenyl group, 2-propyl Group, a 2-butynyl group, and 3-butynyl group.

Specific examples of the unsubstituted alkenyl group as R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include a vinyl group and a 1-propenyl group.

Specific examples of the substituted alkenyl group which is preferable as R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include those having a monovalent nonmetal atomic group other than a hydrogen atom as a substituent on the aforementioned unsubstituted alkenyl group.

When the substituent of the substituted alkenyl group is a monovalent nonmetal atomic group, preferred examples of the substituent include the above-mentioned alkyl group and substituted alkyl group, and examples of the substituent in the substituted alkyl group include the substituents of the substituted alkyl group described above .

Specific examples of preferable unsubstituted aromatic heterocyclic residues as R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include pyridine, thiophene, benzothiophene, dibenzothiophene, furan, benzofuran, dibenzofuran, pyrrole , Pyrazole, thiazole, oxazole, pyrimidine, pyridazine, acridine, imidazole, quinoline, triazole, indole, carbazole and the like.

Specific examples of the substituted aromatic heterocyclic residue preferable as R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include those having a monovalent nonmetal atomic group other than a hydrogen atom as a substituent on the aforementioned unsubstituted aromatic heterocyclic residue have.

When the substituent of the substituted aromatic heterocyclic residue is a monovalent nonmetal atomic group, preferred examples of the substituent include the above-mentioned alkyl group and substituted alkyl group, and examples of the substituent in the substituted alkyl group include the substituents of the above- .

Specific examples of unsubstituted alkoxy groups which are preferable as R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include methoxy, ethoxy, propoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, Ethylhexyloxy group and the like.

Specific examples of the substituted alkoxy group preferable as R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include those having a monovalent nonmetal atomic group excluding a hydrogen atom as a substituent on the aforementioned unsubstituted alkoxy group.

When the substituent of the substituted alkoxy group is a monovalent nonmetal atomic group, preferred examples of the substituent include the above-mentioned alkyl group and substituted alkyl group, and examples of the substituent in the substituted alkyl group include substituents possessed by the above-mentioned substituted alkyl group.

Specific examples of the unsubstituted alkylthio groups which are preferable as R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include methylthio group, ethylthio group, propylthio group, butylthio group, hexylthio group, octylthio group, dodecyl And the like.

Specific examples of the substituted alkylthio groups preferable as R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include those having a monovalent nonmetal atomic group except for a hydrogen atom as a substituent on the unsubstituted alkylthio group.

When the substituent of the substituted alkylthio group is a monovalent nonmetal atomic group, preferred examples of the substituent include the above-mentioned alkyl group and substituted alkyl group, and examples of the substituent in the substituted alkyl group include the substituents of the above-mentioned substituted alkyl group .

Next, A in the general formula (2-I) will be described. As specific examples of the aromatic ring or hetero ring which may have a substituent, R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ in the formula (2-I) May be the same as those described above.

Specific examples of the aromatic ring preferable as A are benzene, methoxybenzene, dimethoxybenzene, trimethoxybenzene, diethylaminobenzene, diphenylaminobenzene, methylthiobenzene, anthracene, phenylthiobenzene, thianthrene, phenothiazine, Dibenzothiophene, dibenzofuran, carbazole, bismethoxyphenylbenzene, triphenylphosphine, and the like.

Specific examples of the heterocycle preferable as A include pyridine, benzothiazole, benzoxazole and the like.

When R ²² , R ²³ , R ²⁴ and A are bonded to each other to form an aliphatic and aromatic ring in the compound represented by the general formula (2-I), the formed ring includes a cycloalkyl ring, A pyrrolidine ring, a pyrrolidine ring, a lactone ring, a lactam ring, a thiazoline ring, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, , A pyrrole ring, a triphenylene ring, a naphthacene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophen ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyran ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, A benzofuran ring, an isobenzofuran ring, a quinoline ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinazoline ring, an isoquinoline ring , Carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, cromene ring, xanthane ring, phenox Tea signet ring, there may be mentioned phenothiazine thiazol jinhwan, Pena jinhwan the like, can be cited more preferably, a cycloalkyl ring, a lactone ring, a benzene ring, blood rolhwan, furan ring, pyran ring, pyridine ring.

In the compound represented by formula ^{(2-I) R 21,} R 22, R 23, R 24, R 25 and A, as a preferred combination than to achieve one of the high sensitivity of the object of the present invention the R ¹ A substituted or unsubstituted aryl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted aryl group having 1 to 20 carbon atoms, R ²² , R ²³ and R ²⁴ are each a hydrogen atom, Branched or cyclic substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, R ⁵ is a linear, branched or cyclic substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group, An aryl group, a substituted or unsubstituted alkoxy group, and A is a substituted or unsubstituted aromatic ring or a hetero ring.

In the case where R ²² , R ²³ , R ²⁴ and A are bonded to each other to form an aliphatic and aromatic ring in the compound represented by the general formula (2-I), the ring, R ²¹ , R ²⁵ And preferred examples of A include a cyclic alkyl group, a lactone ring, a benzene ring, a pyrrole ring, a furan ring, a pyran ring and a pyridine ring, wherein R ²¹ is a straight chain, branched, or cyclic Substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group or carboxyl group, R ²⁵ is a linear, branched, or cyclic substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl A substituted or unsubstituted alkoxy group, and A is a substituted or unsubstituted aromatic ring or a hetero ring.

As a more preferable form of the compound represented by the general formula (2-I), the following general formula (2-II) can be mentioned.

In the general formula (2-II), n represents an integer of 0 to 5. R ²⁶ is a monovalent non-metallic atomic group other than hydrogen. Specific examples of R ²⁶ include the same substituent as the substituent of the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ , or R ²⁵ .

R ^21, a substituent represented by R ^25, the formula (2-I) can be mentioned substituents represented by the compound of R ²¹ and R ²⁵ indicated by, and particularly preferably R ²¹ and R ²⁵ are both a cyclohexyl It can be said that it is practical skill.

As the substituent represented by R ²⁶ , a diphenylamino group, a dimethylamino group and a methoxy group are particularly preferable. It is particularly preferable that n is 0 to 3.

Of the compounds represented by the general formula (2-II), particularly preferred ones include compounds in which the preferred forms of R ²¹ , R ²⁵ , R ²⁶ and n are combined.

Of the compounds represented by the general formula (2-II), the most preferred examples include the compounds synthesized in Synthesis Examples 2-1 to 2-4 and 2-6.

A method of synthesizing a compound represented by the general formula (2-I) will be described.

The compound represented by the general formula (2-I) is usually obtained by a condensation reaction between an acidic nucleus having an active methylene group and a substituted or unsubstituted aromatic ring or heterocycle, and these compounds are disclosed in Japanese Patent Publication No. 59-28329 Can be synthesized. For example, a synthesis method using a condensation reaction of an acidic nucleus compound with a basic nuclear material having an aldehyde group or a carbonyl group on a heterocycle as shown in the following reaction formula (2-1) can be given. The condensation reaction is carried out, if necessary, in the presence of a base. Examples of the base include those generally used for general purposes such as amine, pyridine (trialkylamine, dimethylaminopyridine, diazabicyclo-undecene DBU etc.), metal amides (lithium diisopropylamide and the like), metal alkoxides Sodium methoxide, potassium t-butoxide, etc.), metal hydrides (sodium hydride, potassium hydride, etc.) can be used without limitation. In the formula (2-1), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and A are the same as R ²¹ , R ²² , R ²³ and R ²⁴ in the compound represented by the formula (2-1) , R &lt; ²⁵ &gt;

Another preferred synthesis method is a method according to the following reaction formula (2-2). That is, as an acidic nuclear compound in the above reaction formula (2-1), an acidic nucleus compound in which NR ⁵ is a sulfur atom is used as a starting material, and a condensation reaction of a basic nuclear material having an aldehyde group or a carbonyl group on a heterocycle The process for synthesizing the dye precursor is the same as in the above reaction scheme (2-1), and then a metal salt capable of forming a metal sulfide by chemically interacting with the sulfur atom again to the dye precursor and a water or primary amine compound (R- NH ₂ wherein R represents a monovalent non-metallic atomic group. The monovalent nonmetal atomic group represented by R is preferably the same substituent as R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ described above. In the formula (2-2), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and A are the same as R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ and A, respectively.

Among them, the reaction represented by the reaction formula (2-2) is particularly preferable in view of the synthesis efficiency due to the high yield of each reaction. In the synthesis of the novel compound represented by the general formula (2-I) 2-2) is useful.

In the above reaction formula (2-2), M ^{n +} X _n represents a metal salt capable of forming a metal sulfide by chemically interacting with the sulfur atom of the thiocarbonyl group. As specific examples of the compound, M is at least one element selected from the group consisting of Al, Au, Ag, Hg, Cu, Zn, Fe, Cd, Cr, Co, Ce, Bi, Mn, Mo, Ga, Ni, Pd, AgBr, AgI, AgF, AgO, AgCl, Ag ₂ O such as Sb, Sr, Mg, Ti and the like and X is F, Cl, Br, I, NO ₃ , SO ₄ , NO ₂ , PO ₄ , CH ₃ CO ₂ , _{, Ag (NO 3), AgSO} 4, AgNO 2, Ag 2 CrO 4, Ag 3 PO 4, Hg 2 (NO 3) 2, HgBr 2, Hg 2 Br 2, HgO, HgI 2, Hg (NO 3) 2 , Hg (NO ₂ ) ₂ , HgSO ₄ , Hg ₂ I ₂ , Hg ₂ SO ₄ , Hg (CH ₃ CO ₂ ) ₂ , AuBr, AuBr ₃ , AuI, AuI ₃ , AuF ₃ , Au ₂ O ₃ , AuCl, Compounds such as AuCl ₃ , CuCl, CuI, CuI ₂ , CuF ₂ , CuO, CuO ₂ , Cu (NO ₃ ) ₂ , CuSO ₄ and Cu ₃ (PO ₄ ) ₂ . Of these, silver salts may be used as the most preferable metal salts in that they are easy to interact with sulfur atoms.

Hereinafter, synthesis examples of compounds which are particularly preferable examples of the novel compounds of the present invention and identification data of the obtained compounds are described.

In the compounds represented by the general formula (2-I) of the present invention, synthesis examples of the compounds 2-1 to 2-6 which are particularly preferable examples are shown below.

(Synthesis Example 2-1)

butoxy potassium (0.983 g, 0.0088 mol) was dissolved in THF (20 ml), and 50 ml of 50% aqueous solution of p-diphenylaminocinnamaldehyde (5.0 g, 0.0175 mol), iminooxrazolidone compound (4.63 g, 0.0189 mol) Lt; 0 &gt; C for 2 hours. The reaction was followed by TLC every hour. After completion of the reaction, pH was adjusted to 5 with 1N-HClaq (1 standard hydrochloric acid aqueous solution) (11 ml), and the organic layer was extracted with ethyl acetate and then distilled off under reduced pressure. The obtained crystals were purified by methanol slurry to obtain Compound 1 (yield: 3.94 g, yield: 49%).

The molar extinction coefficient? Is 13773.

Here, the molar absorptivity (?) Was determined by measuring the transmittance spectrum of a sample at 365 nm using a dye solution prepared at a concentration of 0.01 g / l in a 1-methoxy-2-propanol solution as a sample, -visible is obtained by obtaining the absorbance from the absorption spectrum. The measurement apparatus was a UV-Vis-MR spectrophotometer Cary 5G type spectrophotometer manufactured by Varian.

Compound 2-1 shown in Synthesis Example 2-1 was identified by NMR. ¹ H-NMR chart of Compound 1 is shown in Fig. The measurement conditions and the peaks were identified by ¹ H-NMR (CDCl ₃ ): a7.38-7.01 (m, 14H), 6.90 (dd, 1H, J = 15.6, 10.8 Hz) 1H), 6.32 (d, 1H, J = 10.8 Hz), 4.06-3.98 (m, 1H), 3.78-3.71 (m, 1H), 2.32-2.22 (m, 2H), 1.86-1.19 18H).

(Synthesis Example 2-2)

(5.00 g, 0.0189 mol) and t-butoxy potassium (1.06 g, 0.00945 mol) were dissolved in THF (20 ml), and the mixture was stirred at 50 占 폚 And reacted for 2 hours. The reaction was followed by TLC every hour. After completion of the reaction, the mixture was adjusted to pH = 5 with 1N-HClaq (11 ml), and then the organic layer was extracted with ethyl acetate and evaporated under reduced pressure. The obtained crystals were purified with a methanol slurry to obtain Compound 2-2 (yield: 3.94 g, yield 49%) as crystals was purified by being reslurried in water.

The molar extinction coefficient (?) Is 17004.

The compound 2-2 shown in Synthesis Example 2-2 was identified by NMR. A ¹ H-NMR chart of the compound 2-2 is shown in Fig. The measurement conditions and the peaks were identified by ¹ H-NMR (CDCl ₃ ): a 7.40 (d, 2H, J = 9.2 Hz), 6.86-6.68 2H), 1.85 (m, IH), 6.33 (d, IH, J = 9.6 Hz), 4.05-3.99 -1.17 (m, 18H).

(Synthesis Example 2-3)

(1.06 g, 0.00945 mol) was dissolved in THF and treated at 50 DEG C for 2 hours to give 2, 4-methoxycinnamal aldehyde (3.07 g, 0.0189 mol), iminooxazolidinone compound (5.00 g, 0.0189 mol) and t- Lt; / RTI &gt; The reaction was followed by TLC every hour. After completion of the reaction, the reaction solution was followed by TLC every hour. After completion of the reaction, the mixture was adjusted to pH = 5 with 1N-HClaq (11 ml), and the organic layer was extracted with ethyl acetate. The obtained crystals were purified by methanol slurry to obtain Compound 2-3 (yield: 4.27 g, yield: 55%).

The molar extinction coefficient? Is 40814.

The compound 2-3 shown in Synthesis Example 2-3 was identified by NMR. A ¹ H-NMR chart of Compound 3 is shown in Fig. The measurement conditions and the peaks were identified by ¹ H-NMR (CDCl ₃ ): a 7.45 (d, 2H, J = 8.8 Hz), 6.32 ), 3.87 (s, 3H), 2.25 (m, 2H), 2.25-2.30 (m, 2H), 1.81-1.67 (m, 9H), 1.43-1.38 (m, 9H).

(Synthesis Example 2-4)

(2.49 g, 0.0189 mol), AM-6572B (5.00 g, 0.0189 mol) and t-butoxy potassium (1.06 g, 0.00945 mol) were dissolved in 20 ml of THF and reacted at 50 ° C for 2 hours. The reaction was followed by TLC every hour. After completion of the reaction, the mixture was adjusted to pH = 5 with 1N-HClaq (11 ml), and the organic layer was extracted with ethyl acetate. The obtained crystals were purified by methanol slurry to obtain Compound 2-4 (yield: 3.96 g, yield: 55%).

The molar extinction coefficient? Is 20363.

The compound 2-4 shown in Synthesis Example 2-4 was identified by NMR. A ¹ H-NMR chart of the compound 2-4 is shown in Fig. The measurement conditions and the peaks were identified by ¹ H-NMR (CDCl ₃ ): a 7.50 (d, 2H, J = 7.6 Hz), 7.37 1H), 7.04 (dd, 1H, J = 11.6, 15.6 Hz), 6.85 (d, 1H, J = 15.6 Hz), 6.33 , 1H), 2.25-2.29 (m, 2H), 1.64-1.85 (m, 9H), 1.29-1.64 (m, 9H).

(Synthesis Example 2-5)

(2.76 g, 0.0189 mol), iminooxazolidinone compound (5.00 g, 0.0189 mol) and t-butoxy potassium (1.06 g, 0.00945 mol) were dissolved in THF and reacted at 50 ° C for 2 hours Lt; / RTI &gt; The reaction was followed by TLC every hour. After completion of the reaction, the reaction solution was followed by TLC every hour. After completion of the reaction, the mixture was adjusted to pH = 5 with 1N-HClaq (11 ml), and then the organic layer was extracted with ethyl acetate and evaporated under reduced pressure. The obtained crystals were purified by methanol slurry to obtain Compound 2-5 (yield: 3.96 g, yield: 51%).

The molar extinction coefficient (?) Is 8045.

Compound 2-5 shown in Synthesis Example 2-5 was identified by NMR. A ¹ H-NMR chart of the compound 2-5 is shown in Fig. In addition, the identification of conditions for measurement, and a peak is _{^{1 H-NMR (CDCL 3)}} : a7.37 (m, 5H), 6.84 (s, 1H), 6.23 (s, 1H), 4.03 (m, 1H), 3.75 (m, 1H), 2.27 (s, 3H), 2.25-2.29 (m, 2H), 1.67-1.85 (m, 9H), 1.42-1.31 (m, 9H).

(Synthesis Example 2-6)

(2.40 g, 0.0108 mol), iminooxazolidinone compound (2.85 g, 0.0108 mol) and t-butoxy potassium (0.61 g, 0.0054 mol) were dissolved in THF The reaction was carried out at 50 ° C for 2 hours. The reaction was followed by TLC every hour. After completion of the reaction, the reaction solution was followed by TLC every hour. After completion of the reaction, the mixture was adjusted to pH = 5 with 1N-HClaq (11 ml), and then the organic layer was extracted with ethyl acetate and evaporated under reduced pressure. The obtained crystals were purified by methanol slurry to obtain Compound 2-6 (yield: 2.63 g, yield: 52%).

The molar extinction coefficient (?) Is 35366.

Compound 2-6 shown in Synthesis Example 2-6 was identified by NMR. A ¹ H-NMR chart of the compound 2-6 is shown in Fig. The measurement conditions and the peaks were identified by ¹ H-NMR (CDCl ₃ ): a 6.91 (dd, 1H, J = 15.6, 11.2 Hz), 6.77 2H), 6.32 (d, IH, J = 12.0 Hz), 4.09-3.98 (m, IH), 3.92 (s, (m, 2H), 1.87-1.22 (m, 18H).

Examples of the compounds represented by the general formula (2-I) are exemplified as the following compounds (1 to 46) by specifying R ²¹ to R ²⁵ and A. These compounds can be synthesized by the scheme as described above.

Examples of the compound represented by the general formula (2-I) include the following compounds (47-73).

The compound represented by the general formula (2-I) preferably has a molar extinction coefficient of 5,000 to 100,000, more preferably 10,000 to 80,000 from the viewpoint of internal curability.

The compound represented by the general formula (2-I) of the present invention has an absorption wavelength in a wavelength range of 300 nm to 450 nm. And more preferably has an absorption wavelength in the region of 330 nm to 450 nm.

The compound represented by the general formula (2-I) of the present invention can also be used as a sensitizer for a photosensitive material, as an optical brightener and as a polymer-based light emitting material of an electroluminescent element.

In addition to the color filter, a photosensitive resin, a mold resin, a resin for photo-shaping, a sealant, a dental polymeric material, a printing ink, a coating material, a photosensitive resin for a printing plate, a color proof for printing, , A resist for semiconductor manufacturing, a resist for microelectronics, a resist for manufacturing parts for a micromachine, an insulating material, a hologram material, a waveguide material, an overcoat material, an adhesive, a pressure sensitive adhesive, a point adhesive, a release coating material, a UV curable ink, A photosensitive composition for a laser or the like.

The compound represented by the general formula (2-I) of the present invention, particularly when used in a curable composition to be described later, exposes light in the above wavelength range, Migration and energy transfer are excellent, and the photopolymerization initiator can be efficiently decomposed to generate an open species. Therefore, the compound represented by the general formula (2-I) of the present invention can obtain a curable composition with high sensitivity, and can provide a color filter excellent in contrast and color purity even when the content of the colorant is increased, Can be obtained.

When the compound represented by formula (2-I) of the present invention and the compound (specific sensitizer) represented by formula (3-1) according to the present invention described below are used as the curable composition, It is also possible to carry out various chemical modifications for improving the properties such as sensitivity and adhesion of the curable composition.

For example, a specific sensitizer and an addition polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) are bonded by a method such as covalent bonding, ionic bonding, hydrogen bonding, etc. to increase the strength of the exposed film, It is possible to suppress unnecessary precipitation of the specific sensitizer from the subsequent film.

In addition, a partial structure having a radical generating ability in a specific sensitizer and a photopolymerization initiator described later (for example, a reducing decomposable site such as a halogenated alkyl, an onium, a peroxide, a biimidazole, or a borate, an amine, a trimethylsilylmethyl, (Such as carboxymethyl, carbonyl, imine or the like), particularly in the state where the concentration of the indicator clock is low, can be remarkably increased.

In the curable composition for a color filter of the present invention, the compound represented by the general formula (2-I) may be used singly or in combination of two or more kinds.

Next, the compound represented by the general formula (3-I) will be described in detail.

X represents an oxygen atom, a sulfur atom, or -N (R ³³ ) -, Y represents an oxygen atom, a sulfur atom or a sulfur atom, , Or -N (R ³³ ) -. R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a monovalent nonmetal atomic group, and A, R ³¹ , R ³² and R ³³ may be bonded to each other to form an aliphatic or aromatic ring.

The compound represented by the general formula (3-1) will be described in detail.

In the general formula (3-1), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a monovalent non-metallic atomic group. R ^31, R ^32, and when R ³³ represents a monovalent non-metal atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic heterocyclic residue, a substituted or unsubstituted, An alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, and a halogen atom.

Preferable examples of R ³¹ , R ³² and R ^{33 in} the general formula (3-1) will be specifically described.

Preferable examples of the unsubstituted alkyl group represented by R ³¹ , R ³² and R ³³ include the unsubstituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the formula (2-I) This is the same as the preferred example.

Examples of the alkylene group (alkyl moiety) in the substituted alkyl group represented by R ³¹ , R ³² and R ³³ include R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the general formula (2-I) Is the same as the example of the alkylene group (alkyl moiety) in the substituted alkyl group represented by the formula

Examples of the substituent of the substituted alkyl group represented by R ³¹ , R ³² and R ³³ include a substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the general formula (2-I) Is the same as the example of the substituent.

Specific examples of the alkyl group in these substituents include the above-mentioned alkyl groups as unsubstituted alkyl groups represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the general formula (2-I).

Specific examples of the aryl group in these substituents include the aryl group in the substituent of the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the general formula (2-I) This is the same as the specific example.

Examples of the heteroaryl group in these substituents include a heteroaryl group in the substituent of the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the general formula (2-I) .

Examples of the alkenyl group in these substituents include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group and a 2-chloro-1-ethenyl group.

Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a trimethylsilylethynyl group.

Examples of G ₁ in the acyl group in (G ₁ CO-) can be mentioned a hydrogen atom, and the alkyl group, an aryl group of.

Of these substituents, still more preferred examples include those in which the substituent of the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the general formula (2-I) This is the same as the preferred example.

Examples of the substituted alkyl group which is preferable as R ³¹ , R ³² and R ^{33 are the same} as the examples of the preferable substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the general formula (2-I) Do.

Examples of the unsubstituted aryl group preferable as R ³¹ , R ³² and R ^{33 include} a preferable unsubstituted aryl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ , or R ²⁵ in the formula (2-I) .

Examples of the substituted aryl group preferable as R ³¹ , R ³² and R ³³ include an example of a preferable substituted aryl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the formula (2-I) .

Specific examples of unsubstituted alkenyl groups which are preferable as R ³¹ , R ³² and R ³³ include a vinyl group and a 1-propenyl group.

Specific examples of the substituted alkenyl group preferable as R ³¹ , R ³² and R ³³ include those having a monovalent nonmetal atomic group other than a hydrogen atom as a substituent on the unsubstituted alkenyl group.

Specific examples of preferable unsubstituted aromatic heterocyclic residues as R ³¹ , R ³² and R ³³ include thiophene, furan, pyrrole, pyrazole, thiazole, oxazole, pyrimidine, pyridazine, imidazole, quinoline, triazole, indole , Carbazole, and the like.

Specific examples of the substituted aromatic heterocyclic residue preferable as R ³¹ , R ³² and R ³³ include those having a monovalent nonmetal atomic group except for a hydrogen atom as a substituent on the unsubstituted aromatic heterocyclic residue described above.

Examples of the substituted or unsubstituted alkoxy group preferable as R ³¹ , R ³² and R ^{33 include} a preferable substituent represented by R ²¹ , R ²² , R ²³ , R ²⁴ , or R ²⁵ in the general formula (2-I) Are each the same as the examples of unsubstituted alkoxy groups.

R ^31, R ^32, and preferred substituted or embodiment of the came unsubstituted alkyl group as R ³³ is preferred to be represented by ^{R 21, R 22, R 23} , R 24, or R ²⁵ in the formula (2-I) And the specific examples of the substituted or unsubstituted alkylthio group.

Next, A in the general formula (3-1) will be described. A is an aromatic ring or heterocycle which may have a substituent, and specific examples of the aromatic ring or heterocycle which may have a substituent include the same as those described for R ³¹ , R ³² and R ³³ in the general formula (3-1) .

Specific examples of the aromatic ring preferable as A are benzene, methoxybenzene, dimethoxybenzene, trimethoxybenzene, diethylaminobenzene, diphenylaminobenzene, methylthiobenzene, anthracene, phenylthiobenzene, thianthrene, phenothiazine, Dibenzothiophene, dibenzofuran, carbazole, bismethoxyphenylbenzene, and the like.

Specific examples of the heterocycle preferable as A include pyridine, benzthiazole, benzoxazole, benzthiazole and the like.

X in the general formula (3-1) represents an oxygen atom, a sulfur atom, or -N (R ³ ) -, and is preferably an oxygen atom.

Y in the general formula (3-1) represents an oxygen atom, a sulfur atom, or -N (R ³ ) -, and is preferably -N (R ³ ) -.

One of the preferable forms of the compound represented by the general formula (3-1) is a compound represented by the following general formula (3-2) from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator.

In the general formula (3-2), A represents an aromatic ring or a heterocycle which may have a substituent, and Y represents an oxygen atom, a sulfur atom, or -N (R ³³ ) -. R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a monovalent nonmetal atomic group, and A, R ³¹ , R ³² and R ³³ may be bonded to each other to form an aliphatic or aromatic ring.

Details of the A, R ^31, R ³² and R ³³ in the formula (3-2) is the same as A, R ^31, R ³² and R ³³ in the general formula (3-1).

The compound represented by the general formula (3-2) is preferably the following compounds (3-2-1) to (3-2-35), for example.

One of the preferable forms of the compound represented by the general formula (3-1) is a compound represented by the following general formula (3-3) from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator.

In the general formula (3-3), A represents an aromatic ring or a heterocycle which may have a substituent, and X represents an oxygen atom, a sulfur atom, or -N (R ³³ ) -. R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom or a monovalent nonmetal atomic group, and A, R ³³ , R ³⁴ and R ³⁵ may be bonded to each other to form an aliphatic or aromatic ring . Ar represents an aromatic ring or hetero ring having a substituent. However, on the Ar skeleton, the sum of the Hammet values has a substituent larger than zero.

A, R ³³ , R ³⁴ and R ³⁵ in the general formula (3-3) are each a synonymous with A, R ³³ , R ³² and R ³¹ in the general formula (3-1).

Ar represents an aromatic ring or hetero ring having a substituent, and specific examples of the aromatic ring or hetero ring having a substituent among those described in the explanation of A in the general formula (3-1) have.

The substituent that can be introduced into Ar in the general formula (3-3) is required to have a total sum of Hammett values of 0 or more. Examples of such substituents include a trifluoromethyl group, a carbonyl group, an ester group, a halogen atom, , A cyano group, a sulfoxide group, an amide group, and a carboxyl group. The Hammett values of these substituents are shown below. A trifluoromethyl group _{(-CF 3, m: 0.43,} p: 0.54), carbonyl groups (e.g. -COHm: 0.36, p: 0.43) , ester group _{(-COOCH 3, m: 0.37,} p: 0.45), halogen atom (e.g. Cl, m: 0.37, p: 0.23), cyano groups (-CN, m: 0.56, p : 0.66), sulfoxide groups (e.g. _{-SOCH 3, m: 0.52, p} : 0.45) and the like (0.45 -COOH, m:: 0.37 , p), an amide group (e.g. _{-NHCOCH 3, m:: 0.21,} p 0.00), a carboxyl group. (M: 0.50) in the parentheses indicates the introduction position in the aryl skeleton of the substituent and its Hammett value, and (m: 0.50) means that the Hammett value when the substituent is introduced into the meta position is 0.50.

Of these, preferred examples of Ar include a phenyl group having a substituent, and preferable substituents on the Ar skeleton include an ester group and a cyano group. The position of the substitution is particularly preferably located at the ortho position on the Ar skeleton.

Preferable examples of the compound represented by the general formula (3-3) include the following compounds (3-3-1) to (3-3-32).

One of the preferable forms of the compound represented by the general formula (3-1) is a compound represented by the following general formula (3-4) from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator. The specific sensitizer according to the present invention is more preferably a compound represented by the following general formula (3-4).

In the general formula (3-4), A represents an aromatic ring or a heterocycle which may have a substituent, and X represents an oxygen atom, a sulfur atom, or -NR ⁶¹ -. R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁶ each independently represent a hydrogen atom or a monovalent nonmetal atomic group. R ⁶⁴ and R ⁶⁵ each independently represent a monovalent non-metallic atomic group. A, R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ may be bonded to each other to form an aliphatic or aromatic ring.

When R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ represent a monovalent non-metallic atomic group, it preferably represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

Next, preferable examples of R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ in the general formula (3-4) will be described.

Preferable examples of the unsubstituted alkyl group represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are R ²¹ , R ²² , R ²³ , R ²⁴ or R ^{24 in the} formula (2-1) Is the same as the preferred example of the unsubstituted alkyl group represented by R &lt; ^{25 &} gt ;.

Examples of the alkylene group (alkyl moiety) in the substituted alkyl group represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ include R ²¹ , R ²² , (Alkyl moiety) in the substituted alkyl group represented by R ²³ , R ²⁴ , or R ²⁵ .

Examples of the substituent in the substituted alkyl group represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ include R ²¹ , R ²² , R ²³ and R ²⁴ in the general formula (2-I) , Or the substituent group of the substituted alkyl group represented by R ²⁵ .

Specific examples of the alkyl group in these substituents include the above-mentioned alkyl groups as unsubstituted alkyl groups represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ , and they may further have a substituent.

Specific examples of the aryl group in these substituents include the aryl group in the substituent of the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the general formula (2-I) This is the same as the specific example.

Examples of the heteroaryl group in these substituents include a heteroaryl group in the substituent of the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the general formula (2-I) .

Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group and a 2-chloro-1-ethenyl group.

Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a trimethylsilylethynyl group.

Examples of G ₁ in the acyl group in (G ₁ CO-) can be hydrogen, and the alkyl group, an aryl group of.

Among these substituents, still more preferred examples are those exemplified in the substituent group of the substituted alkyl group represented by R ²¹ , R ²² , R ²³ , R ²⁴ or R ²⁵ in the general formula (2-I) Is the same as the more preferable example.

Examples of the substituted alkyl group represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ include R ²¹ , R ²² , R ²³ , R ²⁴ or R ^{25 in the} formula (2-1) Is the same as the preferred examples of the substituted alkyl group represented by the formula

Preferable examples of the substituted or unsubstituted aryl group represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ include R ²¹ , R ²² , R ²³ , R ^24, or represented by R ²⁵ is substituted by the same or each of the preferred examples of the unsubstituted aryl group.

More preferred examples of R ⁶¹ include a substituted or unsubstituted aryl group, and more preferred examples of R ⁶² and R ⁶⁶ include a substituted or unsubstituted alkyl group. Particularly preferred examples of R ²² include an alicyclic alkyl group, and specific examples thereof include a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Preferable examples of R ⁶³ , R ⁶⁴ and R ⁶⁵ include a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group. Particularly preferred examples thereof include R ⁶³ and R ⁶⁴ , or R ⁶⁴ and R ⁶⁵ or R ⁶³ and R ⁶⁵ are bonded to each other through a divalent linking group. Specifically, it is preferable that R ⁶³ , R ⁶⁴ and R ⁶⁵ form a cycloalkyl structure. Preferable examples of the cycloalkyl structure include a cyclohexyl structure, a cycloheptyl structure, a cyclooctyl structure, and an adamantane structure.

The reason why such a substituent is preferable is not clear, but the efficiency of generating radicals, acids or bases of the initiator compound is improved by having the substituent particularly large in the interaction between the electron-excited state generated by light absorption and the initiator compound (Sensitivity enhancement effect), and the introduction of a bulky structure adjacent to the immune structure suppresses the disappearance from the photoresist film due to decomposition of the immune structure, such as hydrolysis and oxidative decomposition.

Next, A in the general formula (3-4) will be described. As specific examples of the aromatic ring or heterocycle which may have a substituent, examples of R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ And the like.

Among them, A is preferably an aryl group having an alkoxy group, a thioalkyl group or an amino group, and more preferably A is an aryl group having an amino group. Examples of the aryl group having a particularly preferable amino group include a dialkylaminoaryl group and a diarylaminoaryl group. Specific examples thereof include a dimethylaminophenyl group, a diethylaminophenyl group, a piperidinophenyl group, a morpholinophenyl group, a julolidine group, a di And a phenylaminophenyl group.

Specific examples (3-D1) to (3-D121) of the compound (specific sensitizer) represented by the general formula (3-1) are shown below, but the present invention is not limited thereto. In addition, it is not clear whether the isomer is a double bond connecting an acidic nucleus and a basic nucleus, and the present invention is not limited to either isomer.

A method of synthesizing the compound represented by the general formula (3-1) will be described.

The compound represented by the general formula (3-1) is usually obtained by a condensation reaction between an acidic nucleus having an active methylene group and a substituted or unsubstituted aromatic ring or a heterocycle, for example, Japanese Patent Publication No. 59-28329 And the like.

For example, a synthesis method using a condensation reaction of an acidic nucleus compound with a basic nucleus raw material having an aldehyde group or a carbonyl group on a heterocycle as shown in the following reaction formula (3-1) can be given. The condensation reaction is carried out, if necessary, in the presence of a base. Examples of the base include those generally used in general use, such as amines, pyridines (trialkylamines, dimethylaminopyridine, diazabicyclo-undecene DBU and the like), metal amides (such as lithium diisopropylamide), metal alkoxides Methoxide, potassium t-butoxide, etc.), metal hydrides (sodium hydride, potassium hydride, etc.) can be used without limitation.

Further, as another preferable synthesis method of the compound represented by the general formula (3-1), a method according to the following reaction formula (3-2) can be mentioned. That is, a condensation reaction of a basic nuclear material having an aldehyde group or a carbonyl group on a heterocycle with an acidic nucleus compound in which Y is a sulfur atom is used as an acidic nucleus compound in the reaction formula (3-1) (3-1), a metal salt capable of forming a metal sulfide by chemically interacting with the sulfur atom in the dye precursor and water or a primary amine compound (R-NH ₂ : Wherein R represents a monovalent non-metallic atomic group.

Among them, the reaction represented by the reaction formula (3-2) is particularly preferable due to the high efficiency of synthesis due to the high yield of each reaction. Among them, in the case of synthesizing the compound represented by the above formula (3-4) -2) is useful.

Equation (3-2) of, M ^{_n +} X ⁿ represents the same metal salt and M ^{n +} X _n in the above equation (2-2).

In the case of synthesizing the compound represented by the above general formula (3-4), R ³¹ , R ³² and Y in the reaction formulas (3-1) and (3-2) ) Correspond to R ⁶⁶ , R ⁶² , and NC (R ⁶³ ) (R ⁶⁴ ) (R ⁶⁵ ).

In the curable composition of the present invention, the compounds (specific sensitizers) represented by the general formula (3-1) may be used singly or in combination of two or more kinds.

The content of the specific sensitizer in the curable composition and color filter curable composition of the present invention is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 20% by mass, based on the total solid content of the curable composition.

Particularly, the compound represented by the general formula (2-I) and the compound represented by the general formula (3-1) according to the present invention described below have a very high concentration of the colorant in the curable composition, (2-1) or a compound represented by the general formula (3-1) according to the present invention described below is not added to the photosensitive layer when the light transmittance of the photosensitive layer is extremely low, And when the transmittance of the light of 365 nm and / or the transmittance of the light of 405 nm is 10% or less, the effect is remarkably exerted.

<(B) Photopolymerization initiator>

The curable composition of the present invention contains a photopolymerization initiator.

The photopolymerization initiator in the present invention is a compound which is decomposed by light to initiate and accelerate the polymerization of a polymerizable compound to be described later, and preferably has absorption in a wavelength region of 300 to 500 nm. The photopolymerization initiator may be used singly or in combination of two or more.

Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, An imidazole-based compound, an organic boric acid compound, a disulfonic acid compound, an oxime ester compound, an onium salt compound, and an acylphosphine (oxide) compound.

Specific examples of the organic halogenated compound include Wakabayashi Co., Ltd., Bull Chem.Soc Japan 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-36281 Japanese Patent Application Laid-open No. Sho 55-32070, Japanese Laid-Open Patent Application No. 60-239736, Japanese Laid-Open Patent Publication No. 61-169835, Japanese Laid-Open Patent Publication No. 61-169837, Japanese Laid- JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, MPHutt "Jurnal of Heterocyclic Chemistry" 1 (No3), (1970) , An oxazole compound substituted with a trihalomethyl group, and an s-triazine compound.

The s-triazine compound is more preferably an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to a s-triazine ring, specifically, for example, 2,4,6-tris (Trichloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (?,?,? - trichloroethyl 4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6- (Trichloromethyl) -s-triazine, 2- (p-chlorophenyl) - 4,6-bis (Trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s -Triazine, 2-styryl-4,6-bis (trickle (Trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4, (Trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio- -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) 6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like.

Examples of the oxadiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4- 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (naphtho- Oxadiazole and the like.

Examples of the carbonyl compound include benzophenone such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, Phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone,? -Hydroxy-2-methylphenylpropanone, 1-hydroxy- 1-methyl-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '- (methylthio) phenyl) -2-morpholino Acetophenone derivatives such as 1,1,1-trichloromethyl- (p-butylphenyl) ketone and 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, , 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4- Thioxanthone derivatives such as oxantone, ethyl p-dimethylaminobenzoate, p-diethylamino And the like can be mentioned benzoic acid ester derivatives such as ethyl Xiangshan expression.

Examples of the ketal compound include benzyl methyl ketal, benzyl-beta-methoxyethyl ethyl acetal and the like.

Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, and methyl o-benzoyl benzoate.

Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- Butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5- Dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumylperoxide, dicumylperoxide, 2,5-dimethyl-2,5-di (tert-butylperoxy ) Hexane, 2,5-oxanooyl peroxide, peroxy succinic acid, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di- Ethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydi Butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert-butyl peroxy octanoate, tert-butyl peroxylaurate, tosyl carbonate, 3, 3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'- , 4,4'-tetra- (p-isopropylcumperperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxy dihydrogen 2 phthalate), carbonyldi (t-hexylperoxy dihydrogen 2 phthalate ) And the like.

Examples of the azo compound include the azo compounds described in JP-A-8-108621.

Examples of the coumarin compound include 3-methyl-5-amino- ((s-triazin-2-yl) amino) 2-yl) amino) -3-phenylcoumarin, and 3-butyl-5-dimethylamino- ((s-triazin-2-yl) amino) -3-phenyl coumarin.

Examples of the azide compounds include organic azide compounds described in USP 2848328, USP 2852379 and USP 2940853, 2,6-bis (4-azidobenzylidene) -4-ethylcyclohexa (BAC-E), and the like.

Examples of the metallocene compound include compounds disclosed in Japanese Patent Application Laid-Open Nos. 59-152396, 61-151197, 63-41484, 2-249, -4705 and JP-A 5-83588, for example, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis Di-cyclopentadienyl-Ti-bis-2,4-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti- Di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti- Bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis- Bis-2,4,6-trifluorophenyi-1-yl, di-methylcyclopentadienyl-Ti-bis- Di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, 304453, and an iron-arene complex described in JP-A-1-152109.

As the imidazole-based compound, for example, a hexaarylbimidazole compound and the like are preferable.

Examples of the hexaarylbimidazole compound include various compounds described in each specification such as Japanese Patent Publication Nos. 6-29285, 3,479,185, 4,311,783 and 4,622,286, specifically 2 , 2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) (O, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o- chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, Bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and the like.

Examples of the organic borate compound include compounds described in Japanese Patent Application Laid-Open Nos. 62-143044, 62-150242, 9-188685, 9-188686, 9- 188710, 2000-131837, 2002-107916, 2764769, 2000-310808, and Kunz, Martin &quot; Rad Tech &quot; Proceeding April 19-22, 1998, Chicago &quot;, JP-A-6-157623, JP-A-6-175564 and JP-A-6-175561 An organic boron iodonium complex described in JP-A-6-175554 and JP-A-6-175553, an organic boron complex described in JP-A-9-188710, Phosphonium complexes, JP-B-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP- Organic boron transition metal coordination complexes such as those described in JP-A-292014, and the like.

Examples of disulfone compounds include compounds described in JP-A-61-166544 and JP-A-2002-328465.

As the oxime ester compound, Perkin II (1979) 1653-1660), J.C.S. Compounds described in Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232 and Japanese Patent Application Laid-Open No. 2000-66385, JP-A 2000-80068, JP 2004-534797 And compounds described in publications.

Examples of the onium salt compounds include diazonium salts described in SISchlesinger, Photogr. Sci. Eng., 18, 387 (1974), TSBal et al, Polymer, 21, 423 (1980), U.S. Patent No. 4,069,055, Ammonium salts described in JP-A-4-365049 and the like, phosphonium salts described in each of U.S. Patent Nos. 4,069,055 and 4,069,056, EP 104,143, U.S. Patent Nos. 339,049 and 410,201, Iodonium salts disclosed in Japanese Patent Application Laid-Open Nos. 2-150848 and 2-296514, and the like.

The iodonium salt which can be preferably used in the present invention is a diaryliodonium salt. From the standpoint of stability, it is preferable that two or more thereof are substituted with an electron donating group such as an alkyl group, an alkoxy group or an aryloxy group. In addition, iodonium salts having one substituent group of a triarylsulfonium salt having a coumarin or anthraquinone structure and having absorption at 300 nm or more are preferable as other preferable sulfonium salt forms.

Examples of sulfonium salts which can be preferably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, US Patent Nos. 4,933,377, 161,811, 410,201, 339,049 , 4,760,013, 4,734,444, 2,833,827, 2,904,626, 3,604,580, 3,604,581, and the sulfonium salts described in the specification of each of these patents are preferably substituted with electron attractive groups . As the electron-withdrawing group, it is preferable that the Hammett value is larger than zero. Preferred examples of the electron-withdrawing group include a halogen atom and a carboxylic acid.

Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorption at 300 nm or more. Other preferable sulfonium salts include sulfonium salts in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more.

As the onium salt compounds, there may be mentioned, for example, J. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. V. Crivello et al., J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), C.S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and the like.

Examples of the acylphosphine (oxide) compound include IRGACURE 819, DAROCURE 4265 and DAROCURE TPO manufactured by Ciba Specialty Chemicals.

The photopolymerization initiator used in the present invention is most preferably at least one compound selected from the group consisting of trihalomethyl triazine compounds, non-imidazole compounds and oxime compounds from the viewpoint of high sensitivity, Is most preferable.

The content of the photopolymerization initiator contained in the curable composition of the present invention is preferably 0.1 to 50 mass%, more preferably 0.1 to 30 mass%, and particularly preferably 0.3 to 20 mass%, based on the total solid content of the curable composition . Good sensitivity and pattern formability can be obtained in this range.

In the present invention, the mass ratio [(B) / (A)] of the photopolymerization initiator (B) and the specific sensitizer (A) is preferably 0.1 or more and 10 or less, more preferably 0.3 or more and 5 or less And more preferably 0.5 or more and 3 or less.

&Lt; (C) Polymerizable compound >

The polymerizable compound usable in the present invention is an addition polymerizable compound having at least one ethylenic unsaturated double bond and is selected from compounds having at least one terminal ethylenic unsaturated bond, preferably at least two terminal ethylenic unsaturated bonds. Such a group of compounds is widely known in the above-mentioned industrial fields, and these compounds can be used without particular limitation. They have chemical forms such as, for example, monomers, prepolymers, i.e., dimers, trimesters and oligomers, or mixtures thereof and copolymers thereof. Examples of the monomers and copolymers thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, An ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound are used. Further, an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group, an addition reaction product of a monofunctional or multifunctional isocyanate or epoxy compound and a monofunctional or polyfunctional carboxyl A dehydration condensation reaction product of an acid is also preferably used. Further, an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group and an addition reaction product of a monofunctional or multifunctional alcohol, amine, or thiol, as well as a halogen group or a leaving group such as a tosyloxy group Substitution reaction products of unsaturated carboxylic acid esters or amides having a substituent with monofunctional or polyfunctional alcohols, amines and thiols are also preferable. As another example, it is also possible to use a group of compounds in which unsaturated carboxylic acids are substituted with unsaturated phosphonic acids, styrene, vinyl ethers or the like.

Specific examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol Diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, hexane diol diacrylate, 1,4 -Cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol tri Acrylate, sor (Acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid EO-modified triacrylate, and the like.

Examples of the methacrylic ester include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol ethane trimethacrylate, ethylene glycol di Methacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, Pentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- 2-methoxyethoxy) phenyl] dimethylmethane and the like.

Examples of itaconic acid esters include ethylene glycol diacetonate, propylene glycol diacetonate, 1,3-butanediol diacetonate, 1,4-butanediol diacetonate, tetramethylene glycol diacetonate, pentaerythritol diacetonate, sorbitol tetra- And Nate. Examples of the crotonic acid ester include ethylene glycol dichlonate, tetramethylene glycol dichlonate, pentaerythritol dichlonate, and sorbitol tetradecrhotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include aliphatic alcohol esters described in Japanese Patent Publication Nos. 51-47334 and 57-196231, Japanese Laid-Open Patent Publication Nos. 59-5240, 59-5241, 59-5241, Those having an aromatic skeleton described in JP-A No. 2-226149, those containing an amino group described in JP-A No. 1-165613, and the like are also preferably used. The above-mentioned ester monomer can also be used as a mixture.

Specific examples of the monomer of the amide of the aliphatic polyvalent amine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, Methacrylamide, diethylenetriamintris acrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, and the like. Examples of other preferable amide-based monomers include those having a cyclohexylene structure described in Japanese Patent Publication No. 54-21726.

Further, a urethane-based addition polymerizable compound produced by the addition reaction of isocyanate and hydroxyl group is also preferable. As specific examples thereof, there can be mentioned, for example, two or more isocyanate groups in a molecule described in Japanese Patent Publication No. 48-41708 , A vinyl urethane compound having at least two polymerizable vinyl groups in one molecule and having a hydroxyl group-containing vinyl monomer represented by the following general formula (A) added thereto.

CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (A)

(In the general formula (A), R ⁴ and R ⁵ represent H or CH _3. )

Urethane acrylates as described in JP-A-51-37193, JP-A-2-32293 and JP-B-2-16765, and JP-A-58-49860, JP-A- Also, urethane compounds having an ethylene oxide skeleton described in JP-A-56-17654, JP-A-62-39417 and JP-A-62-39418 are also preferable. Further, addition polymerizable compounds having an amino structure or sulfide structure in the molecule described in Japanese Patent Application Laid-Open Nos. 63-277653, 63-260909, and 1-105238 are used It is possible to obtain a photopolymerizable composition having a very high photosensitive speed.

Other examples include polyester acrylates, epoxy resins and (meth) acrylates as described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-30490, Epoxy acrylates obtained by reacting acrylic acid with acrylic acid, and polyfunctional acrylates or methacrylates such as epoxy acrylates. Specific unsaturated compounds described in Japanese Patent Publication Nos. 46-43946, 1-40337 and 1-40336, and vinylpolyphosphine-based compounds described in Japanese Patent Application Laid-Open No. 2- 25493 Compounds and the like. In addition, in either case, a structure containing the perfluoroalkyl group described in JP-A-61-22048 is preferably used. Also, those which have been introduced as photocurable monomers and oligomers in Japan Adhesion Society vol.20, No. 7, pages 300 to 308 (1984) can be used.

The structure of the addition polymerizable compound, details of the method of using it alone, whether it is used alone or in combination, can be arbitrarily set in accordance with the final performance design of the curable composition. For example, it is selected from the following viewpoints.

From the viewpoint of sensitivity, a structure having a large amount of unsaturated group per molecule is preferable, and in most cases, bifunctionality or more is preferable. Further, in order to increase the strength of the cured film, it is preferable to use three or more functionalities, and when it is used in combination with other functional water and other polymerizable groups (for example, acrylate ester, methacrylate ester, styrene series compound and vinyl ether series compound) A method of adjusting both strengths is also available.

Also, the compatibility and dispersibility of the curable composition and other components contained in the photosensitive composition (e.g., photopolymerization initiator, colorant (pigment, dye), binder polymer, etc.) , For example, the use of a low-purity compound or the combination of two or more species may improve the compatibility. Also, a specific structure may be selected for the purpose of improving adhesion with a substrate or the like.

&Lt; (D) Colorant >

The curable composition of the present invention contains a colorant.

The colorant to be contained in the curable composition of the present invention is not particularly limited, and various conventionally known dyes and pigments may be used singly or in combination. From the viewpoint of light resistance, the colorant is preferably a pigment.

In the curable composition of the present invention, conventionally known various inorganic pigments or organic pigments may be used. Considering that it is preferable to use an inorganic pigment or an organic pigment with a high transmittance, it is preferable to use as fine as possible. Considering the handling property, the average particle diameter of the pigment is preferably 0.01 탆 to 0.1 탆, More preferably 0.05 mu m. Examples of the inorganic pigments include metal compounds represented by metal oxides and metal complex salts. Specific examples thereof include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, , And composite oxides of the above metals.

As the organic pigment, for example,

CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;

C. I. Pigment Orange 36, 38, 43, 71;

CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C.I. Pigment Violet 19, 23, 32, 39;

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment Green 7, 36, 37;

C.I. Pigment Brown 25, 28;

C. I. Pigment Black 1, 7;

Carbon black, and the like.

In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These basic N atom-bearing pigments exhibit good dispersibility in the compositions of the present invention. Although the cause thereof has not been sufficiently clarified, it is presumed that the excellent affinity between the photosensitive polymer component and the pigment affects the effect.

Examples of pigments that can be preferably used in the present invention include the following pigments. However, the present invention is not limited to these.

CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

CI Pigment Orange 36, 71,

CI Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C.I. Pigment Violet 19, 23, 32,

CI Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,

C.I. Pigment Black 1

These organic pigments may be used alone or in combination of several to enhance color purity. Specific examples of the combination are shown below. For example, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment, or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment Or a mixture of a perylene red pigment and the like. Examples of the anthraquinone pigments include CI Pigment Red 177, the perylene pigments include CI Pigment Red 155 and CI Pigment Red 224, and the diketopyrrolopyrrole pigments include CI Pigment Red 254 And mixing with CI Pigment Yellow 139 is preferable in terms of color reproducibility. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. When the ratio is 100: 4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm and the color purity can not be increased. In the case of 100: 51 or more, the main wavelength becomes short wavelength, and deviation from the NTSC target color may be large. Particularly, the mass ratio is most preferably in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted to the chromaticity.

As the green pigment, a halogenated phthalocyanine pigment may be used singly or in combination with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment. Examples include CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, or CI Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably from 100: 5 to 100: 150. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 nm to 450 nm and the color purity can not be increased. If the ratio is more than 100: 150, the dominant wavelength becomes a long wavelength and the deviation from the NTSC target color may become large. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

As the blue pigment, a phthalocyanine pigment may be used singly or a mixture of the phthalocyanine pigment and 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 mass ratio of the blue pigment to the purple pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

As the pigment for black matrix, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium carbon is preferable. The mass ratio of carbon to titanium carbon is preferably in the range of 100: 0 to 100: 60. At 100: 61 or more, the dispersion stability may be lowered.

In the present invention, when the coloring agent is a dye, it is dissolved uniformly in the composition to obtain a curable composition.

The dye that can be used as the colorant contained in the curable composition of the present invention is not particularly limited, and known dyes for color filters can be used. For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, U.S. Patent No. 4,808,501, U.S. Patent No. 5,667,920, U.S. Patent No. 5,059,500, JP-A-5-333207, JP-A-6-35183, and JP-A-6-51115 , Japanese Patent Application Laid-Open Nos. 6-194828, 8-211599, 4- 249549, 10-123316, and 11-302283 , Japanese Patent Application Laid-Open Nos. 7-286107, 2001-4823, 8-15522, 8-29771, 8-146215, Japanese Unexamined Patent Application Publication No. 11-343437, Japanese Unexamined Patent Application, First Publication No. Hei 8-62416 Japanese Patent Application Laid-Open No. 2002-14220, Japanese Patent Application Laid-Open No. 2002-14221, Japanese Patent Application Laid-Open No. 2002-14222, Japanese Patent Application Laid-Open No. 2002-14223, Japanese Patent Application Laid-Open No. 8-302224, Coloring agents disclosed in JP-A-8-73758, JP-A-8-179120, and JP-A-8-151531 can be used.

Examples of the chemical structure include a pyrazole group, anilino group, triphenylmethane group, anthraquinone group, anthrapyridone group, benzilidene group, oxolin group, pyrazolotriazole group, pyridazo group, cyanine group, phenothiazine group, Dyes such as pyrazolomethane, xanthane, phthalocyanine, benzopyran, indigo and the like can be used.

In the case of a resist system which performs water or alkali development, an acidic dye and / or a derivative thereof may be preferably used from the viewpoint of completely removing the binder and / or the dye of the tailing unit due to development.

In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azo dyes, disperse dyes, oil dyes, food dyes, and / or derivatives thereof may also be usefully used.

The acidic dye is not particularly limited as long as it has an acidic group such as a sulfonic acid or a carboxylic acid, but the acidic dye may be soluble in an organic solvent or a developer, salt-forming property with a basic compound, absorbance, interaction with other components in the composition, Are chosen in view of both the required performance of the &lt; / RTI &gt;

Specific examples of the acidic dyes are shown below, but the present invention is not limited thereto. For example,

acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 45, 62, 70, 74, 80, 83, 86, 87, 90, 92, 103, 112, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 243; Food Yellow 3; And derivatives of these dyes.

Among them, acid dyes such as acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1; acid orange 8, 51, 56, 63, 74; acid red 1, 4, 8, 34, 37, 42, 52, 57, 80, 97, 114, 143, 145, 151, 183, 217; acid violet 7; acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 184, 243; acid green 25 and derivatives of these dyes are preferred.

Acid dyes, xanthane dyes and phthalocyanine dyes other than those described above are also preferable, and C.I. Solvent Blue 44, 38; C.I.Solvent orange 45; Rhodamine B, and Rhodamine 110, and derivatives of these dyes are also preferably used.

Among them, examples of the colorant (D) include triarylmethane, anthraquinone, azomethine, benzilidene, oxolin, cyanine, phenothiazine, pyrrolopyrazolamomethine, xanthene, phthalocyanine, A pyrazolone azo group, an anilino azo group, a pyrazolotriazole azo group, a pyridon azo group, and an anthrapyridone group.

The coloring agent that can be used in the present invention is a dye or a pigment which satisfies an average particle diameter r (unit nm) of 20? R? 300, preferably 125? R? 250, and particularly preferably 30? desirable. By using the pigment having the average particle diameter (r), red and green pixels having a high contrast ratio and a high light transmittance can be obtained. Here, the &quot; average particle diameter &quot; means the average particle diameter of the secondary particles in which the primary particles (short crystals) of the pigment are aggregated.

The particle diameter distribution of the secondary particles of the pigment which can be used in the present invention (hereinafter simply referred to as "particle diameter distribution") is preferably 70% by mass or more of the total of secondary particles having an average particle diameter of 100 nm, It is preferably at least 80% by mass.

The above-mentioned pigment having an average particle diameter and a particle diameter distribution is a pigment mixture in which a commercially available pigment is mixed with other pigments (average particle diameter is usually more than 300 nm) used as occasion demands, preferably with a dispersant and a solvent, For example, by pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained usually takes the form of a pigment dispersion.

The content of the coloring agent (D) contained in the curable composition of the present invention is preferably 25 to 95 mass%, more preferably 30 to 90 mass%, and even more preferably 40 to 80 mass%, based on the total solid content of the curable composition Do.

When the amount of the colorant is too small, there is a tendency that an appropriate chromaticity can not be obtained when the color filter is produced by the curable composition of the present invention. On the other hand, if the amount is too large, the photo-curing will not sufficiently proceed and the strength as a film will decrease, and the development latitude tends to become narrow in the alkali development. However, the specific sensitizer according to the present invention, Is contained at a high concentration, the sensitivity improving effect is remarkably exhibited.

The curable composition of the present invention may further contain optional components described below in detail, if necessary, together with the specific sensitizer (A), the photopolymerization initiator (B), the polymerizable compound (C) and the colorant (D) . Hereinafter, optional components that the curable composition of the present invention can contain will be described.

<(E) Dispersant>

When the curable composition of the present invention contains a pigment as the (D) colorant, it is preferable to add the dispersant (E) from the viewpoint of improving the dispersibility of the pigment.

Examples of the dispersant (pigment dispersant) that can be used in the present invention include polymer dispersants such as polyamide amines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, (Meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkylphosphoric ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative and the like.

The polymer dispersant can also be classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer from the structure.

The polymeric dispersant is adsorbed on the surface of the pigment to prevent re-aggregation. Therefore, an end-modified polymer having an anchor portion on the surface of the pigment, a graft-type polymer, and a block-type polymer can be mentioned as preferable structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

Specific examples of the pigment dispersant usable in the present invention include Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161 BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), EFKA 4047, 4050, 4010, 4165 (polyurethane system) manufactured by EFKA, EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative) (Azo pigment derivative) manufactured by Ajinomoto Chemical Co., Ltd., Ajispa PB821 and PB822 manufactured by Ajinomoto Pan Techno Co., Ltd., Furan TG-710 (urethane oligomer), Kyowa Shokagaku Co., Ltd., Polyflow No.50E, Quot; DiSparon KS-860, 873SN, 874, &amp;num; 2150 (aliphatic polyvalent carboxylate (N-naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic), # 7004 (polyetherester), DA-703-50, DA-705 and DA- (Homopolymer polycarboxylic acid), Emeralgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether), acetamin 86 (stearyl amine) (A polymer having a functional group at the terminal), 24000, 28000, 2500, 2500, 2500, 2500, 2500, 32000, 38500 (graft type polymer), NIKKOL T106 (polyoxyethylene sorbitan monooleate) and MYS-IEX (polyoxyethylene monostearate) manufactured by Nikko Chemical Co.,

These dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of the pigment derivative and the polymer dispersant.

The content of the dispersant in the present invention is preferably from 1 to 80 mass%, more preferably from 5 to 70 mass%, and still more preferably from 10 to 60 mass% with respect to the pigment.

Specifically, in the case of using a polymer dispersant, the amount thereof is preferably in the range of 5 to 100 mass%, more preferably in the range of 10 to 80 mass% with respect to the pigment. In the case of using a pigment derivative, the amount of the pigment to be used is preferably in the range of 1 to 30 mass%, more preferably in the range of 3 to 20 mass%, more preferably in the range of 5 to 15 mass% Is particularly preferable.

In the present invention, when a pigment and a dispersant are used as the colorant, the total content of the colorant and the dispersant is preferably 30% by mass or more and 90% by mass or less with respect to the total solid content constituting the curable composition More preferably 40% by mass or more and 85% by mass or less, and still more preferably 50% by mass or more and 80% by mass or less.

&Lt; (F) Binder polymer &

In the curable composition of the present invention, a binder polymer may be further used if necessary for the purpose of improving the film properties. As the binder, it is preferable to use a linear organic polymer. As such &quot; linear organic polymer &quot;, known ones can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer can be used not only as a film-forming agent, but also as a water, weakly alkaline water or organic solvent developer. For example, water-soluble organic polymers enable water development. Examples of such linear organic polymers include radical polymers having carboxylic acid groups in the side chains, such as those disclosed in Japanese Patent Application Laid-open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication 58-12577, Japanese Patent Publication 54 -25957, JP-A-54-92723, JP-A-59-53836 and JP-A-59-71048, that is, a resin obtained by singly or copolymerizing a monomer having a carboxyl group, an acid A resin in which an acid anhydride unit is hydrolyzed, half-esterified or half-amidated, or an epoxy acrylate in which an epoxy resin is modified with an unsaturated monocarboxylic acid or an acid anhydride. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and 4-carboxystyrene. Monomers having an acid anhydride include maleic anhydride.

Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, it is useful to add a cyclic acid anhydride to the polymer having a hydroxyl group.

When the alkali-soluble resin is used as a copolymer, other monomers other than the monomers exemplified above may be used as a copolymerizable compound. Examples of other monomers include the following compounds (1) to (12).

(1) a polyfunctional monomer selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, Acrylate esters having an aliphatic hydroxyl group such as acrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate, and methacrylic acid esters.

(2) acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, Acrylate such as vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate and the like such as 3,4-epoxycyclohexylmethyl acrylate, Late.

(3) a copolymer obtained by copolymerizing methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, methacryl Methacrylic acid, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, Alkyl methacrylates such as 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate and the like.

(4) A method for producing an acrylic resin composition, which comprises the steps of: (1) mixing acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexylmethacrylamide, N-cyclohexyl acrylamide, N- , N-nitrophenylacrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, Acrylamide or methacrylamide such as allyl methacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether.

(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

(7) styrenes such as styrene,? -Methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.

(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

(9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, and the like.

(11) Unsaturated imides such as maleimide, N-acryloyl acrylamide, N-acetyl methacrylamide, N-propionyl methacrylamide and N- (p-chlorobenzoyl) methacrylamide.

(12) A methacrylic acid-based monomer having a hetero atom bonded to the? -Position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be given.

Among them, a (meth) acrylic resin having an allyl group, a vinyl ester group and a carboxyl group in the side chain, an alkali-soluble resin having a double bond in the side chain described in JP-A-2000-187322 and JP- The alkali-soluble resin having an amide group in the side chain described in JP-A-2001-242612 is preferable because it has excellent balance between film strength, sensitivity and developability.

Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Laid- Japanese Patent Application Laid-open No. Hei 1-271741, Japanese Patent Application No. Hei 10-116232, and the like, or an acid group and a double bond described in Japanese Patent Application Laid-Open No. 2002-107918, Is superior in strength and therefore is advantageous from the standpoint of resistance to abrasion and low exposure.

The acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Laid-Open Publication No. 2001-318463 and the like is preferable because of excellent balance between film strength and developability.

In addition, as the water-soluble linear organic polymer, polyvinyl pyrrolidone, polyethylene oxide and the like are useful. Further, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful for increasing the strength of the cured film.

The weight average molecular weight of the binder polymer that can be used in the present invention is preferably 5,000 or more, more preferably from 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more, 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 to 10.

These binder polymers may be random polymers, block polymers, graft polymers, or the like.

The binder polymer usable in the present invention can be synthesized by a conventionally known method. Examples of the solvent used for the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, ethyl acetate, diethylene glycol dimethyl ether, Methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents may be used alone or in combination of two or more.

Examples of the radical polymerization initiator used in synthesizing the binder polymer usable in the present invention include known compounds such as azo-based initiators and peroxide initiators.

<(G) Notarization>

It is also preferable that the curable composition of the present invention contains a notarization accelerator. In the present invention, the notarized sensitizer has an effect of further enhancing the sensitivity to the active radiation of the sensitizing dye or initiator, or inhibiting polymerization inhibition of the polymerizable compound by oxygen.

Examples of such a notarization agent include amines such as MR Sander et al., Journal of Polymer Society Vol. 10, p. 3173 (1972), JP-A No. 44-20189, JP-A 51-82102, Japanese Patent Laid-Open Nos. 52-134692, 59-138205, 60-84305, 62-18537, 64-33104, And compounds described in Disclosure 33825, and specific examples thereof include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodymethyl aniline.

Other examples of the notarization agent include thiols and sulfides such as the thiol compounds described in JP-A-53-702, JP-A-55-500806 and JP-A-5-142772, And disulfide compounds disclosed in JP 56-75643 A, and specific examples thereof include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto- 4 (3H) -quinazoline,? -Mercaponaphthalene, and the like.

Examples of the notarization agent include amino acid compounds (e.g., N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (e.g., tributyltin acetate), Japanese Patent Publication 55-34414 Hydrogen donors described in JP-A-6-308727 (for example, trithian and the like), and the like.

The content of the notarization agent is preferably in the range of 0.1 to 30 mass%, more preferably in the range of 1 to 25 mass% with respect to the mass of the total solid content of the curable composition from the viewpoint of improvement of the curing rate due to balance of polymerization growth rate and chain transfer. , And more preferably in the range of 0.5 to 20 mass%.

Thiol compound

The curable composition of the present invention is preferably a notarization agent containing a thiol compound. As the thiol compound which can be contained in the curable composition of the present invention, a compound represented by the following general formula (1-IV) is preferable.

In the general formula (1-IV), X represents a sulfur atom, an oxygen atom or -N (R ⁴³ ), and R ⁴³ represents an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 13 carbon atoms. R ⁴¹ and R ^{42 each} represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, a phenyl group optionally substituted with an alkoxy group having 1 to 8 carbon atoms, a nitro group, an alkoxy group having 1 to 8 carbon atoms A carbonyl group, a phenoxycarbonyl group, an acetyl group or a carboxyl group, and R ⁴¹ and R ⁴² and a double bond to which they are bonded may form a benzene ring, and the double bond to which R ⁴¹ and R ⁴² are bonded may be a hydrogen atom .

Examples of the thiol compound include the compounds described in the thiol compounds described in JP-A-53-702, JP-A-55-500806 and JP-A-5-142772.

The thiol compound is preferably represented by the following general formula (1-V). The notarized sensitizer has an effect of further improving the sensitivity to the actinic radiation of the sensitizer or the initiator, or inhibiting polymerization inhibition of the polymerizable compound by oxygen.

In the general formula (1-V), R represents an alkyl group or an aryl group, and A represents an atomic group which forms a heterocycle together with N = C-N.

In the general formula (1-V), R represents an alkyl group or an aryl group.

Examples of the alkyl group include linear, branched or cyclic alkyl groups of 1 to 20 carbon atoms, linear, branched, or cyclic alkyl groups of 1 to 12 carbon atoms, branched groups of 3 to 12 carbon atoms, and carbon atoms of 5 More preferably a cyclic alkyl group having from 1 to 10 carbon atoms.

Specific examples thereof include a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, An isopropyl group, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, an isopentyl group, a neopentyl group, a 1-methylbutyl group, an isohexyl group, a 2-ethylhexyl group, Cyclohexyl group, cyclopentyl group, 2-norbornyl group and the like.

Examples of the aryl group include a benzene ring in which one to three benzene rings form a condensed ring in addition to a monocyclic structure, a benzene ring and a five-membered unsaturated ring in which a condensed ring is formed, and specific examples thereof include phenyl, naphthyl, An anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group, and among these, a phenyl group and a naphthyl group are more preferable.

These alkyl groups and aryl groups may further have a substituent. The substituent which can be introduced is a linear, branched or cyclic alkyl group of 1 to 20 carbon atoms, a linear, branched or cyclic alkyl group of 2 to 20 carbon atoms An alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an alkoxycarbonyloxy group having 2 to 20 carbon atoms, An aryloxycarbonyloxy group having 7 to 20 carbon atoms, a carbamoyloxy group having 1 to 20 carbon atoms, a carboxylamide group having 1 to 20 carbon atoms, a sulfonamide group having 1 to 20 carbon atoms, a carbon atom number of 1 A carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a carbon atom number of 7 to 20 An alkoxycarbonyl group having 2 to 20 carbon atoms, an N-acylsulfamoyl group having 1 to 20 carbon atoms, An N-sulfamoylcarbamoyl group having 1 to 20 atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, an alkoxycarbonylamino group having 2 to 20 carbon atoms, An amino group, a substituted amino group having 1 to 20 carbon atoms, an imino group having 1 to 20 carbon atoms, an ammonia group having 3 to 20 carbon atoms, a carboxyl group, a sulfo group, an oxy group, a mercapto group An arylthio group having 6 to 20 carbon atoms, an arylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, A ureido group having 2 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, a sulfamoylamino group, a substituted sulfamoylamino group having 1 to 2 carbon atoms, a silyl group having 2 to 20 carbon atoms , An isocyanate group, an isocyanide group, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.) Nitro group, onium group, and the like.

In the general formula (1-V), A represents an atomic group which forms a heterocycle together with N = C-N.

Examples of the atom constituting the atomic group include a carbon atom, a nitrogen atom, a hydrogen atom, a sulfur atom, and a selenium atom.

The heterocycle formed by A and N = C-N may further have a substituent, and the substituent which can be introduced includes the same substituent as the substituent that can be introduced into the alkyl group or the aryl group.

The thiol compound is more preferably represented by the following general formula (1-VI) or general formula (1-VII).

In the general formula (1-VI), R ⁵¹ represents an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group.

In the general formula (1-VII), R ⁵² represents an alkyl group or an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group or an aryl group.

The halogen atom in the general formulas (1-VI) and (1-VII) is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the alkoxy group in the general formulas (1-VI) and (1-VII) include a methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, A benzyloxy group, an allyloxy group, a phenethyloxy group, a carboxyethyloxy group, a methoxycarbonylethyloxy group, an ethoxycarbonylethyloxy group, a methoxyethoxy group, a phenoxyethoxy group, a methoxyethoxy group A morpholinoethoxy group, a morpholinoethoxy group, an allyloxyethoxyethoxy group, a phenoxy group, a tolyloxy group, a xylyloxy group, a mesityloxy group, a quinolyloxy group, A methoxyphenyloxy group, an ethoxyphenyloxy group, a chlorophenyloxy group, a bromophenyloxy group, an acetyloxy group, a benzoyloxy group, and a naphthyloxy group.

The alkyl group in the general formula (1-VI) and (1-VII) is the same as the alkyl group represented by R in the general formula (1-V), and the preferable range thereof is also the same.

The aryl groups in the general formulas (1-VI) and (1-VII) are the same as the aryl groups represented by R in the general formula (1-V), and their preferable ranges are also the same.

Each of the groups in the general formulas (1-VI) and (1-VII) may further have a substituent. Examples of the substituent include substituents that can be introduced into an alkyl group or an aryl group represented by R in formula (1-V) It is the same as the one that exists.

Of the general formulas (1-VI) and (1-VII), X is a hydrogen atom from the viewpoint of solubility of PGMEA.

In the general formula (1-VI), R ⁵¹ is preferably a phenyl group in view of sensitivity and solubility of PGMEA.

In the general formula (1-VII), R ⁵² is more preferably a methyl group, an ethyl group, a phenyl group or a benzyl group from the viewpoints of sensitivity and solubility of PGMEA.

Among the general formulas (1-VI) and (1-VII), the compound represented by the general formula (1-VII) is most preferable from the viewpoint of the solubility of PGMEA.

Hereinafter, preferred specific examples of the thiol compounds usable in the present invention are shown, but the present invention is not limited thereto.

In the present specification, the chemical formulas may be described by a simplified structural formula, and particularly, solid lines and the like which do not specify the atoms or substituents represent hydrocarbon groups. In the following specific examples, Me represents a methyl group.

The solubility of these thiol compounds in the PGMEA solvent is preferably 20 g / L or more to 50 g / L or less, more preferably 20 g / L or more to 40 g / L or less, still more preferably 20 g / L or less.

- Method of measuring solubility -

In the present specification, the solubility of the thiol compound is defined as follows

A specific thiol compound was added to 5 mL of a solvent of propylene glycol monomethyl ether acetate (PGMEA), and the solubility was defined as the amount just before the specific thiol compound became insoluble when stirred for 1 hour at 25 ° C.

These thiol compounds can be synthesized by the method described in J. Appl. Chem., 34, 2203-2207 (1961).

The thiol compound may be used singly or in combination of two or more.

When a thiol compound is used in combination, two or more compounds represented by any one of the above general formulas may be used in combination, or compounds represented by other general formulas may be used in combination (for example, a compound represented by general formula (1-VI) And a compound selected from compounds represented by the general formula (1-VII)).

When the curable composition of the present invention contains a thiol compound, the content thereof is preferably in the range of 0.5 to 30 mass% with respect to the mass of the total solid content of the curable composition from the viewpoint of improvement of the curing rate due to balance of polymerization growth rate and chain transfer , More preferably from 1 to 25 mass%, and even more preferably from 3 to 20 mass%.

<(H) Other sensitizers>

The curable composition of the present invention may contain another sensitizer (H) other than the specific sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the wavelength of the photosensitive wavelength within a range that does not impair the effect of the present invention.

As another sensitizer that can be used in the present invention, it is preferable to increase or decrease the radical initiator by an electron transfer mechanism or an energy transfer mechanism.

Other sensitizers which can be used in the present invention include those having the absorption wavelength in the wavelength range of 300 nm to 450 nm belonging to the compounds listed below.

Examples of other preferable sensitizing agents include those having the absorption wavelength in the region of 330 nm to 450 nm, belonging to the following compounds.

Examples of other sensitizers include polynuclear aromatic compounds (e.g., phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (such as fluorene, , Erythrosine, rhodamine B and rose bengal), thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (for example, thiacarbocyanine, oxacarbocyanine) , Thiazines (for example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, etc.) (E.g., anthraquinone), squaluminium (e.g., squalium), coumarins (e.g., 7-diethylamino-4-methylcoumarin ), Ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, tri Pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, benzotriazole derivatives, benzotriazole derivatives, benzotriazole derivatives, benzotriazole derivatives, benzotriazole derivatives, Aromatic ketone compounds such as thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, and Michler's ketone, and heterocyclic compounds such as N-aryloxazolidinone.

The content of the other sensitizer is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass with respect to the total content of the specific sensitizer.

&Lt; (I) Polymerization inhibitor >

In the present invention, it is preferable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated double bond-containing compound during or during the production of the curable composition.

Examples of the thermal polymerization inhibitor usable in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine cerium salt.

The addition amount of the thermal polymerization inhibitor is preferably about 0.01 mass% to about 5 mass% with respect to the mass of the entire composition. Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be localized on the surface of the photosensitive layer during drying after coating. The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

<(J) Adhesion-improving agent>

In the present invention, it is preferable to add an adhesion-improving agent in order to improve the adhesion with a hard surface (substrate). Examples of the adhesion improver include silane coupling agents, titanium coupling agents and aluminum coupling agents.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, Isocyanatopropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ- Trimethoxysilane hydrochloride,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane, aminosilane,? -Mercaptopropyltrimethoxysilane,? -Mercaptopropyltriethoxy Silane, methyltrimethoxysilane, methyltriethoxysil , Vinyltriacetoxysilane,? -Chloropropyltrimethoxysilane, hexamethyldisilazane,? -Anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (? -Me (Methoxymethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride,? -Chloropropylmethyldimethoxysilane,? -Mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane , Trimethylchlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N - (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) (Acryloxymethyl) methyldiethoxysilane, and (acryloxymethyl) methyldimethoxysilane, and Can.

Among these,? -Methacryloxypropyltrimethoxysilane,? -Methacryloxypropyltriethoxysilane,? -Acryloxypropyltrimethoxysilane,? -Acryloxypropyltriethoxysilane,? -Mercaptopropyltri Methoxysilane,? -Aminopropyltriethoxysilane, and? -Trimethoxysilane are preferable, and? -Methacryloxypropyltrimethoxysilane is most preferable.

Examples of the titanium based coupling agent include tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium, tetrastaoxytitanium, di- (Triethanolaminato) titanium, dihydroxy bis (lactate) titanium, tetrakis (2-ethylhexanediolato) titanium, tri-n-butyl Butoxytitanium monostearate, isopropyltriisostearoyl titanate, isopropyltridodecylbenzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctylphosphine) (Ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis Phosphate) oxyacetate titanate, bis (dioctylphosphate Isopropyltriethoxysilane titanate, isopropyltriethoxysilane titanate, isopropyltriethoxysilane titanate, isopropyltriethoxysilane titanate, isopropyltriethoxysilane titanate, isopropyltriethoxysilane titanate, isopropyltriethoxysilane titanate, isopropyltriethoxysilane titanate, Isopropyl tricumyl phenyl titanate, isopropyl tri (N-aminoethyl aminoethyl) titanate, dicumylphenyloxyacetate titanate, and diisostearoyl ethylene titanate.

Examples of the aluminum-based coupling agent include aluminum isopropylate, mono sec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate) , Alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetate bis (ethylacetoacetate), aluminum tris (acetylacetonate), cyclic aluminum oxide isopropylate, and the like.

The addition amount of the adhesion promoter is preferably 0.5 to 30% by mass, more preferably 0.7 to 20% by mass, based on the total solid content of the curable composition.

<Other additives>

In the present invention, in order to improve the physical properties of the cured coating, known additives such as an inorganic filler, a plasticizer, and a sensitizer capable of improving ink deposition of the surface of the photosensitive layer may be added.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate and triacetyl glycerin. When a binder is used And 10% by mass or less based on the total mass of the compound having an ethylenically unsaturated double bond and the binder.

<Thinner>

The curable composition of the present invention may be provided in a state in which it is dissolved in various organic solvents when it is applied on a support in the production of a color filter.

Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl But are not limited to, ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, Propanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , And the like 3-methoxypropyl acetate, N, N- dimethylformamide, dimethyl sulfoxide, butyric γ- lactone, lactic acid, methyl, ethyl lactate.

These solvents may be used alone or in combination. The concentration of the solid content in the organic solvent is preferably 2 to 60% by mass.

The curable composition for a color filter of the present invention is cured with high sensitivity, and storage stability is also good. It also shows high adhesion to the surface of a hard material such as a substrate to which the curable composition is applied.

[Color filter and manufacturing method thereof]

Next, the color filter of the present invention and its manufacturing method will be described.

The color filter of the present invention is characterized by having a coloring pattern formed by using the curable composition for a color filter of the present invention on a support.

Hereinafter, the color filter of the present invention will be described in detail through a manufacturing method thereof (a manufacturing method of a color filter of the present invention).

The method for producing a color filter of the present invention comprises a step of applying a curable composition for a color filter of the present invention on a support to form a layer of a colored curable composition (hereinafter referred to as a "step of forming a colored curable composition layer" , A step of exposing the layer of the colored curable composition through a mask (hereinafter, appropriately referred to as an &quot; exposure step &quot;) and a step of developing the curable composition layer after exposure to form a colored pattern &Quot;). &Lt; / RTI &gt;

Specifically, the curable composition of the present invention is applied directly or through another layer on a support (substrate) to form a photopolymerizable composition layer (a step of forming a colored curable composition layer), exposed through a predetermined mask pattern, The color filter of the present invention can be manufactured by forming only a patterned coating film composed of pixels of each color (three colors or four colors) by curing only the irradiated film portion (exposure process) and developing with a developing solution have.

Hereinafter, each step in the manufacturing method of the present invention will be described.

&Lt; Coloring curable composition layer forming step >

In the step of forming the colored curable composition layer, the curable composition of the present invention is applied onto a support to form a colored curable composition layer.

Examples of the support that can be used in the present step include soda glass, Pyrex (registered trademark) glass, quartz glass and a transparent conductive film adhered thereto, photoelectric conversion element substrates used for imaging elements, For example, a silicon substrate, or a complementary metal oxide semiconductor (CMOS). These substrates may be formed with black stripes for isolating each pixel.

On the support, a primer layer may be formed on the support in order to improve adhesion with the upper layer, prevent diffusion of the material, or planarize the surface of the substrate.

As a method of applying the curable composition of the present invention on a support, various coating methods such as slit coating, inkjet coating, spin coating, flex coating, roll coating, screen printing and the like can be applied.

The coating film thickness of the curable composition is preferably 0.1 to 10 占 퐉, more preferably 0.2 to 5 占 퐉, and even more preferably 0.2 to 3 占 퐉.

The curable composition applied on the support is usually dried at 70 to 110 DEG C for about 2 to 4 minutes to form a colored curable composition layer.

<Exposure Step>

In the exposure step, the layer of the colored curable composition formed in the step of forming the colored curable composition layer is exposed through a mask to cure only the portion of the coated film which is irradiated with light.

The exposure is preferably performed by irradiation of radiation, and ultraviolet rays such as g-line and i-line are preferably used as the radiation usable for exposure, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably 5 mJ to 1500 mJ, more preferably 10 mJ to 1000 mJ, and most preferably 10 mJ to 800 mJ.

<Development Process>

Subsequent to the exposure step, an alkali development treatment (development step) is carried out, and the irradiated portion in the exposure step is eluted into an alkali aqueous solution. As a result, only the photo-cured portion remains.

As the developer, an organic alkali developing solution which does not cause damage to the underlying circuit or the like is preferable. The developing temperature is usually 20 ° C to 30 ° C, and the developing time is 20 to 90 seconds.

Examples of the alkali used in the developing solution include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8- An alkaline aqueous solution in which an organic alkaline compound such as cyclo- [5,4,0] -7-undecene is diluted with pure water to a concentration of 0.001 to 10 mass%, preferably 0.01 to 1 mass%, is used. When a developer comprising such an alkaline aqueous solution is used, it is generally cleaned (rinsed) with purified water after development.

Further, in the manufacturing method of the present invention, the curable composition layer forming step, the exposing step, and the developing step described above are carried out, and then a curing step of curing the colored pattern formed as necessary by heating and / or exposure is included good.

By repeating the above-described steps of forming the color-curable composition layer, the exposure step, and the development step (and, if necessary, the curing step) as many times as the desired number of colors, a color filter having a desired color is produced.

Since the color filter of the present invention uses the curable composition of the present invention as described above, the formed colored pattern exhibits high adhesion with the support substrate and the cured composition is excellent in developing resistance, so that it has excellent exposure sensitivity, It is possible to form a high-resolution pattern having good adherence to the negative substrate and giving a desired cross-sectional shape. Therefore, it can be preferably used for a solid-state image pickup device such as a liquid crystal display device or a CCD, and is particularly preferable for a high-resolution CCD device or CMOS exceeding one million pixels. The color filter of the present invention can be used, for example, as a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing.

(Example)

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples. Unless otherwise stated, &quot;% &quot; and &quot; part &quot; are based on mass.

&Lt; Synthesis of specific sensitizer >

Compounds 1-1 to 1-18 which are compounds represented by the general formula (1-I) of the present invention or compounds represented by the general formula (1-II) are shown in the following Synthesis Examples 1-1 to 1-18 Respectively.

(Synthesis Example 1-1)

4-methoxybenzyl chloride (0.19 mol, 1 eq), triphenylphosphine (PPh ₃ ) (0.19 mol, 1 eq) and N-methylpyrrolidone (NMP) (100 ml) were added to a 300 ml three- Lt; 0 &gt; C for 4 hours. KPF ₆ (0.23 mol, 1.2 eq) was added thereto, and the mixture was stirred at room temperature for 1 hour. As a result, a solid precipitated. The precipitate was filtered, washed with water and dried to obtain a phosphonium salt A. Yield 94%.

Phosphonium salt A (30.8 mmol, 1 eq) and tetrahydrofuran (THF) (100 ml) were added to a 500 ml three-necked flask and stirred in an ice bath. Sodium hydride (NaH) (46.2 mmol, 1.5 eq) / THF (20 ml) was slowly added thereto. After completion of the addition, the mixture was stirred on the ice bath for 15 minutes and then returned to room temperature. To this was added 4-methoxycinnamic aldehyde (30.8 mmol, 1 eq) and the mixture was refluxed for 4 hours. Thereafter, the solution was poured into ice water to precipitate a solid. Filtration was conducted, and further methanol washing was conducted to obtain Compound 1-1. Yield 40%.

(Synthesis Example 1-2)

The above phosphonium salt A (37.8 mmol, 1 eq) and THF (100 ml) were added to a 500 ml three-necked flask and stirred in an ice bath. NaH (56.7 mmol, 1.5 eq) / THF (20 ml) was slowly added thereto, and after completion of the addition, the mixture was stirred on the ice bath for 15 minutes and then returned to room temperature. To it, trans-cinnamaldehyde (37.8 mmol, 1 eq) was added and refluxed for 4 hours. Thereafter, the mixture was poured into ice water to precipitate a solid. Filtration was conducted, and further washing with methanol was carried out to obtain Compound 1-2. Yield 45%.

(Synthesis Example 1-3)

Α-bromo-p-xylene (0.14 mol, 1 eq), triphenylphosphine (0.14 mol, 1 eq) and NMP (100 ml) were added to a 300 ml three-necked flask and the mixture was heated and stirred at 140 ° C. for 2 hours The object was settled. Thereafter, the mixture was poured into water, stirred for 1 hour on an ice bath, filtered, washed with water, and dried to obtain a phosphonium salt B. Yield 87%.

Phosphonium salt B (37.8 mmol, 1 eq) and THF (100 ml) were added to a 500 ml three-necked flask and stirred in an ice bath. NaH (56.7 mmol, 1.5 eq) / THF (20 ml) was slowly added thereto, and after completion of the addition, the mixture was stirred on the ice bath for 15 minutes and then returned to room temperature. To it, trans-cinnamaldehyde (37.8 mmol, 1 eq) was added and refluxed for 3 hours. Thereafter, the reaction mixture was poured into ice water to precipitate a solid. Filtration was conducted, and methanol slurry was carried out to obtain Compound 1-3. Yield 60%.

(Synthesis Example 1-4)

The above phosphonium salt B (34.2 mmol, 1 eq) and THF (100 ml) were added to a 500 ml three-necked flask and stirred in an ice bath. NaH (51.3 mmol, 1.5 eq) / THF (40 ml) was slowly added thereto, and after completion of the addition, the mixture was stirred on the ice bath for 15 minutes and then returned to room temperature. To this was added a-methyl cinnamaldehyde (34.2 mmol, 1 eq) and the mixture was refluxed for 3 hours. Thereafter, the mixture was poured into ice water to precipitate a solid. Filtration was conducted, and further methanol slurry was carried out to obtain Compound 1-4. Yield 40%.

(Synthesis Example 1-5)

NaH (78.6 mmol, 1.5 eq), phosphonium salt C (52.4 mmol, 1 eq) and THF (100 ml) were added to a 500 ml three-necked flask and stirred in an ice bath. A sulfonium salt (52.4 mmol, 1 eq) was slowly added thereto, and after completion of the addition, the mixture was stirred on an ice bath for 15 minutes and then returned to room temperature. To it, trans-cinnamaldehyde (52.4 mmol, 1 eq) was added and refluxed for 3 hours. Thereafter, the mixture was poured into ice water to precipitate a solid. Filtration was conducted, and methanol slurry was carried out to obtain Compound 1-5. Yield 40%.

(Synthesis Example 1-6)

NaH (78.6 mmol, 1.5 eq), phosphonium salt D (52.4 mmol, 1 eq) and THF (100 ml) were added to a 500 ml three-necked flask and stirred in an ice bath. NaH (52.4 mmol, 1 eq) was slowly added thereto, and after the addition was completed, the mixture was stirred on the ice bath for 15 minutes, and then returned to room temperature. To it, trans-cinnamaldehyde (52.4 mmol, 1 eq) was added and refluxed for 3 hours. Thereafter, solid was precipitated as a result of filtration. The solid was filtered, and the filtrate was concentrated. The filtrate was concentrated and purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1) to obtain compound 1-6. Yield 5%.

(Synthesis Example 1-7)

In the synthesis examples of the compounds 1-5, the following compounds 1-7 were obtained in the same manner as the phosphonium salt C, except that the following phosphonium salt E was used.

(Synthesis Example 1-8)

In the synthesis examples of the compounds 1-5, the following compounds 1-8 were obtained in the same manner as the phosphonium salt C, except that the following phosphonium salt F was used.

(Synthesis Example 1-9)

In the synthesis examples of the compounds 1-5, the following compounds 1-9 were obtained in the same manner as the phosphonium salt C, except that the phosphonium salt C was replaced with the following phosphonium salt G.

(Synthesis Example 1-10)

In the synthesis examples of the compounds 1-5, the following compounds 1-10 were obtained in the same manner as the phosphonium salt C except that the phosphonium salt C was replaced with the following phosphonium salt H.

(Synthesis Example 1-11)

In the synthesis examples of the compounds 1-5, the following compound 1-11 was obtained in the same manner as the phosphonium salt C, except that the following phosphonium salt I was used.

(Synthesis Example 1-12)

In the synthesis examples of the compounds 1-5, the following compound 1-12 was obtained in the same manner as the phosphonium salt C, except that the following phosphonium salt J was used.

(Synthesis Example 1-13)

In the synthesis examples of the compounds 1-5, the following compounds 1-13 were obtained in the same manner as the phosphonium salt C, except that the following phosphonium salt K was used.

(Synthesis Example 1-14)

16.9 g (40.7 mmol) of phosphonium salt L and tetrahydrofuran (THF) (100 ml) were added to a 500 ml three-necked flask, and the mixture was stirred in an ice bath. 7.4 g (38.4 mmol) of SM-28 (28 wt% MeOH solution of NaOMe) was slowly added thereto, and after completion of the addition, the mixture was stirred on the ice bath for 15 minutes and then returned to room temperature. 10 g (36.6 mmol) of p-diphenylaminobenzaldehyde was added thereto, and the mixture was heated under reflux for 2 hours. Thereafter, the reaction mixture was poured into ice water to precipitate a solid. Filtration was conducted, and further methanol washing was carried out to obtain Compound 1-14. Yield 40%.

(Synthesis Example 1-15)

In the synthesis example of the compound 1-14, the following compound 1-15 was obtained in the same manner as in the synthesis of p-diphenylaminobenzaldehyde, except that p-diphenylaminobenzaldehyde was replaced with diethylaminobenzaldehyde.

(Synthesis Example 1-16)

In the synthesis examples of the compound 1-14, the following compound 1-16 was obtained in the same manner as in the synthesis of p-diphenylaminobenzaldehyde, except that p-diphenylaminobenzaldehyde was replaced with 3,4,5-trimethoxybenzaldehyde.

(Synthesis Example 1-17)

In the synthesis example of the compound 1-14, the following compound 1-17 was obtained in the same manner as in the synthesis of p-diphenylaminobenzaldehyde except that 4-diethylamino-2-methoxybenzaldehyde was used.

(Synthesis Example 1-18)

In the synthesis example of the compound 1-14, the following compound 1-18 was obtained in the same manner as in p-diphenylaminobenzaldehyde except that 2,4-dimethoxybenzaldehyde was used.

(Synthesis Example 1-19)

In the synthesis example of the compound 1-14, the following compound 1-19 was obtained in the same manner as the phosphonium salt L except that the following phosphonium salt M was used.

The synthesis of the phosphonium salts C to K used in Synthesis Examples 1-5 to 1-13 was carried out in the same manner as in Synthesis Examples 1-3 except that? -Bromo-p-xylene in the synthesis of the phosphonium salt B used in Synthesis Example 1-3 was replaced with a suitable compound , The synthesis was carried out in the same manner as the synthesis of the phosphonium salt B.

&Lt; Measurement of molar extinction coefficient &

Methoxy-2-propanol solution of 0.01 g / L of the compounds 1-1 to 1-19 and Comparative Compounds 1-1 to 1-4 (the structures of which are shown in the following Table 3) was prepared, 5 uv-vis-NIR SPECTROPHOTMETERS, and the molar extinction coefficient? (Mol ^-1 · L · cm ^-1 ) at 365 nm was calculated.

The structures of the compounds 1-1 to 1-19 and the molar extinction coefficient (?) At 365 nm are collectively shown in Tables 1 and 2 below. The structures of Comparative Compounds 1-1 to 1-4 and the molar extinction coefficient (?) At 365 nm used in Comparative Examples to be described later are shown in Table 3.

Hereinafter, the curable composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the scope thereof is exceeded.

[Example 1-1-1]

〔One. Preparation of colored curable composition 1-A-1]

Here, an example in which a colored curable composition 1-A-1 containing a coloring agent (pigment) is prepared for forming a color filter for use in a liquid crystal display device is described.

1-1. Preparation of pigment dispersion (P1)

40 parts by mass of a 30/70 (by mass) mixture of CI Pigment Green 36 and CI Pigment Yellow 219 as a pigment and 10 parts by mass of BYK2001 (Disperbyk, manufactured by BYK, solid content concentration of 45.1% by mass) About 4.51 parts by mass), and ethyl 3-ethoxypropionate as a solvent (150 parts by mass) were mixed and dispersed for 15 hours by a bead mill to prepare a pigment dispersion (P1).

The average particle diameter of the pigment for the obtained pigment dispersion (P1) was measured by a dynamic light scattering method and found to be 200 nm.

1-2. Preparation of colored curable composition 1-A-1 (coating liquid)

The components of the following composition 1-A-1 were mixed and dissolved to prepare a colored curable composition 1-A-1.

&Lt; Composition 1-A-1 &

Pigment dispersion (P1) 600 parts by mass

· Alkali-soluble resin

  (Benzyl methacrylate / methacrylic acid / hydroxyethyl

   Methacrylate copolymer, mol ratio: 80/10/10,

   Mw: 10000) 190 parts by mass

Dipentaerythritol hexaacrylate [polymerizable compound] 60 parts by weight

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-

  1,2'-biimidazole [photopolymerization initiator] 60 parts by mass

占 Compound 1-1 (specific sensitizer) 40 parts by mass

Notarization: 40 parts by mass of 2-mercaptobenzimidazole

Surfactant: 1 part by mass (trade name: tetronick 150R1, BASF)

Solvent: 1000 parts by mass of propylene glycol monomethyl ether acetate

? -Methacryloxypropyltriethoxysilane 10 parts by mass

〔2. Fabrication of color filter]

2-1. Formation of Curable Composition Layer

The colored curable composition 1-A-1 containing the pigment obtained above was applied as a resist solution to a glass substrate of 550 mm x 650 mm under the following conditions, and then allowed to stand in this state for 10 minutes to be applied to a new glass substrate , Followed by vacuum drying and prebaking (100 DEG C for 80 seconds) to form a colored curable composition coating film (colored curable composition layer).

(Slit application condition)

Clearance at the opening of the coating head tip: 50 탆

Coating speed: 100 mm / sec

Clearance between substrate and coating head: 150 m

Coating thickness (dry thickness): 2 탆

Application temperature: 23 ℃

2-2. Exposure, development

Thereafter, the coated film of the colored curable composition was exposed in a pattern using a 2.5 kW ultra-high pressure mercury lamp, and after the exposure, the entire surface of the coated film was covered with a 10% aqueous solution of an organic developer (trade name: CD, manufactured by Fuji Film Arch Co., Ltd.) I stopped for 60 seconds.

2-3. Heat treatment

After stopping, the pure water was sprayed into a shower, the developer was washed away, and the coated film subjected to the photo-curing treatment and the developing treatment was heated in an oven at 220 캜 for 1 hour (post-baking). As a result, a colored pattern was formed on the glass substrate to obtain a color filter.

[3. Performance evaluation]

The storage stability of the colored curable composition 1-A-1 (coating liquid) prepared above and the exposure sensitivity of the colored curable composition film (colored layer) formed on the glass substrate using the colored curable composition 1-A- , Substrate adhesion, developability, and cross-sectional shape of the colored pattern were evaluated as follows. The results are shown in Table 4.

3-1. The storage stability of the colored curable composition 1-A-1

After curing the coating solution for one month at room temperature, the degree of precipitation of the foreign matter was visually confirmed and evaluated according to the following criteria.

<Criteria>

○: Precipitation was not confirmed.

B: A little precipitation was confirmed.

X: precipitation was confirmed.

3-2. The exposure sensitivity of the coating film (colored layer)

The colored curable composition 1-A-1 (coating liquid) was coated on a glass substrate and dried to give a film thickness of 1.0 탆. The conditions for spin coating were 5 seconds at 300 rpm, 20 seconds at 800 rpm, and drying conditions at 100 캜 for 80 seconds. Next, exposure was performed at various exposure amounts of 10 to 1600 mJ / cm &lt; 2 &gt; using a test photomask having a line width of 2.0 mu m. Next, development was carried out using a developer of 60% CD-2000 (manufactured by Fuji Film Electronics Materials Co., Ltd.) at 25 캜 for 60 seconds. After rinsing with flowing water for 20 seconds, spray drying was performed to complete the patterning. The minimum exposure amount at which the film thickness after development in the light-irradiated area in the exposure step was 95% or more with respect to 100% of the film thickness before exposure was evaluated as exposure sensitivity. The smaller the value of the exposure sensitivity, the higher the sensitivity.

3-3. Developability, pattern cross-sectional shape, substrate adhesion

The substrate surface and cross-sectional shape after post-baking were evaluated by an optical microscope and an SEM photographic observation by a conventional method to evaluate developability, substrate adhesion, and cross-sectional shape of the pattern. Details of the evaluation method are as follows.

<Developability>

In the exposure step, the presence or absence of a residue of a region not exposed to light (unexposed portion) was observed to evaluate developability.

○: No residues were observed in minerals.

?: A small amount of residue was found on the unexposed portion, but there was no practical problem.

X: Remnant was remarkably confirmed in the unexposed area.

&Lt; Substrate adhesion property &

As the evaluation of the substrate adhesion, whether or not a pattern defect occurred was observed. These evaluation items were evaluated based on the following criteria

?: No pattern defect was observed at all.

DELTA: The pattern defect was hardly observed, but a partial defect was observed.

X: Pattern defects were remarkably observed.

&Lt; Pattern cross-sectional shape &

Sectional shape of the formed pattern was observed. The pattern cross-sectional shape is most preferably a net taper, and the rectangle is next preferred. Reverse taper is not preferred.

[Examples 1-1-2 to 1-1-26]

A specific sensitizer, a photopolymerization initiator, and a notarized sensitizer in the composition 1-A-1 used in the preparation of the colored curable composition 1-A-1 in Example 1-1-1 were changed as shown in Table 4 Except that coloring curable compositions 1-A-2 to A-26 were prepared in the same manner as in Example 1-1-1, and a color filter having a coloring pattern using the same was obtained. In addition, the same evaluation as in Example 1-1-1 was carried out. The results are shown in Table 4.

[Comparative Example 1-1-1]

The same procedures as in Examples 1-1-1 and 1-1-1 were conducted except that the composition 1-A-1 used in the preparation of the colored curable composition 1-A-1 in Example 1-1-1 was changed to the composition 1-B-1 described below. Similarly, a color filter was prepared by preparing a coloring curable composition 1-B-1 for comparison and forming a coloring pattern. In addition, the same evaluation as in Example 1-1-1 was carried out. The results are shown in Table 4.

<Composition 1-B-1>

Pigment dispersion (P1) 600 parts by mass

· Alkali-soluble resin

 (Benzyl methacrylate / methacrylic acid / hydroxyethyl

  Methacrylate copolymer, mol ratio: 80/10/10,

  Mw: 10000) 200 parts by mass

Dipentaerythritol hexaacrylate [polymerizable compound] 60 parts by weight

· 1- [4- (phenylthio) phenyl] -2-

  (O-benzoyloxime) [Photopolymerization initiator] 140 parts by mass

Solvent: 1000 parts by mass of propylene glycol monomethyl ether acetate

1 part by mass of a surfactant (trade name: tetronick 150R1, BASF)

[Comparative Examples 1-1-2 to 1-1-5]

Except that the specific color sensitizing agent, the photopolymerization initiator, and the notarization sensitizer were changed to the comparative compounds, photopolymerization initiators, and co-sensitizers shown in Table 4 below in the colored curable composition 1-A-1 prepared in Example 1-1-1 2 to B-5 for comparison were prepared in the same manner as in Example 1-1-1, and a color filter having a coloring pattern using the color-curable compositions B-2 to B-5 was obtained. In addition, the same evaluation as in Example 1-1-1 was carried out. The results are shown in Table 4.

The photopolymerization initiators D1 to D3 and the notarization sensitizers F1 to F3 shown in Table 4 are the following compounds.

D1: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-

    Tetraphenyl-1,2'-biimidazole

D2: 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime)

D3: 4-benzoxorane-2,6-di (trichloromethyl) -s-triazine

F1: 2-mercaptobenzoimidazole

F2: 2-Mercaptobenzothiazole

F3: 4,4'-bis (diethylamino) benzophenone

F4: N-phenyl-2-mercaptobenzoimidazole

From the results shown in Table 4, it can be seen that the colored curable compositions of the respective Examples containing specific sensitizers (Compounds 1-1 to 1-18) are excellent in storage stability in the solution state. In the case of forming a colored pattern on the support using this colored curable composition, it is preferable to use a coloring composition which does not contain a specific sensitizer or each of comparative examples using Comparative Compounds 1-1 to 1-4 in place of a specific sensitizer It is understood that a color filter having high exposure sensitivity and excellent developability as well as excellent substrate adhesion and pattern cross-sectional shape can be obtained.

Hereinafter, an example in which a curable composition containing a colorant (dye) is prepared for forming a color filter for a solid-state image sensor will be described.

[Example 1-2-1]

〔One. Preparation of resist solution]

The components of the following composition were mixed and dissolved to prepare a resist solution.

- Composition of resist solution -

Propylene glycol monomethyl ether acetate 19.20 parts by mass

  (PGMEA)

· Ethyl acetate 36.67 parts by mass

Resin 30.51 parts by mass

 [Benzyl methacrylate / methacrylic acid / methacrylic acid

   -2-hydroxyethyl copolymer (molar ratio = 60/22/18)

   Of 40% PGMEA solution]

12.20 parts by mass of dipentaerythritol hexaacrylate

Polymerization inhibitor (p-methoxyphenol) 0.0061 parts by mass

· Fluorine-based surfactant 0.83 parts by mass

  [F-475, manufactured by Dainippon Ink &amp; Chemicals, Incorporated)

Photopolymerization initiator 0.586 parts by mass

  [TAZ-107 (trihalomethyl triazine-based photopolymerization initiator), Midorikagaku]

〔2. Preparation of a silicon wafer substrate on which a primer layer was formed]

A 6-inch silicon wafer was heated in an oven at 200 ° C for 30 minutes. Subsequently, the resist solution was coated on the silicon wafer so that the dry film thickness became 2 탆, and further heated and dried in an oven at 220 캜 for 1 hour to form a primer layer to obtain a silicon wafer substrate having a primer layer formed thereon.

[3. Preparation of colored curable composition 1-C-1]

The following compound 1-C-1 was mixed and dissolved to prepare a colored photosensitive resin composition 1-C-1.

&Lt; Composition 1-C-1 >

Cyclohexanone (solvent) 80 parts by mass

C.I.Acid Blue 108 [Colorant] 7.5 parts by mass

C.I. Solvent Yellow 162 [Colorant] 2.5 parts by mass

· Tetra-erythritol triacrylate and

  Dipentaerythritol hexaacrylate

  Of 3: 7 [Polymerizable compound] 7.0 parts by mass

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-

  1,2'-biimidazole [photopolymerization initiator] 1 part by mass

占 Compound 1-1 [specific sensitizer] 0.7 parts by mass

Notarizing agent: 2-mercaptobenzoimidazole 0.8 part by weight

0.5 parts by mass of glycerol propoxylate

  (Number average molecular weight Mn: 1,500, molar extinction coefficient? = 0, colorless compound)

4. Evaluation of storage stability of colored curable composition 1-C-1 (coating liquid)

After the colored curable composition 1-C-1 was stored at room temperature for one month, the degree of precipitation of the foreign matter was visually confirmed and evaluated according to the following criteria.

<Criteria>

○: Precipitation was not confirmed.

B: A little precipitation was confirmed.

X: precipitation was confirmed.

5. Production and Evaluation of Color Filter by Coloring Curable Composition 1-C-1

The colored photosensitive resin composition 1-C-1 prepared in the above 3. was coated on a primer layer of a silicon wafer substrate on which the primer layer obtained in the above 2. was formed, to form a photocurable coating film. Then, a heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 캜 so that the dried film thickness of the coated film became 0.9 탆.

Subsequently, an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) was used to irradiate an exposure dose of 10 to 1600 mJ / cm 2 through an island pattern mask having a pattern of 2 μm × 2 μm at a wavelength of 365 nm.

Thereafter, the silicon wafer substrate having the coated film formed thereon was mounted on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemtronics Co., Ltd.), and a CD-2000 (manufactured by FUJIFILM ELECTRONICS MATERIALS Ltd.) was used for paddle development at 23 ° C for 60 seconds to form a colored pattern on a silicon wafer substrate.

The silicon wafer substrate on which the coloring pattern was formed was fixed to the horizontal rotary table by a vacuum chucking method. The silicon wafer substrate was rotated at a rotation speed of 50 rpm by a rotary device, pure water was sprayed from a spray nozzle Followed by rinsing, and then spray-dried to prepare a color filter.

&Lt; Exposure sensitivity >

The minimum exposure amount at which the film thickness after development in the light-irradiated area in the exposure step was 95% or more with respect to 100% of the film thickness before exposure was evaluated as exposure sensitivity. The smaller the value of the exposure sensitivity, the higher the sensitivity. The size of the coloring pattern was measured using a measurement SEM "S-9260A" (manufactured by Hitachi High-Technologies Corporation) at that time. The closer the pattern size is to 2 mu m, the better the curability and the better the sensitivity.

The results of the measurement evaluation are shown in Table 5 below.

&Lt; Substrate adhesion property &

The occurrence of pattern defects was observed as an evaluation of substrate adhesion. These evaluation items were evaluated based on the following criteria

?: No pattern defect was observed at all.

DELTA: The pattern defect was hardly observed, but a partial defect was observed.

X: Pattern defects were remarkably observed.

&Lt; Pattern cross-sectional shape &

Sectional shape of the formed pattern was observed. The pattern cross-sectional shape is most preferably a net taper, followed by a rectangle and reverse taper.

[Comparative Example 1-2-1]

In all of Examples 1-2-1, except that the composition 1-C-1 used in the preparation of the colored curable composition 1-C-1 was changed to the following composition 1-D-1, In the same manner, a colored curable composition D-1 for comparison was prepared, and a colored pattern was formed to obtain a color filter. The same evaluation as in Example 1-2-1 was carried out. The results are shown in Table 5.

&Lt; Composition 1-D-1 >

80 parts by mass of cyclohexanone

Colorant CI Acid Blue 108 7.5 parts by mass

Colorant C.I. Solvent Yellow 162 2.5 parts by mass

· Tetra-erythritol triacrylate and

  Of dipentaerythritol hexaacrylate

  3: 7 [Polymerizable compound] 7.0 parts by mass

· Oxime type photopolymerization initiator

  (CGI-124, manufactured by Ciba Specialty Chemicals,

  Photopolymerization initiator) 2.5 parts by mass

Glycerol propoxylate (number-average molecular weight Mn: 1500) 0.5 parts by mass

[Examples 1-2-2 to 1-2-26, Comparative Examples 1-2-2 to 1-2-5]

The specific sensitizer, the photopolymerization initiator and the notarized sensitizer in the composition 1-C-1 used in the preparation of the colored photosensitive resin composition 1-C-1 in Example 1-2-1 were changed as shown in Table 5 below C-2 to 1-C-26 and the comparative colored curable compositions 1-C-27 to 1-C-30 were prepared in the same manner as in Example 1-2-1 except that the coloring photosensitive resin compositions 1-C- Formation of a coloring pattern, and evaluation were carried out. The results are shown in Table 5 below.

[Examples 1-2-24]

In all of Examples 1-2-1, except that the composition 1-C-1 used for the preparation of the colored curable composition 1-C-1 was changed to the following composition 1-E-1, In the same manner, the colored curable composition 1-E-1 was prepared and a colored pattern was formed to obtain a color filter. The same evaluation as in Example 1-2-1 was carried out. The results are shown in Table 5.

<Composition 1-E-1>

80 parts by mass of cyclohexanone

Colorant C.I. Pigment Red 254 6.0 parts by mass

Colorant CI Pigment Yellow 139 4.0 parts by mass

· Tetra-erythritol triacrylate and

  Of dipentaerythritol hexaacrylate

  3: 7 [Polymerizable compound] 7.0 parts by mass

- 2,2'-bis (2-chlorophenyl) -

  4,4 ', 5,5'-tetraphenyl-

  1,2'-biimidazole [photopolymerization initiator] 1 part by mass

占 Compound 1-1 [specific sensitizer] 0.7 parts by mass

Notarizing agent: 2-mercaptobenzoimidazole 0.8 part by weight

Glycerol propoxylate (number-average molecular weight Mn: 1500) 0.5 parts by mass

[Examples 1-2-25 and Comparative Examples 1-2-6]

The specific sensitizers, photopolymerization initiators and notarization sensitizers in the composition 1-E-1 used in the preparation of the colored photosensitive resin composition 1-E-1 in Examples 1-2-24 were changed as shown in Table 5 below , The colored photosensitive resin composition 1-E-2 and the comparative colored curable composition 1-E-3 were prepared in the same manner as in Examples 1-2-24, and coloring patterns were formed and evaluated. The results are shown in Table 5 below.

[Comparative Example 1-2-7]

In all of Examples 1-2-1, except that the composition 1-C-1 used in the preparation of the colored curable composition 1-C-1 was changed to the following composition 1-F-1, In the same manner, a color-curable composition 1-F-1 for comparison was prepared and a coloring pattern was formed to obtain a color filter. The same evaluation as in Example 1-2-1 was carried out. The results are shown in Table 5.

<Composition 1-F-1>

80 parts by mass of cyclohexanone

Colorant C.I. Pigment Red 254 6.0 parts by mass

Colorant CI Pigment Yellow 139 4.0 parts by mass

· Tetra-erythritol triacrylate and

  Of dipentaerythritol hexaacrylate

  3: 7 [Polymerizable compound] 7.0 parts by mass

· Oxime type photopolymerization initiator

  (CGI-124, manufactured by Ciba Specialty Chemicals,

   Photopolymerization initiator) 2.5 parts by mass

Glycerol propoxylate (number-average molecular weight Mn: 1500) 0.5 parts by mass

The photopolymerization initiators D1 to D3, notarization sensitizers F1 to F3, and Comparative Compounds 1-1 to 1-4 shown in Table 5 are the above-mentioned compounds.

From the results in Table 5, it can be seen that each of the color-curing compositions of Examples containing specific sensitizers (Compounds 1-1 to 1-19) is excellent in storage stability in the solution state, and even when images are formed on a support, Or both of the substrate adhesion and the cross-sectional shape of the pattern were excellent in comparison with the comparative examples using Comparative Compounds 1-1 to 1-4 in place of specific sensitizers Able to know.

[Example 2-1-1]

An example of preparing a curable composition coating film by preparing the curable composition 2-A-1 and using the curable composition 2-A-1 will be described.

〔One. Preparation of Curable Composition 2-A-1 (Coating Liquid)]

The following composition 2-A-1 was uniformly mixed and dissolved to prepare a curable composition 2-A-1.

&Lt; Composition 2-A-1 &

Photopolymerization initiator [UVI-6992 (manufactured by Dow Chemical)] 0.08 mmol

Polymerizable compound (pentaerythritol tetraacrylate) 1 g

Binder resin (polymethyl methacrylate (reagent manufactured by Aldrich,

  Mw: c.a. 996000) 1 g

Specific sensitizer (Compound 2-1) 0.08 mmol

Solvent (cyclohexanone) 16 g

〔2. Preparation of curable composition coating film]

The curable composition 2-A-1 obtained above was applied to a 10 cm x 10 cm glass substrate (AN635, manufactured by Asahi Glass Co., Ltd.) as a resist solution by a spin coater and dried at 40 占 폚 for 10 minutes to form a 1.5 占 퐉 film Thick curable composition coating film.

[3. Performance evaluation]

Using the curable composition 2-A-1 (coating solution) prepared above, the sensitivity stage number of the curable composition coating film formed on a glass substrate was evaluated as follows. The results are shown in Table 7.

- Sensitivity stage of curable composition coating film -

A 21 square step tablet (gray scale film made by Dainippon Screen) was placed on the curable composition coating film formed as described above, and light of a high pressure mercury lamp of 500 mW manufactured by Ushio DENKI Co., Ltd. was exposed through a hot-wire cut filter for 30 seconds , And impregnated in toluene for 60 seconds to carry out development processing, and the number of stages of completely cured and insoluble portions corresponding to the step tablets was evaluated as sensitivity. The higher the number, the higher the sensitivity.

[Examples 2-1-2 to 2-1-12, Comparative Examples 2-1-1 to 2-1-7]

A-2 to A-19 were obtained in the same manner as in Example 2-1-1, except that the specific sensitizer and the photopolymerization initiator were changed to those shown in Table 7 below. And a color filter having a curable composition coating film formed by using the coating film was obtained. The same evaluation as in Example 2-1-1 was performed. The results are shown in Table 7.

The compounds 1 to 6 shown in Table 7 and the comparative compounds 1 to 3 show the compounds shown in Table 6. Irgacure OXE-01, Compound E, LD-5, and Compound I shown in Table 7 are the compounds shown below.

From the results in Table 7, the curable compositions of the respective Examples containing specific sensitizers (Compounds 2-1 to 2-6) were compared with Comparative Compounds 2-1 to 2-3 It can be seen that the exposure sensitivity is high.

[Example 2-1]

Next, an example of preparing a color filter for a liquid crystal display element using the colored curable composition 2-B-1 containing a coloring agent (pigment) and preparing the colored curable composition 2-B-1 will be described.

〔One. Preparation of colored curable composition 2-B-1]

1-1. Preparation of pigment dispersion (P1)

A pigment dispersion prepared in the same manner as in Example 1-1-1 was used.

1-2. Preparation of colored curable composition 2-B-1 (coating liquid)

The components of the following composition 2-B-1 were mixed and dissolved to prepare a colored curable composition 2-B-1.

&Lt; Composition 2-B-1 >

Pigment dispersion (P1) 600 parts by mass

200 parts by mass of an alkali-soluble resin (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, mol ratio: 80/10/10, Mw: 10000)

60 parts by mass of a polymerizable compound (dipentaerythritol hexaacrylate)

Photopolymerization initiator (2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole): D1 60 parts by mass

Specific sensitizer (Compound 2-1) 40 parts by mass

1 part by mass of a surfactant (trade name: tetronick 150R1, BASF)

· Notarization agent (mercaptobenzothiazole): A1 40 parts by mass

Adhesion improving agent (? -Methacryloxypropyltriethoxysilane) 5 parts by mass

Solvent (propylene glycol monomethyl ether acetate) 1000 parts by mass

〔2. Fabrication of color filter]

A colored curable composition film (colored curable composition layer) was formed in the same manner as in Example 1-1-1 except that the colored curable composition 2-B-1 was used instead of the colored curable composition 1-A-1, , Development and heat treatment to obtain a color filter.

[3. Performance evaluation]

The colored curable composition 2-B-1 (coating liquid) prepared above was evaluated in the same manner as in Example 1-1-1. The results are shown in Table 7.

[Comparative Example 2-1]

A color filter having a coloring pattern was obtained in the same manner as in Example 2-2-1, except that the color photosensitive composition 2-B-1 was changed to the composition shown below in Example 2-2-1. The same evaluation as in Example 2-2-1 was performed. The results are shown in Table 8.

The components of the following composition 2-B-11 were mixed and dissolved to prepare a colored curable composition 2-B-11.

&Lt; Composition 2-B-11 >

Pigment dispersion (P1) 600 parts by mass

200 parts by mass of an alkali-soluble resin (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, mol ratio: 80/10/10, Mw: 10000)

60 parts by mass of a polymerizable compound (dipentaerythritol hexaacrylate)

Photopolymerization initiator (1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime): 60 parts by mass of D2

1 part by mass of a surfactant (trade name: tetronick 150R1, BASF)

Solvent (propylene glycol monomethyl ether acetate) 1,000 parts by mass

[Examples 2-2-2 to 2-10, Comparative Examples 2-2-2 to 2-4]

Except that the specific sensitizer, the photopolymerization initiator, and the notarized sensitizer in the composition 2-B-1 used in the preparation of the colored curable composition 2-B-1 in Example 2-2-1 were changed to those shown in the following Table 8 Coloring photosensitive compositions 2-B-2 to 2-B-10 and 2-B-12 to 2-B-14 were prepared in the same manner as in Example 2-2-1, A filter was obtained. The same evaluation as in Example 2-2-1 was performed. The results are shown in Table 8.

The photopolymerization initiators D1 to D4 and the notarization sensitizers A1 and A2 shown in Table 8 are the following compounds.

D1: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-

D2: 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime)

D3: 4-benzoxorane-2,6-di (trichloromethyl) -s-triazine

D4: Irgacure 784 (manufactured by ciba)

A1: Mercaptobenzothiazole

A2: N-phenylmercaptobenzimidazole

From the results shown in Table 8, it can be seen that the colored curable compositions of the respective Examples containing specific sensitizers (Compounds 2-1 to 2-6) have excellent storage stability in the solution state. When the colored curable composition was used to form a colored pattern on the support, each of Comparative Examples 2-1 to 2-3 was replaced with a specific sensitizer in place of the specific sensitizer, It can be seen that a color filter having high sensitivity and excellent developability as well as excellent substrate adhesion and pattern cross-sectional shape can be obtained.

Hereinafter, an example will be described in which a colored curable composition containing a colorant (pigment) for use in a solid-state imaging device is prepared, and a color filter for a solid-state imaging device is manufactured using the colored curable composition.

[Example 2-3-1]

〔One. Preparation of resist solution]

A resist solution was prepared in the same manner as in Example 1-2-1.

〔2. Preparation of a silicon wafer substrate on which a primer layer was formed]

A silicon wafer substrate on which a primer layer was formed was obtained in the same manner as in Example 1-2-1.

[3. Preparation of colored curable composition 2-C-1]

The following 2-C-1 compounds were mixed and dissolved to prepare a colored curable composition 2-C-1.

&Lt; Composition 2-C-1 &

Solvent (cyclohexanone) 80 parts by mass

Colorant (CI Acid Blue 108) 7.5 parts by mass

Colorant (CI Solvent Yellow 162) 2.5 parts by mass

7.0 parts by mass of a polymerizable compound (3: 7 mixture of tetramethylolpropane triacrylate and dipentaerythritol hexaacrylate)

Photopolymerization initiator (2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole): 1 part by mass

Specific sensitizer (Compound 2-1) 0.8 parts by mass

Notifiable Substance (Mercaptobenzothiazole): 0.7 parts by mass of the above-mentioned (A1)

0.5 parts by mass of glycerol propoxylate

(Number average molecular weight Mn: 1,500, molar extinction coefficient? = 0, colorless compound)

〔4. Evaluation of storage stability of colored curable composition 2-C-1 (coating liquid)] [

As in Example 1-2-1, the colored curable composition 2-C-1 was stored at room temperature for one month and evaluated. The results of the measurement evaluation are shown in Table 9 below.

[5. Preparation and evaluation of color filter using colored curable composition 2-C-1]

A color filter was produced in the same manner as in Example 1-2-1 except that the colored photosensitive resin composition 2-C-1 was used instead of the colored curable composition 1-C-1.

&Lt; Exposure sensitivity >

The exposure sensitivity was evaluated in the same manner as in Example 1-2-1. The results of the measurement evaluation are shown in Table 9 below.

<Developability, substrate adhesion, pattern cross-sectional shape>

Developability, substrate adhesion, and pattern cross-sectional shape were evaluated based on the evaluation criteria described in Examples 2-2-1 to 2-2-10. The results of the measurement evaluation are shown in Table 9 below.

[Example 2-3-2]

In the same manner as in Example 2-3-1 except that the colored photosensitive composition 2-C-1 was changed to the composition 2-C-2 shown below in Example 2-3-1, a color having a coloring pattern A filter was obtained. The same evaluation as in Example 2-3-1 was carried out. The results are shown in Table 9.

The components of the following composition 2-C-2 were mixed and dissolved to prepare a colored curable composition 2-C-2.

&Lt; Composition 2-C-2 &

Solvent (cyclohexanone) 80 parts by mass

Colorant (CI Pigment Red 254) 6.0 parts by mass

Colorant (CI Pigment Yellow 139) 4.0 parts by mass

7.0 parts by mass of a polymerizable compound (3: 7 mixture of tetramethylolpropane triacrylate and dipentaerythritol hexaacrylate)

Photopolymerization initiator (1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime)

  : (D2 above) 1 part by mass

Specific sensitizer (Compound 2-1) 0.8 parts by mass

Notifiable Substance (Mercaptobenzothiazole): 0.7 parts by mass of the above-mentioned (A1)

0.5 parts by mass of glycerol propoxylate

(Number average molecular weight Mn: 1,500, molar extinction coefficient? = 0, colorless compound)

[Examples 2-3-3 to 2-3-12]

Except that the specific sensitizer, the photopolymerization initiator, and the notarized sensitizer in the composition 2-C-1 used in the preparation of the colored curable composition 2-C-1 in Example 2-3-1 were changed to those shown in the following Table 9 , Color photosensitive compositions 2-C-3 to 2-C-12 were prepared in the same manner as in Example 2-3-1 to obtain a color filter having a coloring pattern using the same. The same evaluation as in Example 2-3-1 was carried out. The results are shown in Table 9.

[Comparative Example 2-3-1]

The procedure of Example 2-3-1 was repeated except that the composition 2-C-1 used in the preparation of the colored curable composition 2-C-1 in Example 2-3-1 was changed to the following composition 2-C-13, , A coloring curable composition 2-C-13 for comparison was prepared, and a coloring pattern was formed to obtain a color filter. The same evaluation as in Example 2-3-1 was carried out. The results are shown in Table 9.

&Lt; Composition 2-C-13 >

80 parts by mass of cyclohexanone

Colorant (CI Acid Blue 108) 7.5 parts by mass

Colorant (CI Solvent Yellow 162) 2.5 parts by mass

7.0 parts by mass of a polymerizable compound (3: 7 mixture of tetramethylolpropane triacrylate and dipentaerythritol hexaacrylate)

??? 2.5 parts by mass of a photopolymerization initiator (oxime-based photopolymerization initiator: CGI-124, manufactured by Ciba Specialty Chemicals)

0.5 parts by mass of glycerol propoxylate

(Number average molecular weight Mn: 1,500, molar extinction coefficient? = 0, colorless compound)

[Comparative Example 2-3-5]

In all of Examples 2-3-1, except that the composition 2-C-1 used in the preparation of the colored curable composition 2-C-1 was changed to the following composition 2-C-17, , A coloring curable composition 2-C-17 for comparison was prepared, and a coloring pattern was formed to obtain a color filter. The same evaluation as in Example 2-3-1 was carried out. The results are shown in Table 9.

&Lt; Composition 2-C-17 >

80 parts by mass of cyclohexanone

Colorant (CI Pigment Red 254) 6.0 parts by mass

Colorant (CI Pigment Yellow 139) 4.0 parts by mass

7.0 parts by mass of a polymerizable compound (3: 7 mixture of tetramethylolpropane triacrylate and dipentaerythritol hexaacrylate)

??? 2.5 parts by mass of a photopolymerization initiator (oxime-based photopolymerization initiator: CGI-124, manufactured by Ciba Specialty Chemicals)

0.5 parts by mass of glycerol propoxylate

(Number average molecular weight Mn: 1,500, molar extinction coefficient? = 0, colorless compound)

[Comparative Examples 2-3-2 to 2-3-4, 2-3-6]

Except that the specific sensitizer, the photopolymerization initiator, and the notarized sensitizer in the composition 2-C-1 used in the preparation of the colored curable resin composition C-1 in Example 2-3-1 were changed as shown in Table 9 C-14 to 2-C-16 and 2-C-18 were prepared in the same manner as in Example 2-3-1, coloring patterns were formed on the support, And evaluated. The results are shown in Table 9 below.

The photopolymerization initiators D1 to D3, notarization sensitizers A1 and A2, and Comparative Compounds 2-1 to 2-3 shown in Table 9 are the above-mentioned compounds.

From the results shown in Table 9, it can be seen that the colored curable compositions of the respective Examples containing specific sensitizers (Compounds 2-1 to 2-6) have excellent storage stability in the solution state. When a colored pattern is formed on a support using this colored curable composition, it is preferable that the coloring pattern is formed on a support without containing a specific sensitizer, or for each Comparative Example using Comparative Compounds 2-1 to 2-3 in place of a specific sensitizer , The exposure sensitivity is high, the developing property is excellent, and a color filter excellent in both substrate adhesion and pattern cross-sectional shape is obtained.

Examples of the synthesis of the compounds 3-1 to 3-7 which are the compounds represented by the general formula (3-1) according to the present invention are shown below.

(Synthesis Example 3-1)

27 g of diphenylaminobenzoaldehyde and 3.5 g of piperidine were dissolved in 450 ml of methanol and stirred for 1 hour while refluxing. Then, 17 g of 3-ethyl-2-allylimino-oxazolidin-4-one was added and stirred for 1 hour while refluxing. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and yellow crystals were precipitated. The precipitated crystals were filtered and added to 1000 ml of methanol, which was stirred for 1 hour. The crystal was filtered and dried to obtain 23 g (yield 55%) of Compound 1 having the following structure. ¹ H-NMR (solvent: CDCl ₃ ), infrared absorption spectrum, mass spectrometry spectrum and elemental analysis. Melting point (67 ° C), electronic absorption spectrum (THF): absorption maximum wavelength 388 nm, absorption maximum molar extinction coefficient 29400. oxidation potential (CH ₃ CN, vs Ag / AgCl) + 0.89 V.

(Synthesis Example 3-2)

35 g of diphenylaminobenzoaldehyde and 2.0 g of piperidine were dissolved in 500 ml of methanol, and the mixture was stirred for 1 hour while refluxing. Then, 20 g of 3-ethyl-2-thioxo-4-oxazolidione was added and stirred for 4 hours while refluxing. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and yellow crystals were precipitated. The precipitated crystals were filtered and added to 1000 ml of methanol, which was stirred for 1 hour. The crystals were filtered and dried to obtain 48 g (yield: 91%) of Compound 3-2 having the following structure. Identification was carried out by ¹ H-NMR.

Next, 1.7 g of silver nitrate was dissolved in 20 ml of acetonitrile, 2.0 g of Compound 2 was added, and the mixture was stirred at room temperature for 0.5 hours. Then, 1.0 g of benzylamine was added dropwise, and the mixture was stirred for 1.5 hours. Then, 1.0 g of triethylamine was added dropwise, and the mixture was further stirred for 1.5 hours. After completion of the reaction, 30 ml of acetone was added, and the precipitated silver salt was filtered off using Celite, and the filtrate was added to 150 ml of water. The precipitated crystals were filtered off and then slurry was reslurried in methanol to obtain 1.9 g (yield: 88%) of the same compound 3-1 as obtained in Synthesis Example 3-1. Identification was carried out by ¹ H-NMR.

(Synthesis Example 3-3)

20 g of 2,3,6,7-tetrahydro-1H, 5H-pyrido- [3,2,1-eta] -quinoline-9-carbaldehyde and 3.5 g of pyrrolidine were dissolved in 400 ml of methanol, And the mixture was stirred while refluxing for 1.5 hours. Then, 21 g of 3-phenylethyl-1,3-oxazolidin-2,4-dione was added and stirred for 4 hours while refluxing. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and yellow crystals were precipitated. The precipitated crystals were filtered and added to 800 ml of methanol, which was stirred for 1 hour. The crystal was filtered and dried to obtain 33 g (yield: 85%) of 3-3 of the following structure. ¹ H-NMR (solvent: CDCl ₃ ), infrared absorption spectrum, mass spectrometry spectrum and elemental analysis. Melting point (162 ℃), electron absorption spectrum (THF): absorption maximum wavelength 412㎚, absorption maximum molar absorbance coefficient 35500. Oxidation potential _{(CH 3 CN, vs Ag /} AgCl) + 0.64V.

(Synthesis Example 3-4)

Compound 3-2 was synthesized by the same method as described in Synthesis Example 3-2.

Then, 2.8 g of silver nitrate was dissolved in 40 ml of acetonitrile, 3.0 g of compound 2 was added, and the mixture was stirred for 0.5 hours. Then, 5 g of 2,4,6-trimethylaniline was added and stirred for 1.5 hours. Then, 1.0 g of triethylamine was added dropwise, and the mixture was stirred at 70 ° C for 1 hour. After completion of the reaction, 60 ml of acetone was added, and the precipitated silver salt was separated by filtration using Celite, and the filtrate was added to 300 ml of water. The precipitated crystals were filtered off and then slurry was reslurried in methanol to obtain 3.5 g (yield 92%) of Compound 3-4 having the following structure. ¹ H-NMR (solvent: CDCl ₃ ), infrared absorption spectrum, mass spectrometry spectrum and elemental analysis. Melting point (117 ℃), electron absorption spectrum (THF): absorption maximum wavelength 395㎚, absorption maximum molar absorbance coefficient 30900. Oxidation potential _{(CH 3 CN, vs Ag /} AgCl) + 0.82V.

(Synthesis Example 3-5)

1.8 g of diethylaminobenzoaldehyde, 0.7 g of piperidine and 2.1 g of 3-ethyl-2-cyclohexylimino-oxazolidin-4-one were dissolved in 50 ml of ethanol, and the mixture was stirred for 8 hours while refluxing. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and yellow crystals were precipitated. The precipitated crystals were filtered and added to 50 ml of methanol, which was stirred for 1 hour. The crystals were filtered and dried to obtain 1.4 g (yield 38%) of 3-5 of the following structure. ¹ H-NMR (solvent: CDCl ₃ ), infrared absorption spectrum, mass spectrometry spectrum and elemental analysis. Electron absorption spectrum (THF): absorption maximum wavelength 385 nm, absorption maximum molar absorption coefficient 37200.

(Synthesis Example 3-6)

17.7 g of diethylaminobenzoaldehyde and 1.0 g of piperidine were dissolved in 250 ml of methanol and stirred for 1 hour while refluxing. Then, 19.9 g of 3-cyclohexyl-2-thioxo-4-oxazolidione was added and stirred for 4 hours while refluxing. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and orange crystals precipitated. The precipitated crystals were filtered and added to 500 ml of methanol, which was stirred for 1 hour. The crystals were filtered and dried to obtain 30.4 g (yield: 85%) of Compound 3-6 having the following structure, which is a dye precursor. Identification was carried out by ¹ H-NMR.

(Synthesis Example 3-7)

Nitric acid was dissolved in 20 ml of acetonitrile, 1.8 g of the compound 3-6 obtained by the same method as in Synthesis Example 3-6 was added, and the mixture was stirred at room temperature for 0.5 hours. Then, 1.0 g of cyclohexylamine was added dropwise, and the mixture was stirred for 1.5 hours. Then, 1.0 g of triethylamine was added dropwise, and the mixture was further stirred for 1.5 hours. After completion of the reaction, 30 ml of acetone was added, and the precipitated silver salt was filtered off using Celite, and the filtrate was added to 150 ml of water. The precipitated crystals were filtered off and then slurry was reslurried in methanol to obtain 1.9 g (yield: 88%) of Compound 3-7 of the following structure. ¹ H-NMR (solvent: CDCl ₃ ), infrared absorption spectrum, mass spectrometry spectrum and elemental analysis. Electron absorption spectrum (THF): absorption maximum wavelength 384 nm, absorption maximum absorption coefficient 38300.

The structures of the compounds 3-1 to 3-7 are collectively shown in Table 10 below. The structures of Comparative Compounds 3-1 to 3-3 used in Comparative Examples to be described later are shown in Table 11.

Hereinafter, the color filter of the present invention and the manufacturing method thereof will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it is beyond the ordinary knowledge.

[Example 3-1-1]

Here, an example of preparing a color filter for a liquid crystal display element using the colored curable composition 3-A-1 containing a coloring agent (pigment) is prepared and the colored curable composition 3-A-1 is used.

〔One. Preparation of colored curable composition 3-A-1]

1-1. Preparation of pigment dispersion (P1)

A pigment dispersion prepared in the same manner as in Example 1-1-1 was used.

1-2. Preparation of colored curable composition 3-A-1 (coating liquid)

The components of the following composition 3-A-1 were mixed and dissolved to prepare a colored curable composition 3-A-1.

&Lt; Composition 3-A-1 &

Pigment dispersion (P1) 600 parts by mass

· Alkali-soluble resin

 (Benzyl methacrylate / methacrylic acid / hydroxyethyl

  Methacrylate copolymer, mol ratio: 80/10/10,

  Mw: 10000) 190 parts by mass

Dipentaerythritol hexaacrylate [polymerizable compound] 60 parts by weight

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-

  1,2'-biimidazole [photopolymerization initiator] 60 parts by mass

Compound 3-1 [Specific sensitizer] 40 parts by mass

Notarization: 40 parts by mass of 2-mercaptobenzimidazole

Surfactant: 1 part by mass (trade name: tetronick 150R1, BASF)

Solvent: 1000 parts by mass of propylene glycol monomethyl ether acetate

? -Methacryloxypropyltriethoxysilane 10 parts by mass

〔2. Fabrication of color filter]

2-1. Formation of Curable Composition Layer

A colored curable composition film (colored curable composition layer) was formed in the same manner as in Example 1-1-1 except that the colored curable composition 3-A-1 was used instead of the colored curable composition 1-A-1, , Development and heat treatment to obtain a color filter.

[3. Performance evaluation]

The colored curable composition 3-A-1 (coating liquid) prepared above was evaluated in the same manner as in Example 1-1-1. The results are shown in Table 12.

[Examples 3-1-2 to 3-1-10]

Except that the specific sensitizer, the photopolymerization initiator, and the notarized sensitizer in the composition 3-A-1 used in the preparation of the colored curable composition 3-A-1 in Example 3-1-1 were changed to those shown in Table 12 , All of the color-curable compositions 3-A-2 to A-10 were prepared in the same manner as in Example 3-1-1, and a color filter having a coloring pattern using the same was obtained. Further, the same evaluations as in Example 3-1-1 were carried out. The results are shown in Table 12.

[Comparative Example 1-1]

The same procedures as in Example 3-1-1 were repeated except that the composition 3-A-1 used in the preparation of the colored curable composition 3-A-1 was changed to the following composition 3-B-1, , The coloring curable composition for comparison B-1 was prepared and a coloring pattern was formed to obtain a color filter. Further, the same evaluations as in Example 3-1-1 were carried out. The results are shown in Table 12.

&Lt; Composition 3-B-1 >

Pigment dispersion (P1) 600 parts by mass

· Alkali-soluble resin

  (Benzyl methacrylate / methacrylic acid / hydroxyethyl

   Methacrylate copolymer, mol ratio: 80/10/10,

   Mw: 10000,) 200 parts by mass

Dipentaerythritol hexaacrylate [polymerizable compound] 60 parts by weight

· 1- [4- (phenylthio) phenyl] -2-

  (O-benzoyloxime) [Photopolymerization initiator] 140 parts by mass

Solvent: 1000 parts by mass of propylene glycol monomethyl ether acetate

1 part by mass of a surfactant (trade name: tetronick 150R1, BASF)

[Comparative Examples 1-2 to 1-4]

Except that the specific sensitizer, the photopolymerization initiator, and the notarization sensitizer were changed to the comparative compounds, photopolymerization initiators, and co-sensitizers shown in Table 12 below in the colored curable composition 3-A-1 prepared in Example 3-1-1 , All of the comparative color-curable compositions 3-B-2 to 3-B-4 were prepared in the same manner as in Example 3-1-1 to obtain a color filter having a coloring pattern using the same. Further, the same evaluations as in Example 3-1-1 were carried out. The results are shown in Table 12.

The photopolymerization initiators D1 to D3 and notarization sensitizers F1 and F2 shown in Table 12 are the same as the photopolymerization initiators D1 to D3 and notarization sensitizers F1 and F2 shown in Table 4, respectively.

From the results shown in Table 12, it can be seen that the colored curable compositions of the respective Examples containing specific sensitizers (Compounds 3-1 to 3-7) have excellent storage stability in the solution state. When a colored pattern is formed on a support using this colored curable composition, it is preferable that a specific color sensitizing agent is not contained, or each comparative example using Comparative Compounds 3-1 to 3-3 in place of a specific sensitizer is exposed It can be seen that a color filter having high sensitivity and excellent developability as well as excellent substrate adhesion and pattern cross-sectional shape can be obtained.

Hereinafter, an example will be described in which a colored curable composition containing a colorant (pigment) for use in a solid-state imaging device is prepared, and a color filter for a solid-state imaging device is manufactured using the colored curable composition.

[Example 3-2-1]

〔One. Preparation of resist solution]

A resist solution was prepared in the same manner as in Example 1-2-1.

〔2. Preparation of a silicon wafer substrate on which a primer layer was formed]

A silicon wafer substrate on which a primer layer was formed was obtained in the same manner as in Example 1-2-1.

[3. Preparation of colored curable composition 3-C-1]

A compound of the following composition 3-C-1 was mixed and dissolved to prepare a colored photosensitive resin composition 3-C-1.

&Lt; Composition 3-C-1 &

Cyclohexanone (solvent) 80 parts by mass

C.I.Acid Blue 108 [Colorant] 7.5 parts by mass

C.I. Solvent Yellow 162 [Colorant] 2.5 parts by mass

· Pentaerythritol triacrylate and

  Dipentaerythritol hexaacrylate

  Of 3: 7 [Polymerizable compound] 7.0 parts by mass

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-

  1,2'-biimidazole [photopolymerization initiator] 1 part by mass

Compound 3-1 [specific sensitizer] 0.7 parts by mass

Notarizing agent: 2-mercaptobenzoimidazole 0.8 part by weight

0.5 parts by mass of glycerol propoxylate

(Number average molecular weight Mn: 1,500, molar extinction coefficient? = 0, colorless compound)

〔4. Evaluation of storage stability of colored curable composition 3-C-1 (coating liquid)] [

Similarly to Example 1-2-1, the colored curable composition 3-C-1 was stored at room temperature for one month and evaluated.

[5. Fabrication and Evaluation of Color Filter Using Color-curable Composition 3-C-1]

A color filter was produced in the same manner as in Example 1-2-1 except that the colored photosensitive resin composition 3-C-1 was used in place of the colored curable composition 1-C-1.

&Lt; Exposure sensitivity >

The exposure sensitivity, the substrate adhesion, and the cross-sectional shape of the pattern were evaluated in the same manner as in Example 1-2-1. The results of the measurement evaluation are shown in Table 13 below.

<Developability>

The developability was evaluated in the same manner as in Example 1-1-1.

[Comparative Example 3-2-1]

All of the examples 3-2-1 to 3-2-1 were obtained in the same manner as in Example 3-2-1 except that the composition 3-C-1 used in the preparation of the colored curable composition 3-C-1 was changed to the following composition 3-D-1. , A coloring curable composition for comparison 3-D-1 was prepared and a coloring pattern was formed to obtain a color filter. Further, the same evaluations as in Example 3-2-1 were carried out. The results are shown in Table 13.

&Lt; Composition 3-D-1 >

80 parts by mass of cyclohexanone

Colorant CI Acid Blue 108 7.5 parts by mass

Colorant C.I. Solvent Yellow 162 2.5 parts by mass

· Pentaerythritol triacrylate and

  Of dipentaerythritol hexaacrylate

  3: 7 [Polymerizable compound] 7.0 parts by mass

· Oxime type photopolymerization initiator

  (CGI-124, manufactured by Ciba Specialty Chemicals,

  Photopolymerization initiator) 2.5 parts by mass

Glycerol propoxylate (number-average molecular weight Mn: 1500) 0.5 parts by mass

[Examples 3-2-2 to 2-10, Comparative Examples 2-2 to 2-4]

A specific sensitizer, a photopolymerization initiator, and a notarized sensitizer in the composition 3-C-1 used in the preparation of the colored photosensitive resin composition 3-C-1 in Example 3-2-1 were changed as shown in Table 13 Except that the colored photosensitive resin compositions 3-C-2 to 3-C-10 and the comparative colored curable compositions 3-C-11 to 3-C-13 were prepared in the same manner as in Example 3-2-1, In addition, a colored pattern was formed on the support to prepare a color filter, and evaluation was carried out. The results are shown in Table 13 below.

[Example 3-2-11]

In all cases, except that the composition 3-C-1 used in the preparation of the colored curable composition 3-C-1 in Example 3-2-1 was changed to the following composition 3-E-1, , The colored curable composition 3-E-1 was prepared and a colored pattern was formed to obtain a color filter. Further, the same evaluations as in Example 3-2-1 were carried out. The results are shown in Table 13.

<Composition 3-E-1>

80 parts by mass of cyclohexanone

Colorant C.I. Pigment Red 254 6.0 parts by mass

Colorant CI Pigment Yellow 139 4.0 parts by mass

· Pentaerythritol triacrylate and

  Of dipentaerythritol hexaacrylate

  3: 7 [Polymerizable compound] 7.0 parts by mass

- 2,2'-bis (2-chlorophenyl) -

  4,4 ', 5,5'-tetraphenyl-

  1,2'-biimidazole [photopolymerization initiator] 1 part by mass

Compound 3-1 [specific sensitizer] 0.7 parts by mass

Notarizing agent: 2-mercaptobenzoimidazole 0.8 part by weight

Glycerol propoxylate (number-average molecular weight Mn: 1500) 0.5 parts by mass

[Comparative Example 3-2-5]

A specific sensitizer, a photopolymerization initiator, and a notarized sensitizer in the composition 3-E-1 used in the preparation of the colored photosensitive resin composition 3-E-1 in Examples 3-2-11 were changed as shown in Table 13 , A coloring curable composition 3-E-2 for comparison was prepared in the same manner as in Example 3-2-11, and a coloring pattern was formed on a support to prepare a color filter, and evaluation was carried out. The results are shown in Table 13 below.

[Comparative Example 3-2-6]

In all of Examples 3-2-1 to 3-1-2, except that the composition 3-C-1 used in the preparation of the colored curable composition 3-C-1 was changed to the following composition 3-F-1, , A coloring curable composition for comparison 3-F-1 was prepared and a coloring pattern was formed to obtain a color filter. Further, the same evaluations as in Example 3-2-1 were carried out. The results are shown in Table 13.

&Lt; Composition 3-F-1 >

80 parts by mass of cyclohexanone

Colorant C.I. Pigment Red 254 6.0 parts by mass

Colorant CI Pigment Yellow 139 4.0 parts by mass

· Pentaerythritol triacrylate and

  Of dipentaerythritol hexaacrylate

  3: 7 [Polymerizable compound] 7.0 parts by mass

· Oxime type photopolymerization initiator

  (CGI-124, manufactured by Ciba Specialty Chemicals,

  Photopolymerization initiator) 2.5 parts by mass

Glycerol propoxylate (number-average molecular weight Mn: 1500) 0.5 parts by mass

The photopolymerization initiators D1 to D3, notarization sensitizers F1 and F2, and Comparative Compounds 3-1 to 3-3 shown in Table 13 are the above-mentioned compounds.

From the results shown in Table 13, it can be seen that the colored curable compositions of the respective Examples containing specific sensitizers (Compounds 3-1 to 3-7) are excellent in storage stability in the solution state. Further, when the coloring curable composition was used to form a colored pattern on the support, it was found that, for each Comparative Example using no specific sensitizer or using Comparative Compounds 3-1 to 3-3 instead of specific sensitizers It can be seen that a color filter having high exposure sensitivity and excellent developability as well as excellent substrate adhesion and pattern cross-sectional shape can be obtained.

As described above, according to the present invention, even when a colorant is contained at a high concentration, it is useful for high sensitivity of a curable composition which can be cured at a high sensitivity to form a colored pattern having good pattern formability and excellent adhesion with a support A novel compound, a photosensitive composition, a curable composition, and a curable composition for a color filter can be provided.

Further, according to the production method of the present invention, it is possible to provide a color filter having a coloring pattern excellent in resolution and adhesion to a support obtained by using the curable composition for a color filter of the present invention, and a color filter capable of producing the color filter with high productivity have.

Claims (17)

A compound represented by the following general formula (1-I), a compound represented by the general formula (1-II), a compound represented by the following general formula (2-1), and a compound represented by the general formula (3-1) At least one compound selected from the group consisting of: A photopolymerization initiator; Polymerizable compounds; And A colorant, Wherein the content of the coloring agent is 40 to 80 mass% with respect to the total solid content of the curable composition for a color filter.

In the general formulas (1-I) and (1-II), R ¹¹ and R ¹² each independently represent a monovalent substituent; R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent; n represents an integer of 0 to 5; n 'represents an integer of 0 to 5; n and n 'are not both 0; When n is 2 or more, plural R ^{11 s} present may be the same or different; When n 'is 2 or more, plural R ^{12 s} may be the same or different,

In the general formula (2-I), A represents an aromatic ring or a heterocycle which may have a substituent; R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent nonmetal atomic group; A, R ²² , R ²³ and R ²⁴ may be bonded to each other to form an aliphatic or aromatic ring;

In the general formula (3-1), A represents an aromatic ring or a heterocycle which may have a substituent; X represents an oxygen atom, a sulfur atom or -N (R ³³ ) -; Y represents an oxygen atom, a sulfur atom or -N (R ³³ ) -; R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a monovalent nonmetal atomic group; A, R ³¹ , R ³² and R ³³ may be bonded to each other to form an aliphatic or aromatic ring. The curable composition for a color filter according to claim 1, which contains the compound represented by the general formula (1-I) or the general formula (1-II). The positive resist composition according to claim 2, wherein in the general formula (1-I) or the general formula (1-II), n is an integer of 1 to 5, and at least one of R ¹¹ is an alkyl group or an alkoxy group Curable composition for a color filter. The curable composition for a color filter according to claim 2, further comprising a thiol compound. The curable composition for a color filter according to claim 1, which contains a compound represented by the general formula (2-I). The curable composition for a color filter according to claim 1, which contains a compound represented by the general formula (3-1). The curable composition for a color filter according to any one of claims 1 to 6, which contains a nonimidazole-based compound as the photopolymerization initiator. A color filter having a coloring pattern formed by using the curable composition for a color filter according to any one of claims 1 to 6 on a support. The color filter according to claim 8, wherein the curable composition for a color filter contains a non-imidazole-based compound as the photopolymerization initiator. A process for producing a colored curable composition, comprising the steps of: applying a curable composition for a color filter according to any one of claims 1 to 6 on a support to form a colored curable composition layer; exposing the colored curable composition layer through a mask; And a step of developing the colored curable composition layer to form a colored pattern. The method for producing a color filter according to claim 10, wherein the curable composition for a color filter contains a non-imidazole-based compound as the photopolymerization initiator. A compound represented by the following formula (2-I):

In the general formula (2-I), A represents an aromatic ring or a heterocycle which may have a substituent; R ²¹ and R ²⁵ each independently represent a hydrogen atom or a monovalent nonmetal atomic group; R ²² , R ²³ , and R ²⁴ each independently represent a hydrogen atom or a methyl group. A photosensitive composition comprising a compound represented by the following general formula (2-I):

In the general formula (2-I), A represents an aromatic ring or a heterocycle which may have a substituent; R ²¹ and R ²⁵ each independently represent a hydrogen atom or a monovalent nonmetal atomic group; R ²² , R ²³ , and R ²⁴ each independently represent a hydrogen atom or a methyl group. A compound represented by the following general formula (2-I); A photopolymerization initiator; Polymerizable compounds; And a colorant, Wherein the content of the coloring agent is 40 to 80 mass% with respect to the total solid content of the curable composition:

In the general formula (2-I), A represents an aromatic ring or a heterocycle which may have a substituent; R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent nonmetal atomic group; A, R ²² , R ²³ and R ²⁴ may be bonded to each other to form an aliphatic or aromatic ring. 15. The curable composition according to claim 14, which contains a nonimidazole-based compound as the photopolymerization initiator. 6. The compound according to claim 5, wherein A in the general formula (2-I) represents an aromatic ring or a heterocycle which may have a substituent; R ²¹ and R ²⁵ each independently represent a hydrogen atom or a monovalent nonmetal atomic group; R ²² , R ²³ , and R ²⁴ each independently represent a hydrogen atom or a methyl group. The positive resist composition according to claim 1, wherein the compound represented by the general formula (1-I), the compound represented by the general formula (1-II), the compound represented by the general formula (2-1) Wherein the mass ratio of the photopolymerization initiator to the at least one compound selected from the group consisting of a compound represented by the following formula (1) is 0.5 or more and 3 or less.

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