KR20070018850A - Oxime ester compound, photopolymerizable composition and color filter utilizing the same - Google Patents

Abstract

An oxime ester compound having a specific structure is provided. In particular, the oxime ester compound constitutes component (c) in a photopolymerizable composition containing (a) a black material, (b) an organic binder and (c) a photopolymerization initiator.

The said oxime ester compound can be used as a high sensitivity photoinitiator. The photopolymerizable composition containing the oxime ester compound exhibits high light shielding properties in the form of a thin film and is excellent in sensitivity and resolution, thereby forming a high quality resin black matrix (BM) at low cost. The color filter using the said resin BM is excellent in precision, flatness, and durability, and can improve the display quality of a liquid crystal element. In addition, the manufacturing process and the color filter itself do not contain harmful substances, so that the risk to the human body can be reduced and the environmental stability can be improved. Moreover, it is applicable also to the use which does not use a color material like a photo spacer or a rib (liquid crystal division orientation protrusion).

Description

Oxime ester compound, photopolymerizable composition and color filter using same {OXIME ESTER COMPOUND, PHOTOPOLYMERIZABLE COMPOSITION AND COLOR FILTER UTILIZING THE SAME}

The present invention relates to oxime ester compounds useful as photopolymerization initiators and to photopolymerizable compositions containing them. More specifically, the present invention is, for example, a photopolymerizable composition for color filters used in the production of optical color filters used in color televisions, liquid crystal display devices, solid-state imaging devices and cameras, and color filters obtained from the compositions. The present invention is also effective in, and the present invention is a photopolymerizable composition for color filters suitable for the production of a black matrix (hereinafter abbreviated as BM) having high light blocking property as well as high sensitivity and excellent resolution, and high light blocking property The branch relates to a color filter having a high precision resin BM.

In addition, the oxime ester compound according to the present invention is a high sensitivity photopolymerization initiator, and therefore its use is not limited to BM, and is transparent, for example, without using a color material for photo spacers or ribs (liquid crystal division orientation protrusions). It can be used in photosensitive compositions and can be widely used in various technical fields.

Color filters are typically formed by forming a black matrix on the surface of a transparent substrate, such as a glass or plastic sheet, and then sequentially forming, for example, three or more different colors of red, green and blue in a color pattern of stripes or mosaics. do. The pattern size depends on the use and color of the color filter and is usually on the order of 5 to 700 μm. In addition, the overlap position accuracy is several micrometers to several tens of micrometers, and a color filter is manufactured by the microfabrication technique with high dimensional accuracy.

As a typical manufacturing method of a color filter, a dyeing method, a printing method, a pigment dispersion method, an electrodeposition method, etc. can be mentioned. Among these, the pigment dispersion method which apply | coats the photopolymerizable composition containing a color material on a transparent board | substrate, and repeatedly performs image exposure, image development, and as needed, and forms a color filter image is a color filter pixel. It is widely used because it tends to have high precision in position, film thickness and the like, excellent durability such as light resistance and heat resistance is obtained, and defects such as pinholes are less likely to be formed.

In general, BMs are arranged in grids, stripes, or mosaics between red, green, and blue color patterns, improving the contrast by suppressing the color mixing of each color, or malfunctioning thin film transistors (TFTs) due to light leakage. Serves to prevent. Therefore, BM is required to have high light shielding property. Until now, it was common to form BM with the metal film of chromium, for example. This technique deposits a metal such as chromium on a transparent substrate and etches the chromium layer by a photolithography process. Therefore, high light-shielding property can be obtained with high precision with a thin film thickness. On the other hand, the above method involves a long manufacturing process, is poor in productivity and expensive, and may also cause environmental problems due to waste water during etching and the like.

Therefore, the method of forming pollution-free resin BM at low cost from the photosensitive resin which disperse | distributed the light-shielding pigment or dye was actively researched. However, since resin BM has the problem mentioned later, it has not been put to practical use yet. In order for the resin BM to have a light shielding property (optical density) equivalent to that of the BM formed, for example, by the metal film of chromium, it is necessary to increase the content of the light shielding pigment, dye, or the like, or increase the film thickness.

In the method of increasing the film thickness, the flatness of RGB colored pixels formed on the BM will be impaired due to the influence of the irregularities of the BM. Therefore, the liquid crystal cell gap tends to be nonuniform or the alignment of the liquid crystal tends to be disturbed, so that the display capability will be lowered. In addition, this problem can also cause disconnection (breakage of the planar film) of the transparent electrode ITO (indium tin oxide) film formed on the color filter.

In addition, in the method of increasing the content of light-shielding pigments or dyes, the sensitivity, developability, resolution, adhesiveness, etc. of the photosensitive resin (black resist) may be deteriorated, and the productivity is not only reduced, but also required for the color filter. Precision and reliability will not be obtained. That is, a photosensitive material capable of exhibiting sensitivity and resolution in a high light-shielding thin film form has not yet been realized, which hinders practical use of the resin BM.

Conventionally, the method of improving a sensitivity and the resolution is known about the photosensitive resin which has specific light transmittance like general photosensitive resin or the coloring photosensitive composition for color filters. For example, as a coloring composition for color filters which disperse | distributed a pigment, the photosensitive composition containing the initiator containing a binder resin, a polyfunctional acrylic monomer, and a triazine compound is known (patent documents 1-4). Similar compositions are also known in which the initiator is bisimidazole (Patent Documents 5 and 6). However, the composition described in the above document inhibits polymerization by oxygen when exposed in air, and practical sensitivity cannot be obtained.

In the case where light shielding ability is required in all wavelength ranges of light as in the case of resin BM, it is very difficult to make a crosslinking density difference between the exposed portion and the unexposed portion, and (2) in the film thickness direction even in the exposed portion. There is a difference in crosslinking density, i.e., even when sufficient curing is achieved on the light irradiation surface, hardening is not performed on the base surface, and (3) developability is remarkably decreased because a large amount of insoluble black material is added to the developing solution. As such, there is a significant obstacle to imparting photosensitive properties.

In particular, the above developments (1) and (2) are mutually opposite, and since the difference in curing density in the film thickness direction becomes more remarkable by the composition in which the exposed portion is further cured, the resolution is lowered. In addition, when the difference in crosslinking density between the exposed portion and the unexposed portion and the curing density of the exposed portion cannot be made uniform, the use of a developer having a high solvent power tends to be difficult, and the improvement of developability also tends to be difficult. . Conventionally known photosensitive compositions for resin BM formation (for example, Patent Documents 7 and 8) avoid such a situation, and do not form resin BM having the same light shielding properties as metal BM, but the photosensitive ability by light transmission to some extent Since resin BM which has a form is formed, light-shielding ability falls remarkably and it is not practical. Therefore, the resin BM of the high light-shielding thin film form obtained by forming, hardening and shrinking the resin BM of the low light-shielding thick film form once was also proposed (patent document 9). However, such resins are not practical because the process is complicated and the adhesion tends to be lowered due to the accumulation of distortion during film shrinkage. Therefore, the practical resin BM was difficult due to the seemingly contradictory problem of causing the photoreaction under the light-shielding conditions incompatible with the original photoreaction.

Moreover, the technique of using a specific oxime ester compound as a photoinitiator is known (patent document 10). However, by simply replacing the initiator (for example, bisimidazole or triazine initiator) used in the conventional resin BM with an oxime compound, the image characteristics required for the resin BM, i.e., sensitivity and resolution cannot be improved.

In addition, high-sensitivity photopolymerizable compositions are widely required not only for BM having a black pigment, but also for compositions for forming red, green and blue pixels, compositions for photo spacers, compositions for ribs, and the like. have.

Patent Document 1: JP-A-1-152449

Patent Document 2: JP-A-1-254918

Patent document 3: JP-A-2-153353

Patent Document 4: JP-A-2-804

Patent Document 5: JP-A-6-75372

Patent Document 6: JP-A-6-75373

Patent Document 7: JP-A-6-51499

Patent Document 8: JP-A-6-3518

Patent Document 9: JP-A-8-44050

Patent Document 10: JP-A-2000-80068

Problems to be Solved by the Invention

The present invention solves the above problems and provides a resist material having sufficient sensitivity and resolution, which can easily form a thin film pattern having high light blocking property by photolithography, which is a resin BM of a color filter. It can be manufactured at low cost and with high precision. Moreover, the liquid crystal display device using the color filter manufactured using the said resin is excellent in the display capability like contrast. In addition, according to the present invention, by using the resin for BM, a high-quality, pollution-free color filter can be obtained.

Moreover, in recent years, in order to achieve the "high density | concentration" required for a color filter, it was necessary to increase the color material density | concentration in the coloring composition to be used. On the other hand, since the light transmittance of the said colored resin composition falls, in order to maintain and improve image formation performance, the photopolymerizable material which has high sensitivity was calculated | required. This invention solves the said subject.

In addition, it is further required to produce photosensitive compositions for photo spacers or ribs, and also general photosensitive compositions using photopolymerizable materials with low cost and high precision, which are used in the manufacture of liquid crystal display devices, and have photosensitive polymers having high sensitivity. Forming material is required. This invention solves the said subject.

Means to solve the problem

As a result of intensive studies, the present inventors have used a photopolymerizable composition containing a specific oxime ester compound having a structure that further improves the efficiency of photopolymerization as a photopolymerization initiator and an epoxy acrylate resin having a carboxyl group as an organic binder. It has been found that this object can be achieved.

In addition, the present inventors have found that this specific oxime ester compound itself is a novel compound and is effective as an excellent photopolymerization initiator regardless of the presence or absence of a color material, and completed the present invention.

That is, an object of the present invention is to provide an oxime ester compound represented by the formula (1) or (2):

(In the above formula,

R ^1a is optionally substituted C _{2 -25} alkenyl, C _{1 -20} alkyl-heteroaryl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group, C _{1 -20} heteroaryloxy carbonyl alkyl group or a hetero arylthio group, a C _{0 -20} amino group, or a C _{1 -20} represents an amino group, with the proviso that, R ^1a is C _{1 -10,} which can form a ring with R1 ', the linking group may have a substituent An alkylene group,-(CH = CH) _n -,-(C≡C) _n -or a combination thereof (n is an integer from 0 to 3);

R ^2a is optionally substituted C _{2 -12} alkanoyl groups, C _{3 -25} noilgi alkenyl, C _{3 -8} cycloalkyl alkanoyl, C _{7 -20} benzoyl group, C _{1 -20} group, C ₂ to _{heteroaryl- 10} alkoxy group or a C _{7 -20} phenoxy represents a carbonyl group;

R 1 ′ represents any substituent containing an aromatic ring or a heteroaromatic ring):

(In the above formula,

R ^1b is optionally substituted C _{6 -20} phenyl group, C _{1 -20} alkyl, C _{5 -8} cycloalkyl group, C _{2 -20} alkanoyl groups, C _{7 -20} benzoyl group, C _{2 -12} alkoxy group or a phenoxy a carbonyl group, C _{1 -20} amide group, a nitro group, a C _{2 -25} alkenyl, C _{1 -10} alkyl-heteroaryl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group, C _{1 -20} heteroaryloxy-carbonyl group or a hetero arylthio group, a C _{0 -20} amino group, or represents a C _{1 -20} amino group, with the proviso that, R ^1b may form a ring with the R1 ', the linking group may have a substituent in C _{1 -10} alkylene _{group, - (CH = CH) n} -, - (C≡C) n - or a combination thereof (n is an integer of 0 to 3);

R ^2b is optionally substituted C _{1 -20} heteroaryl group, C _{1 -20} heteroaryl alkanoyl, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl group, C _{3 - 20} heteroaryloxy carbonyl nilal Kano represents a group, or C _{2 -10} amino group;

R 1 ′ represents any substituent containing an aromatic ring or a heteroaromatic ring).

Another object of the present invention is in the formula (1),

R ^1a is a ring which may be substituted with a C _{2 -25} alkenyl, C _{3 -20} alkoxycarbonyl group, a C _{8 -20} phenoxycarbonyl group or C _{1 -20} alkyl, or amino, or R ^1a is R1 ' the formation, and the linking group which may have a substituent, C _{1 -10} alkylene _{group, - (CH = CH) n} -, - (C≡C) n - or a combination thereof (n is an integer of 0 to 3),

R ^2a is to provide a C _{2 -12} alkanoyl group of the oxime ester compound which may be substituted.

Another object of the present invention is in formula (2),

R ^1b is an optionally substituted C _{1 -20} alkyl,

R ^2b is optionally substituted C _{1 -20} heteroaryl group, C _{1 -20} heteroaryl alkanoyl, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl group or a C _{2 - It} is providing the said oxime ester compound which is a ₁₀ aminocarbonyl group.

Another object of the present invention is to provide an oxime ester compound represented by the formula (3) or (4):

(In the above formula,

R ^1a is optionally substituted C _{2 -25} alkenyl, C _{1 -20} alkyl-heteroaryl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group, C _{1 -20} heteroaryloxy carbonyl represents an alkyl group or a hetero arylthio group, a C _{0 -20} amino group, or a C _{1 -20} amino group, with the proviso that, R ^1a may form a ring together with R ³ or R ^7, in this case, R ^1a and R ³ and / or R ⁷ are bonded to each other to form a divalent or trivalent linking group, the linking group is C _{1 -10} alkylene group which may have a _{substituent, - (CH = CH) n} -, - (C≡C) n - Or a combination thereof (n is an integer from 0 to 3);

R ^2a is optionally substituted C _{2 -12} alkanoyl groups, C _{3 -25} noilgi alkenyl, C _{3 -8} cycloalkyl alkanoyl, C _{7 -20} benzoyl group, C _{1 -20} group, C ₂ to _{heteroaryl- 10} alkoxy group or a C _{7 -20} phenoxy represents a carbonyl group;

^{R 3, R 4, R 5} , R 6 and R ⁷ is C _{1 -12} alkyl, C _{1 -12} alkoxy group, C _{5 -8} cycloalkyl group each independently of the other, may be hydrogen atom, a halogen atom, or a substituted , C _{6 -20} phenyl, C _{7 -20} benzyl group, C _{7 -20} benzoyl group, C _{2 -12} alkanoyl groups, C _{1 -20} in the heteroaryl group, C _{3 -20} alkoxy carbonyl nilal alkanoyl group, C _8-20 phenoxycarbonyl nilal alkanoyl, C _{3 -20} heteroaryloxy carbonyl nilal alkanoyl group, C _{2 -12} alkoxycarbonyl group or phenoxycarbonyl group, or ^{-OR 8, -SR 9, -SOR 9} , -SO 2 R ⁹ or NR ¹⁰ R ¹¹ , wherein at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represents -OR ⁸ , -SR ⁹ or -NR ¹⁰ R ¹¹ , wherein R ⁸ is C _{1 -12} alkyl group which hydrogen atom or may be substituted, C _{2 -8} alkanoyl, C _{3 -12} alkenyl, C _{3 -20} noilgi alkenyl, C _{6 -20 phenyl, - (CH 2 CH 2 O} ) _m H (m is an integer of 1 to 20) or C _{3 -15} trialkyl represents a silyl, R ⁹ is Bovine atom or C _{1 -12} alkyl group which may be substituted, C _{2 -8} alkanoyl, C _{3 -12} alkenyl group, C ₆ represents a phenyl group or a C _{3 -20 -15} trialkylsilyl, R ¹⁰ and R ¹¹ are each independently of the other, hydrogen atom or C _{1 -12} alkyl group which may be substituted, C _{2 -4} hydroxyl group, C _{3 -5} alkenyl group or represents a C _6-20 phenyl group, with the proviso that, R ³ to R ⁷ May combine with each other or each of them with R ¹ to form a cyclic structure):

(In the above formula,

R ^1b is optionally substituted C _{6 -20} phenyl group, C _{1 -20} alkyl, C _{5 -8} cycloalkyl group, C _{2 -20} alkanoyl groups, C _{7 -20} benzoyl group, C _{2 -12} alkoxy group or a phenoxy a carbonyl group, C _{1 -20} amide group, a nitro group, a C _{2 -25} alkenyl, C _{1 -10} alkyl-heteroaryl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group, C _{1 -20} heteroaryloxy-carbonyl group or a hetero arylthio group, a C _{0 -20} amino group, or represents a C _{1 -20} amino group, with the proviso that, R ^1b may form a ring together with R ³ or R ^7, in this case, R ^1b and a R ³ and / or R ⁷ is a bivalent or trivalent form a linking group, C _{1 -10} alkylene group, which linking group may have a substituent and bonded to each other _{- (CH = CH) n -} , - (C ≡C) _n -or a combination thereof (n is an integer from 0 to 3);

R ^2b is optionally substituted C _{1 -20} heteroaryl group, C _{1 -20} heteroaryl alkanoyl, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl group, C _{3 - 20} heteroaryloxy carbonyl nilal alkanoyl group, or C _{2 -10} represents an amino group;

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same as in formula (3)).

Another object of the present invention is to formula (3),

R ^1a is optionally substituted C _{2 -25} alkenyl, C _{3 -20} alkoxycarbonyl group, a C _{8 -20} phenoxycarbonyl group or C _{1 -20} alkyl, or amino, or R ^1a is R ³ or R ⁷ form a ring together with, and in this case, R ^1b and R ³ and / or R ⁷ are bonded to each other, and divalent or trivalent form a linkage group, the linking group which may have a substituent, C _{1 -10} alkylene group, - ( CH = CH) _n -,-(C≡C) _n -or a combination thereof (n is an integer from 0 to 3),

R ^2a is a C _{2 -12} alkanoyl group which may be substituted,

^{R 3, R 4, R 5} , R 6 and R ⁷ are each independently of each other, C _{1 -12} alkyl group which may be a hydrogen atom, a halogen atom, or a substituted, C _{6 -20} phenyl group, C _{1 -20} heteroaryl Diary or —NR ¹⁰ R ¹¹ , wherein at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is —NR ¹⁰ R ¹¹ (wherein R ¹⁰ and R ¹¹ are each independently of one another a hydrogen atom; , or which may be substituted with a C _{1 -12} alkyl, C _{2 -4} hydroxyl group, C _{3 -5} alkenyl or C _{6 -20} shows a represents a phenyl group), provided that, R ³ to R ⁷ are bonded to each other or Each of these provides an oxime ester compound capable of combining with R ^1a to form a cyclic structure.

Another object of the present invention is in formula (4),

R ^1b is an optionally substituted C _{1 -20} alkyl,

R ^2b is optionally substituted C _{1 -20} heteroaryl group, C _{1 -20} heteroaryl alkanoyl, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl group or a C _{2 - 10} aminocarbonyl group,

^{R 3, R 4, R 5} , R 6 and R ⁷ are each independently of each other, C _{1 -12} alkyl group which may be a hydrogen atom, a halogen atom, or a substituted, C _{6 -20} phenyl group, C _{1 -20} heteroaryl Diary or —NR ¹⁰ R ¹¹ , wherein at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is —NR ¹⁰ R ¹¹ (wherein R ¹⁰ and R ¹¹ are each independently of one another a hydrogen atom; , or which may be substituted with a C _{1 -12} alkyl, C _{2 -4} hydroxyl group, C _{3 -5} alkenyl or C _{6 -20} shows a represents a phenyl group), provided that, R ³ to R ⁷ are bonded to each other or It is to provide the oxime ester compound capable of combining with R ^1b to form a cyclic structure.

Another object of the present invention is to provide an oxime ester compound represented by any one of formulas (5) to (7):

(In the above formula,

R ^1a and R ^2a are the same as in formula (3) as defined in claim 4;

R ^3, R ^6, R ⁷ and R ¹² to R ¹⁶ is C _{1 -12} alkyl, C _{2 -12} alkenyl noilgi, C _{6 -20} phenyl, C _{7 -20,} which may be each substituted with a hydrogen atom, a halogen atom, or Benzyl or benzoyl, or —NR ¹⁰ R ¹¹ , provided that R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ may combine with each other to form a cyclic structure):

(In the above formula,

R ^1b and R ^2b are the same as in the above formula (4);

R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ are the same as in the above formula (5)):

(In the above formula,

R ^1b is the same as in formula (4) above;

R ^2b represents R ^2a in Formula (3) or R ^2b in Formula (4);

R ^3, R ^6, R ⁷ and R ¹² to R ¹⁶ is C _{1 -12} alkyl, C _{2 -12} alkenyl noilgi, C _{6 -20} phenyl, C _{7 -20,} which may be each substituted with a hydrogen atom, a halogen atom, or Benzyl or benzoyl, or —NR ¹⁰ R ¹¹ , provided that R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ may be bonded to each other to form a cyclic structure, and R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ is one or more of the at least one selected from the group, and C _{3 -15} tree group consisting alkylsilyl a C _{1 -20} alkyl, heteroaryl, heteroaryl-alkanoyl and heteroaryl which may be substituted Containing).

Another object of the present invention is in formula (5),

R ^1a is optionally substituted C _{2 -25} alkenyl, C _{3 -20} alkoxycarbonyl group, a C _{8 -20} phenoxycarbonyl group or C _{1 -20} alkyl, or amino, or R ^1a is R ³ or R ⁷ form a ring together with, and in this case, R ^1a and R ³ and / or R ⁷ are bonded to each other, and divalent or trivalent form a linkage group, the linking group which may have a substituent, C _{1 -10} alkylene group, - ( CH = CH) _n -,-(C≡C) _n- , or a combination thereof (n is an integer from 0 to 3);

R ^2a is optionally substituted C _{2 -12} alkanoyl group and;

R ^3, R ^6, R ⁷ and R ¹² to R ¹⁶ is C _{1 -12} alkyl, C _{2 -12} alkenyl noilgi, C _{6 -20} phenyl, C _{7 -20,} which may be each substituted with a hydrogen atom, a halogen atom, or Benzyl or benzoyl, or —NR ¹⁰ R ¹¹ , provided that R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ are bonded to each other to form the oxime ester compound which may form a cyclic structure. .

Another object of the present invention is in formula (6),

R ^1b is an optionally substituted C _{1 -20} alkyl,

R ^2b is optionally substituted C _{1 -20} heteroaryl alkanoyl, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl group, or C _{2 -10} and amino group,

R ^3, R ^6, R ⁷ and R ¹² to R ¹⁶ is C _{1 -12} alkyl, C _{2 -12} alkenyl noilgi, C _{6 -20} phenyl, C _{7 -20,} which may be each substituted with a hydrogen atom, a halogen atom, or Benzyl or benzoyl, or —NR ¹⁰ R ¹¹ , provided that R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ are bonded to each other to form the oxime ester compound which may form a cyclic structure. .

Another object of the present invention is to provide an oxime ester compound represented by the formula (8) or (9):

(In the above formula,

R ^1a is optionally substituted C _{2 -25} alkenyl, C _{1 -20} alkyl-heteroaryl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group, C _{1 -20} heteroaryloxy carbonyl alkyl group or a hetero arylthio group, a C _{0 -20} amino group, or a C _{1 -20} represents an amino group, with the proviso that, R ^1a is C _{1 -10,} which can form a ring together with Ar _1, the linking group may have a substituent An alkylene group,-(CH = CH) _n -,-(C≡C) _n -or a combination thereof (n is an integer from 0 to 3);

R ^2a is the same as in formula (1) as defined in claim 1;

Ar ₁ represents an aromatic ring, heteroaromatic ring, condensed aromatic ring or condensed heteroaromatic ring which may have a substituent;

p represents an integer from 2 to 5):

(In the above formula,

R ^1b is optionally substituted C _{6 -20} phenyl group, C _{1 -20} alkyl, C _{5 -8} cycloalkyl group, C _{2 -20} alkanoyl groups, C _{7 -20} benzoyl group, C _{2 -12} alkoxy group or a phenoxy a carbonyl group, C _{1 -20} amide group, a nitro group, a C _{2 -25} alkenyl, C _{1 -10} alkyl-heteroaryl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group, C _{1 -20} heteroaryloxy-carbonyl group or a hetero arylthio group, a C _{-20 0} represents an amino group or C _{1 -20} amino group, with the proviso that, R ^1b may form a ring together with Ar _1, the linking group which may have a substituent C _{1 -10} alkylene _{group, - (CH = CH) n} -, - (C≡C) n - or a combination thereof (n is an integer of 0 to 3);

R ^2b is the same as in formula (2) as defined in claim 1;

Ar ₁ represents an aromatic ring, heteroaromatic ring, condensed aromatic ring or condensed heteroaromatic ring which may have a substituent;

p represents an integer of 2 to 5).

Another object of the present invention is that in formula (8),

R ^1a is C _{2 -25} alkenyl group which may be substituted, C _{3 -20} alkoxycarbonyl group, a C _{8 -20} phenoxycarbonyl group, or C _{1 -20} represents an amino group, with the proviso that, R ^1a is Ar ₁ It can form a ring with, in this case, R ^1a and Ar ₁ may be bonded to each other to form a divalent or trivalent linking group, the linking group which may have a substituent, C _{1 -10} alkylene group, - (CH = CH ) _n -,-(C≡C) _n -or a combination thereof (n is an integer from 0 to 3),

R ^2a is to provide a C _{2 -12} alkanoyl group of the oxime ester compound which may be substituted.

Another object of the present invention is in the formula (9),

R ^1b is an optionally substituted C _{1 -20} alkyl,

R ^2b is optionally substituted C _{1 -20} heteroaryl group, C _{1 -20} heteroaryl alkanoyl, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl group or a C _{2 - It} is providing the said oxime ester compound which is a ₁₀ aminocarbonyl group.

Another object of the present invention is to provide a photopolymerizable composition comprising an organic binder (b) and a photopolymerization initiator (c), wherein the component (c) contains the oxime ester compound.

It is another object of the present invention to provide the photopolymerizable composition wherein the organic binder (b) is an epoxy acrylate resin having a carboxyl group.

It is another object of the present invention to provide the photopolymerizable composition wherein the organic binder (b) is an epoxy acrylate obtained by reacting (hydro) phthalic anhydride with a reaction product of a novolak epoxy resin with (meth) acrylic acid.

It is another object of the present invention to provide the photopolymerizable composition further containing a photopolymerizable monomer (d).

Another object of the present invention is to provide the photopolymerizable composition further containing a polymer dispersant (e) containing a basic functional group.

Another object of the present invention is to provide the photopolymerizable composition further containing a color material (a).

Another object of the present invention is to provide a color filter having an image formed by the photopolymerizable composition.

Another object of the present invention is to provide a liquid crystal display device having an image formed by the photopolymerizable composition.

Effects of the Invention

The oxime ester compound of this invention can be used as a novel and highly sensitive photoinitiator. By combining this with an organic binder and a color material, the photopolymerizable composition useful for a color filter can be comprised. In particular, when combined with a black material, the obtained photopolymerizable composition is excellent in sensitivity and resolution even in the form of a high light-shielding thin film, and can form high quality resin BM at low cost. The color filter using resin BM of this invention is excellent in precision, flatness, and durability, and can improve the display quality of a liquid crystal element. In addition, since the manufacturing process and the color filter itself do not use harmful substances, the risk to the human body can be reduced and the environmental stability is improved. In addition, the present invention is not limited to BM, but can be used in a transparent photosensitive composition that does not use color materials, for example, for photo spacers or ribs (liquid crystal division alignment projections), and is widely used in various technical fields. .

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows typically the state of the change of the contact angle by heating.

Explanation of the sign

W1: Contact angle formed by the side of the thin line image and the substrate plane before heating.

W2: Contact angle formed by the side of the thin line image and the substrate plane after heating.

To practice the invention  Best form for

(a) color material

Although the color material is not an essential component in the present invention, the color material is used in combination in many applications. Here, the color material is to color the photosensitive composition. As the color material, dyes and pigments may be mentioned, and pigments are preferable in terms of heat resistance, light resistance and the like. As the pigment, pigments of various colors such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments and black pigments can be used. Moreover, about these structures, organic pigments, such as azo system, phthalocyanine system, quinacridone system, benzoimidazolone system, isoindolinone system, dioxadine system, indanthrene system, and perylene system, and also various inorganic pigments, etc. Can be used. The specific example of the pigment which can be used is shown below as a pigment number (pigment number, pigment No.). Terms such as “C.I. Pigment Red 2” below mean color index (C.I.).

As a red pigment, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48 , 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53 : 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81 : 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 , 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208 , 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254 , 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275 and 276. Among these, C.I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242 and 254 are preferred, and C.I. Pigment Red 177, 209, 224 and 254 are more preferred.

As a blue pigment, C.I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33 , 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 and 79. Among these, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4 and 15: 6 are preferred, and C.I. Pigment Blue 15: 6 is more preferred.

As a green pigment, C.I. Pigment greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54 and 55. Among these, C.I. Pigment Greens 7 and 36 are preferred.

As a yellow pigment, C.I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36 : 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94 , 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139 , 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174 , 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203 , 204, 205, 206, 207 and 208 may be mentioned. Among these, C.I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 and 185 are preferred, and C.I. Pigment Yellow 83, 138, 139, 150 and 180 are more preferred.

As an orange pigment, C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65 , 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 and 79. Among these, C.I. Pigment Orange 38 and 71 are preferred.

As a purple pigment, C.I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32 , 37, 39, 42, 44, 47, 49 and 50 may be mentioned. Among these, C.I. Pigment violets 19 and 23 are preferred, and C.I. Pigment violet 23 is more preferred.

As the black material, a black material mixed with the black material itself or red, green, blue and the like can be used. Such black materials may be optionally selected from inorganic and organic pigments and dyes, and may be used alone or as a mixture of plural kinds.

The single black material can be, for example, carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black or titanium black. Among them, carbon black and titanium black are particularly preferable in view of light shielding rate and image characteristics. As examples of commercially available carbon blacks, the following brands may be mentioned.

Mitsubishi Chemical Corporation Products: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900, etc.

DEGGUSA products: Printex 95, Printex 90, Printex 85, Printex 75, Printex 55, Printex 45, Printex 40, Printex 30, Printex 3, Printex A, Printex G, Special Black 550, Special Black 350, Special Black 250, Special Black 100 etc.

Cabot Corporation products: Monarch 460, Monarch 430, Monarch 280, Monarch 120, Monarch 800, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, BLACK PEARLS 480, PEARLS 130, etc. .

Columbian Chemicals products: RAVEN 11, RAVEN 15, RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN 890H, RAVEN 1000, RAVEN 1020, RAVEN 1040, etc.

Next, the black material by mixing will be described. Specific examples of the color material that is the base of the mixing include Victoria Pure Blue (42595), Oramine O (41000), Catyl Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK 70: 100 (50240), Erio Grausin X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Cymilor First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Cymilor First Red 4015 (12355), Lionol Red 7B4401 (15850), Pastgen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36) may be mentioned (wherein the numbers in parentheses refer to the color index (CI)).

Moreover, as an example of the other pigment which can be mixed and used, C.I. No. By C.I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154 and 166, C.I. Orange pigments 36, 43, 51, 55, 59 and 61, C.I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228 and 240, C.I. Purple pigments 19, 23, 29, 30, 37, 40 and 50, C.I. Blue pigments 15, 15: 1, 15: 4, 22, 60 and 64, C.I. Green pigment 7 and C.I. Mention may be made of the brown pigments 23, 25 and 26.

The carbon black can be used with other black or colored inorganic or organic pigments. Since the other pigments have lower light shielding or image characteristics than carbon black, the mixing ratio thereof is limited.

As a method for producing titanium black, for example, a method of heating and reducing a mixture of titanium dioxide and metal titanium in a reducing atmosphere (JP-A-49-5432), ultrafine titanium dioxide obtained by high temperature hydrolysis of titanium tetrachloride To reduce hydrogen in a reducing atmosphere containing hydrogen (JP-A-57-205322), or to reduce titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (JP-A-60-65069, JP-A-61 -201610), and a method (JP-A-61-201610) of attaching a vanadium compound to titanium dioxide or titanium hydroxide and then high temperature reduction in the presence of ammonia, but is not limited thereto.

As an example of commercially available titanium black, the titanium black 10S, 12S, 13R, 13M, 13M-C by Mitsubishi Material Corporation can be mentioned.

(b) organic binder

When constructing the photopolymerizable composition in the present invention, an organic binder (b) is used. The organic binder is not particularly limited, but an epoxy acrylate resin having a carboxyl group is particularly preferably used.

The epoxy acrylate resin is obtained by adding α, β-unsaturated monocarboxylate having a carboxyl group in the α, β-unsaturated monocarboxylic acid or ester moiety to the epoxy resin and further reacting the polybasic acid anhydride. Such reaction products are substantially free of epoxy groups in chemical structure and are not limited to "acrylates", but are conventionally so named because epoxy resins are raw materials and "acrylates" are representative examples.

As a raw material epoxy resin, it is represented by (o, m, p-) cresol novolak epoxy resin, a phenol novolak epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a trisphenol methane epoxy resin, or the following general formula, for example. Epoxy resins can preferably be used (Japanese Patent No. 2878486):

The molecular weight of an epoxy resin is 200-200,000, Preferably it is 300-100,000 as a weight average molecular weight measured by GPC. If the molecular weight is less than the above range, there is a problem in film formation in many cases. On the other hand, when it exceeds the said range, gelation will arise easily at the time of addition of (alpha), (beta)-unsaturated monocarboxylic acid, and it exists in the tendency which manufacture of the said resin is difficult.

The α, β-unsaturated monocarboxylic acid may be, for example, itaconic acid, crotonic acid, cinnamic acid, acrylic acid or methacrylic acid, acrylic acid or methacrylic acid is preferred, and acrylic acid is particularly preferred in view of high reactivity. Α, β-unsaturated monocarboxylates having a carboxyl group in the ester moiety are, for example, acrylic acid 2-succinoyloxyethyl ester, acrylic acid 2-maleinoyloxyethyl ester, acrylic acid 2-phthaloyloxyethyl ester, acrylic acid 2 Hexahydrophthaloyloxyethyl ester, methacrylic acid 2-succinoyloxyethyl ester, methacrylic acid 2-maleinoyloxyethyl ester, methacrylic acid 2-phthaloyloxyethyl ester, methacrylic acid 2-hexa Hydrophthaloyloxyethyl ester or crotonic acid 2-succinoyloxyethyl ester. Acrylic acid 2-maleinoyloxyethyl ester or acrylic acid 2-phthaloyloxyethyl ester is preferred, and acrylic acid 2-maleinoyloxyethyl ester is particularly preferred.

The addition reaction of the α, β-unsaturated monocarboxylic acid or ester thereof with the epoxy resin can be carried out by a known method. For example, the reaction can be carried out at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. The esterification catalyst is, for example, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine or benzyldiethylamine, or quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride or dodecyltrimethylammonium chloride Can be.

The amount of the α, β-unsaturated monocarboxylic acid or ester thereof is preferably 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1 equivalents, relative to 1 equivalent of the epoxy group of the raw material epoxy resin. When the amount of the α, β-unsaturated monocarboxylic acid or ester thereof is small, the amount of the unsaturated group to be introduced tends to be insufficient, and subsequent reaction with the polybasic acid anhydride tends to be insufficient. In addition, the residual of a large amount of epoxy groups is not advantageous. On the other hand, if the amount is large, α, β-unsaturated monocarboxylic acids or esters thereof remain as unreacted products. In any case, the curing characteristics tend to deteriorate.

The polybasic acid anhydrides further added to the epoxy resin to which the α, β-unsaturated monocarboxylic acid or its ester is added include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chloric anhydride, methyltetrahydrophthalic anhydride or biphenyl Tetracarboxylic acid may be an anhydride. Maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride or biphenyltetracarboxylic dianhydride are preferred, and tetrahydrophthalic anhydride Or biphenyltetracarboxylic dianhydride is particularly preferred.

The addition reaction of the polybasic acid anhydride can also be carried out by known techniques, and the reaction can be continued under the same conditions as the addition reaction of the α, β-unsaturated carboxylic acid or ester thereof. The addition amount of the polybasic acid anhydride is preferably such that the acid value of the epoxy acrylate resin formed is in the range of 10 to 150 mg KOH / g, more preferably 20 to 140 mg KOH / g. If the resin acid value is less than the above range, alkali developability tends to be poor, and if it exceeds the above range, curing performance tends to be poor.

As an organic binder (b), in addition to the epoxy acrylate resin which has a carboxyl group, the following resin can also be used. The following resins include resins belonging to epoxy acrylate resins, which are not necessarily classified as completely different materials.

That is, for example, homopolymers of (meth) acrylic acid, (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride or maleimide Or copolymers, carboxyl group-containing vinyl resins, and polyamides, polyesters, polyethers, polyurethanes, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone and acetyl cellulose. Among them, epoxy acrylate resins having a carboxyl group and carboxyl group-containing vinyl resins are preferred from the viewpoint of alkali developability and image forming property, and epoxy acrylate resins having carboxyl groups are more preferable.

The carboxyl group-containing vinyl resin is, for example, unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid or citraconic acid, and styrene, α-methylstyrene and hydroxystyrene. , Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, benzyl (Meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloyl morpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) Acrylamide, N, N-dimeth (Meth) acrylamide may be, N, N- dimethylaminoethyl (meth) copolymers of vinyl compounds such as acrylamide or vinyl acetate.

Of the above copolymers, styrene / (meth) acrylate / (meth) acrylic acid copolymers are preferred, and 3 to 30 mol% of styrene, 10 to 70 mol% of (meth) acrylate and 10 to 60 mol% of ( More preferred are copolymers comprising meth) acrylic acid. In particular, copolymers comprising 5 to 25 mol% styrene, 20 to 60 mol% (meth) acrylate and 15 to 55 mol% (meth) acrylic acid are preferred. In addition, such carboxyl group-containing vinyl resin has an acid value of 30 to 250 mg KOH / g, preferably 50 to 200 mg KOH / g, more preferably 70 to 150 mg KOH / g.

The carboxyl group-containing vinyl resin is preferably one having an ethylenically unsaturated bond in the side chain. This is, for example, a carboxyl group-containing polymer, allyl glycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocroto Aliphatic epoxy group-containing unsaturated compounds such as nates, crotonyl glycidyl ethers, monoalkyl monoglycidyl itaconates, monoalkyl monoglycidyl fumarates or monoalkyl monoglycidyl maleates, or 3,4-epoxy With cyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate or 7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl] oxymethyl (meth) acrylate Reaction products obtained by reacting the same alicyclic epoxy group-containing unsaturated compound in an amount of 5 to 90 mol%, preferably about 30 to about 70 mol%, based on the carboxyl group of the carboxyl group-containing polymer; Or allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamil (meth) acrylate, crotonyl (meth) acrylate, metalyl (meth) acrylate or N, Compounds having two or more unsaturated groups such as N-diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-pro A compound having two or more unsaturated groups such as phenyl (meth) acrylate, vinyl crotonate or vinyl (meth) acrylamide, an unsaturated carboxylic acid such as (meth) acrylic acid, or further unsaturated carboxylate, It may be a reaction product obtained by copolymerizing a compound having an electron unsaturated group with respect to the whole compound at a ratio of 10 to 90 mol%, preferably about 30 to about 80 mol%.

In addition, when using a photopolymerizable composition for formation of a liquid crystal division orientation protrusion, especially the weight average molecular weight of polystyrene conversion by a gel permeation chromatography (GPC) measurement is usually 1,000 or more, when epoxy acrylate resin which has a carboxyl group, It is preferably at least 1,500, usually at most 30,000, preferably at most 20,000, even more preferably at most 10,000, particularly preferably at most 5,000. In the case of the carboxyl group-containing vinyl resin, it is usually 1,000 or more, preferably 1,500 or more, more preferably 2,000 or more, and usually 100,000 or less, preferably 50,000 or less, even more preferably 20,000 or less, particularly preferably 10,000 or less. . In the case of containing an organic binder having a molecular weight within the above range, the deformation during heating of the photopolymerizable composition tends to be remarkable, and thus an arcuate protrusion which is a good shape of the liquid crystal split alignment protrusion can be formed.

(c) photopolymerization initiator

The photopolymerizable composition of the present invention contains an oxime ester compound represented by the formula (1) or (2) as a photopolymerization initiator:

(In said formula, a symbol is as defined in the said General formula (1).).

In formula (1), preferably, R ^1a is a C _{2 -25} alkenyl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group or C _{1 -20} amino group which may be substituted represents, R ^1a is R1 'and may form a ring together, and the linking group which may have a substituent C _1-10 alkylene _{group, - (CH = CH) n} -, - (C≡C) n - , or a combination thereof and (n is an integer of 0 to 3), R ^2a represents a C _{2 -12} alkanoyl group which may be substituted, R1 'represents any substituent containing an aromatic ring or a heteroaromatic ring.

(In said formula, a symbol is as defined in the said General formula (2).).

In formula (2), preferably, R ^1b represents a C _{1 -20} alkyl, R ^2b is optionally substituted C _{1 -20} heteroaryl group, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 - 20} phenoxycarbonyl nilal represents an alkanoyl group or a C _{2 -10-amino} group, R1 'represents any substituent containing an aromatic ring or a heteroaromatic ring.

Among the oxime ester compounds represented by the formulas (1) and (2), the compounds represented by the formula (3) or (4) are preferred:

(In said formula, a symbol is as defined in the said General formula (3).).

Formula (3), preferably, R ^1a is an optionally substituted C _{2 -25} alkenyl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group or C _{1 -20} alkyl amino R ^1a may form a ring together with R ³ or R ⁷ . In this case, R ^1a and R ³ and / or R ⁷ is combined with a divalent or trivalent linking group formed of, a linking group is C _{1 -10} alkylene group, which may be substituted, and each _{- (CH = CH) n -} , - (C≡C) _n -, or combinations thereof, and (n is an integer of 0 to 3), R ^2a represents a C _{2 -12} alkanoyl group which may be ^{substituted, R 3, R 4, R} 5, R 6 , and R ⁷ are each independently of the other, a hydrogen atom, a halogen atom, or which may be substituted with a C _{1 -12} alkyl, C _6-20 phenyl group, C ₁ group or -NR ¹⁰ R ¹¹ _to-20 heteroaryl group, R ³ , R ^4, R ^5, R ⁶ and R ⁷ represents at least one of the -NR ¹⁰ R ^11, stage, R ¹⁰ and R ¹¹ is C _{1 -12} alkyl groups which each independently of the other, may be hydrogen atom, substituted or , C _{2 -4} hydroxyl group, C _{3 -5} alkenyl group or represents a C _{6 -20} phenyl group, R ³ to R ⁷ are bonded to each other or each of which may form a cyclic structure in combination with R ¹ .

(In said formula, a symbol is as defined in the said General formula (4).).

It is as in formula (4), preferably, R ^1b is an optionally substituted C _{1 -20} alkyl, R ^2b is optionally substituted C _{1 -20} heteroaryl group, C _{1 -20} heteroaryl alkanoyl group, C _3-20 alkoxy carbonyl nilal alkanoyl group, C _{8 -20} phenoxycarbonyl nilal Kano a group or C _{2 -10-amino} group, R ^3, R ^4, R ^5, R ^6, and R ⁷ are each independently of the other hydrogen atom, a halogen atom, or which may be substituted with a C _{1 -12} alkyl, C _{6 -20} phenyl group, C _{1 -20} heteroaryl group or ^{-NR 10 R 11, R 3,} R 4, R 5, R 6 , and one or more of R ⁷ is -NR ¹⁰ R ¹¹ (wherein, R ¹⁰ and R ¹¹ is C _{1 -12} alkyl, C _{2 -4} hydroxyl group which each independently of the other, may be hydrogen atoms, or substituted, C _{3 -5} it represents a represents an alkenyl group or C _{6 -20} phenyl group), provided that, R ³ to R ⁷ are bonded to each other or each of which may form a cyclic structure in combination with R ^1b.

More preferably, the oxime ester compound is a compound represented by any one of the following formulas (5) to (7):

(In said formula, a symbol is as defined in the said General formula (5).).

Preferably, R ^1a is C _{2 -25} alkenyl, C _{1 -10} alkyl-heteroaryl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group, C _{1 -15} heteroaryl which may be substituted arylthio group, a C _{2 -12} dialkylamino group, C _{1 -15} alkyl or C ₃ dialkylamino _-15 N- -N- acyloxy or acylamino group, or R ^1a and R ³ and / or R ⁷ are to each other coupled may have a substituent, C _{1 -15} alkylene group, which by-forms or a combination thereof, - (CH = CH) _n.

More preferably, R ^1a is C _{2 -12} alkenyl group which may be substituted, C _{3 -12} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group, C _{1 -10} alkyl group or a hetero arylthio C _{2 -} to form or a combination thereof - _8, or an amino group, or R ^1a and R ³ and / or R ⁷ are bonded to each other which may have a substituent, C _{1 -10} alkylene _{group, - (CH = CH) n} .

In the above, n is an integer of 0 to 3, preferably 1 or 2.

Preferably, R ^2a is optionally substituted C _{2 -12} alkanoyl groups, C _{3 -12} noilgi alkenyl, C _{3 -8} cycloalkyl alkanoyl, C _{7 -15} benzoyl group, C _{1 -15} group with heteroaryl , C _{2 -10} represents an alkoxycarbonyl group or C _{7 -20} phenoxy group, C _{3 -12} dialkylamino group or a C _{7 -15} phenylamino group.

Preferably, R ^3, R ^6, R ⁷ and R ¹² to R ¹⁵ are each independently of the other a hydrogen atom, a halogen atom, or which may be substituted with a C _{1 -12} alkyl, C _{2 -12} alkenyl, C ₂ noilgi _-12 alkenyl, C _{5 -8} cycloalkyl group, C _{6 -12} phenyl group, C _{3 -20} heteroaryl group, C _{7 -12} benzoyl group, C group with _2-12 alkanoyl, C _{3 -20} heteroaryl, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl, C _{3 -20} heteroaryloxy carbonyl nilal alkanoyl group, C _3-20 alkoxycarbonyl group, C _8-20 phenoxy Brassica A carbonylalkyl group, a C _3-20 heteroaryloxycarbonylalkyl group, a C _2-12 alkoxycarbonyl group or a phenoxycarbonyl group, or —OR ⁸ or NR ¹⁰ R ¹¹ , wherein R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁵ may be bonded to each other or each of them may be bonded to R ^1a to form a cyclic structure.

Preferably, R ¹⁶ is optionally substituted C _{1 -12} alkyl, C _{2 -12} alkenyl, C _{2 -12} alkenyl noilgi, C _{5 -8} cycloalkyl group, C _{6 -12} phenyl group, C _{3 -20} heteroaryl group, C _{7 -12} benzyl group, C _{7 -12} benzoyl group, C _{2 -12} alkanoyl groups, C _{3 -20} heteroaryl as weather, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl alkyl group, a C _{3 -20} heteroaryloxy carbonyl group, a C _2-12 alkoxy group or a phenoxy group, C _{3 -15} trialkylsilyl group or a C _{2 -4} represents a hydroxyl group, with the proviso that, R ^3, R ⁶ , R ⁷ and R ¹² to R ¹⁶ may be bonded to each other or each of them may be bonded to R ^1a to form a cyclic structure.

Here, R ⁸ is C _{1 -12} alkyl group which may be hydrogen, or substituted, C _{2 -8} alkanoyl, C _{3 -12} alkenyl, C _{3 -20} noilgi alkenyl, C _{6 -12} phenyl, - ( _{CH 2 CH 2 O) m H} (m is a number ranging from 1 to 20, preferably an integer of 1 to 5) or C _{3 -15} tree represents an alkylsilyl group, R ⁹ is C _{1 -12,} which may be a hydrogen atom or a substituted alkyl group, C _{2 -8} alkanoyl, C _{3 -12} alkenyl group or represents a C _6-12 phenyl group, R ¹⁰ and R ¹¹ is C _{1 -12} alkyl groups which each independently of the other, may be hydrogen atoms, or substituted, C _{2 -4} hydroxyl group, C _{3 -5} alkenyl group represents a phenyl group or a C _{6 -20.}

(In said formula, a symbol is as defined in the said General formula (6).).

Preferably, R ^1b is optionally substituted C _{6 -15} phenyl group, C _{1 -10} alkyl, C _{5 -8} cycloalkyl group, C _{2 -15} alkanoyl groups, C _{7 -15} benzoyl group, C _{2 -12} alkoxy group or a C _{7 -12} phenoxy group, C _{1 -15} amide group, a nitro group, a C _{2 -15} alkenyl, C _{1 -10} alkyl-heteroaryl, C _{3 -20} alkoxycarbonylalkyl group, C _{1 -15} heteroaryl alkylthio group, a C _{2 -12} dialkylamino group, C _{1 -15} alkyl or C ₃ dialkylamino or acylamino _-15 N- oxy -N- acylamino group, or R ^1a and R ³ and / or R ⁷ are bonded to each other may have a substituent, C _{1 -15} alkylene group, which by-forms or a combination thereof, - (CH = CH) _n.

More preferably, R ^1b is optionally substituted C _{6 -15} phenyl group, C _{1 -10} alkyl, C _{5 -8} cycloalkyl group, C _{2 -12} alkanoyl groups, C _{7 -12} benzoyl group, C _{2 -12} alkoxycarbonyl group or C _{7 -12} phenoxycarbonyl group, C _1-10 amide group, nitro group, C _2-12 alkenyl, C _3-12 alkoxycarbonyl group, C _{8 -20} phenoxycarbonyl group, C _{1 - 10} hetero arylthio group or an amino group or a C _{2 -8,} or R ^1a and R ³ and / or R ⁷ is C _{1 -10} alkylene group which may have a substituent bonded to each _{other, - (CH = CH) n} - or a Form a combination.

In the above, n is an integer of 0 to 3, preferably 1 or 2.

Preferably, R ^2a is C _{1 -15} heteroaryl group, C _{1 -15} heteroaryl alkanoyl, C _{3 -15} alkoxy carbonyl nilal alkanoyl groups, C _{8 -15} phenoxycarbonyl nilal alkanoyl group which may be substituted , C _{3 -15} heteroaryloxy carbonyl nilal Kano a group or C _{2 -10-amino} group.

Preferred R ^3, R ^6, R ⁷ and R ¹² to R ¹⁵ is the same as the preferred R ^3, R ^6, R ⁷ and R ¹² to R ¹⁵ in the above formula (6).

(Wherein, R ^1b is as defined in formula (4) above;

R ^2b represents R ^2a in Formula (3) or R ^2b in Formula (4);

R ^3, R ^6, R ⁷ and R ¹² to R ¹⁶ is C _{1 -12} alkyl, C _{2 -12} alkenyl noilgi, C _{6 -20} phenyl, C _{7 -20,} which may be each substituted with a hydrogen atom, a halogen atom, or Benzyl or benzoyl, or —NR ¹⁰ R ¹¹ , provided that R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ may be bonded to each other to form a cyclic structure, and R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ is one or more of the group by C _{1 -20} alkyl hete Loa reel, heteroaryl, alkanoyl and heteroaryl which may be substituted, and C _{3 -15} tree least one selected from the group consisting alkylsilyl ).

In the formulas representing the oxime ester compounds of the invention, the "substitutable substituents" for R ^1a , R ^1b , R ^2a , R ^2b and R ² to R ¹⁶ are each independently of one another, for example, a fluorine atom Halogen atoms such as chlorine, bromine or iodine atoms; Hydroxyl group; Nitro group; Cyano group; Or any organic group, and any organic group may be, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, t-amyl group , n- hexyl, n- heptyl, n- octyl group or a t- octyl groups such as C _{1 -18} linear or branched alkyl group; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group or adamantyl group, such as C _{3 -18} cycloalkyl; Vinyl group, propenyl group or a hexenyl group and C _{2 -18} straight-chain or branched alkenyl groups such as; Cyclopentenyl group or a cyclohexenyl C _{3 -18} cycloalkenyl group, such group; Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, amyloxy group, t-amyloxy group, n-hexyloxy group, n- tilok heptyl group, n- or t- oxide tilok time octyloxy group and C _{1 -18} linear or branched alkoxy group such as; Methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, s-butylthio group, t-butylthio group, amylthio group, t-amylthio group, n-hex silti come, n- heptyl tilti come, n- or t- oxide tilti come octylthio group and import of C _{1 -18} linear or branched alkyl group; C _{6 -18} aryl group such as phenyl group, tolyl group, xylyl group or a mesityl group; C _{7 -18} aralkyl groups such as benzyl group or phenethyl group; C _2-18 straight or branched alkenyloxy groups such as vinyloxy group, propenyloxy group or hexenyloxy group; Vinyl thio, phenylthio or pro-hexenylthio C _{2 -18} coming straight-chain or branched alkenyl groups such nilti; Acyl group represented by -COR ¹⁷ ; Carboxyl groups; An acyloxy group represented by -OCOR ¹⁸ ; Amino group represented by -NR ¹⁹ R ²⁰ ; Acylamino group represented by -NHCOR ²¹ ; Carbamate groups represented by -NHCOOR ²² ; Carbamoyl group represented by -CONR ²³ R ²⁴ ; Carboxylate group represented by -COOR ²⁵ ; Sulfamoyl group represented by -SO ₃ NR ²⁶ R ²⁷ ; Sulfonate groups represented by -SO ₃ R ²⁸ ; Saturated or unsaturated such as 2-thienyl group, 2-pyridyl group, furyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group or tetrahydrothiophene dioxide group Trialkylsilyl groups such as heterocyclic groups or trimethylsilyl groups.

In addition, as the substituent in the present invention, a substituent such as = N-OC (= 0) R ² may be mentioned in addition to the above. As such a compound, R ^1a and R ^1b are each = N-OC (= O) C _{1 -20} alkyl group which is substituted with R ^2, C _{5 -8} cycloalkyl group, C _{2 -20} alkanoyl groups, C _{7 -20} benzo group, may be a C _{2 -12} alkoxycarbonyl group or phenoxycarbonyl group, or C _{1 -20} amides.

In the above, a plurality of substituents may combine to form a ring, the ring formed may be a saturated or unsaturated aromatic ring or a heterocyclic ring, may further have a substituent in cyclic form, and the substituent may also Can be formed.

R ¹⁷ to R ²⁸ each represent a hydrogen atom, a substituted alkyl group, a substituted alkenyl group, a substituted allyl group or a substituted aralkyl group. Their positional relationship is not particularly limited, and when they have a plurality of substituents, the substituents may be the same or different.

In the above, the compound represented by General formula (5)-(7) was demonstrated in detail, and the compound which has a preferable combination of a substituent is summarized below.

In the formula (5),

R ^1a is optionally substituted C _{2 -25} alkenyl, C _{3 -20} alkoxycarbonyl group, a C _{8 -20} phenoxycarbonyl group or C _{1 -20} alkyl, or amino, or R ^1a is R ³ or R ⁷ form a ring together with, and in this case, R ^1a and R ³ and / or R ⁷ are bonded to each other, and divalent or trivalent form a linkage group, the linking group which may have a substituent, C _{1 -10} alkylene group, - ( CH = CH) _n -,-(C≡C) _n- , or a combination thereof (n is an integer from 0 to 3),

R ^2a is a C _{2 -12} alkanoyl group which may be substituted,

R ^3, R ^6, R ⁷ and R ¹² to R ¹⁶ is C _{1 -12} alkyl, C _{2 -12} alkenyl noilgi, C _{6 -20} phenyl, C _{7 -20,} which may be each substituted with a hydrogen atom, a halogen atom, or A benzyl group or a benzoyl group, or -NR ¹⁰ R ¹¹ , provided that R ³ , R ⁶ , R ^7, and R ¹² to R ¹⁶ are bonded to each other to form a cyclic structure.

In formula (6),

R ^1b is an optionally substituted C _{1 -20} alkyl,

R ^2b is optionally substituted C _{1 -20} heteroaryl alkanoyl, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl group, or C _{2 -10} and amino group,

R ^3, R ^6, R ⁷ and R ¹² to R ¹⁶ is C _{1 -12} alkyl, C _{2 -12} alkenyl noilgi, C _{6 -20} phenyl, C _{7 -20,} which may be each substituted with a hydrogen atom, a halogen atom, or A benzyl group or a benzoyl group, or -NR ¹⁰ R ¹¹ , provided that R ³ , R ⁶ , R ^7, and R ¹² to R ¹⁶ are bonded to each other to form a cyclic structure.

In formula (7),

R ^1b is optionally substituted C _{1 -20} alkyl, C _{2 -25} alkenyl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group or C _{1 -20} alkyl, or amino, or R ^1a is R ³ or form a ring with R ^7, and in this case, R ^1a and R ³ and / or R ⁷ are bonded to each other, and divalent or trivalent form a linking group, the linking group is C _1, which may have a substituent _-10 alkylene group,-(CH = CH) _n -,-(C≡C) _n -or a combination thereof (n is an integer from 0 to 3),

R ² is C _{2 -12} alkanoyl groups, C _{1 -20} hetero arylalkenyl which may be substituted alkanoyl group, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl group or a C _{2 - 10} aminocarbonyl group,

R ^3, R ^6, R ⁷ and R ¹² to R ¹⁶ is C _{1 -12} alkyl, C _{2 -12} alkenyl noilgi, C _{6 -20} phenyl, C _{7 -20,} which may be each substituted with a hydrogen atom, a halogen atom, or Benzyl or benzoyl, or —NR ¹⁰ R ¹¹ , provided that R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ may be bonded to each other to form a cyclic structure, and R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ is one or more of the at least one selected from the group, and C _{3 -15} tree group consisting alkylsilyl a C _{1 -20} alkyl, heteroaryl, heteroaryl-alkanoyl and heteroaryl which may be substituted Containing compounds.

Further preferred as oxime ester compounds are compounds represented by the following general formula (8) or (9):

(In said formula, a symbol is as defined in the said General formula (8).).

In formula (8), preferably, R ^1a is a C _{2 -25} alkenyl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group or C _{1 -20} amino group which may be substituted represents, with the proviso that, R ^1a may form a ring together with Ar _1, in this case, R ^1a and Ar ₁ may be bonded to each other to form a divalent or trivalent linking group, the linking group is C _1- which may have a substituent _{10 alkylene, - (CH = CH) n} -, - (C≡C) n - , or combinations thereof, and (n is an integer of 0 to 3), R ^2a is a C _{2 -12} know the alkanoyl group which may be substituted .

(In said formula, a symbol is as defined in the said General formula (9).).

It is as in formula (9), preferably, R ^1a is an optionally substituted C _{1 -20} alkyl, R ^2b is optionally substituted C _{1 -20} heteroaryl group, C _{1 -20} heteroaryl alkanoyl group, C _3-20 alkoxy carbonyloxy a nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl group or a C _{2 -10-amino} group.

In addition, Ar ₁ is a portion required for the compound of the present invention to absorb light, and a compound which absorbs light having a wavelength of 200 nm or more, preferably 200 to 500 nm, more preferably 250 to 500 nm is preferable. Is used. Specifically, Ar ₁ is, for example, an aromatic ring containing a benzene ring, phenanthrene ring, azulene ring, fluorene ring, acenaphthylene ring, indene ring or condensed ring thereof, furan ring, thiophene ring, Pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazan ring, triazole ring, pyran ring, thiadiazole ring, oxadiazole ring, pyridine Ring, pyridazine ring, pyrimidine ring, ring containing pyrazine ring or condensed ring thereof, or acridine ring, phenanthridine ring, xanthene ring, carbazole ring, phenazine ring, phenothiazine ring, phenoxy Condensed rings containing aromatic rings and heterocyclic rings, such as photographic rings or benzothiazole rings.

p corresponds to the number of substitutable hydrogen atoms present in Ar ₁ selected from the above aromatic rings, heteroaromatic rings, condensed aromatic rings and condensed heteroaromatic rings, and is usually 2 to 5, preferably 2 to 3.

Specific examples of preferred compounds of the present invention are shown in Tables 1 (1) to 1 (6) below with respect to combinations of substituents.

In addition, as said photoinitiator, the said oxime ester compound can be used individually, or can be used in combination with another photoinitiator. Sensitivity improvement can be anticipated by using together another photoinitiator. For example, the following compounds may be mentioned.

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine or 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloro Halomethylated triazine derivatives such as rommethyl) -s-triazine; 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2'-benzofuryl) vinyl] -1,3 , 4-oxadiazole, 2-trichloromethyl-5- [β- (2 '-(6 "-benzofuryl) vinyl)]-1,3,4-oxadiazole or 2-trichloromethyl-5 Halomethylated oxadiazole derivatives such as furyl-1,3,4-oxadiazole; 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chloro Phenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'- Imidazole derivatives such as methoxyphenyl) -4,5-diphenylimidazole dimer or (4'-methoxyphenyl) -4,5-diphenylimidazole dimer; benzoin methyl ether, benzoin Benzoin alkyl ethers such as phenyl ether, benzoin isobutyl ether or benzoin isopropyl ether; anthra such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone or 1-chloroanthraquinone Non derivatives; benzanthrone derivatives; with benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone or 2-carboxybenzophenone Benzophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy Hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '-(methylthio) phenyl) -2-mor Acetophenone derivatives such as polyno-1-propanone or 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, Thioxanthone derivatives such as 2-chlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone or 2,4-diisopropyl thioxanthone; ethyl p-dimethylamino benzoate Or ethyl p-di Benzoate derivatives such as ethylamino benzoate, acridine derivatives such as 9-phenylacridine or 9- (p-methoxyphenyl) acridine, phenazine derivatives such as 9,10-dimethylbenzophenazine; Or bis-cyclopentadienyl-Ti-dichloride, bis-cyclopentadienyl-Ti-bis-phenyl, bis-cyclopentadienyl-Ti-bis- (2,3,4,5,6-pentafluoro Lofen-1-yl), bis-cyclopentadienyl-Ti-bis- (2,3,5,6-tetrafluorophen-1-yl), bis-cyclopentadienyl-Ti-bis- ( 2,4,6-trifluorophen-1-yl), bis-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, bis-cyclopentadienyl-Ti-2, 4-di-fluorophen-1-yl, bis-methylcyclopentadienyl-Ti-bis- (2,3,4,5,6-pentafluorophen-1-yl), bis-methylcyclopenta Dienyl-Ti-bis- (2,6-di-fluorophen-1-yl) or bis-cyclopentadienyl-Ti-2,6-di-fluoro-3- (pyrrole-1-yl) Titanocene derivatives such as phenen-1-yl.

A sensitizing dye can be added to the photopolymerizable composition of this invention further in addition to the said initiator component. In order for a photopolymerizable composition to produce a photopolymerization reaction under light-shielding conditions, it is preferable to add a sensitizing dye. Such sensitizing dyes are, for example, coumarin compounds having a heterocyclic ring as described in JP-A-3-239703 or JP-A-5-289335, 3-ketocoumarin compound as described in JP-A-63-221110, Xanthene dyes described in JP-A-4-221958 or JP-A-4-219756, pyrromethene dyes described in JP-A-6-19240, JP-A-47-2528, JP-A-54-155292, (P-dialkylaminobenzylidene) ketones described in JP-A-56-166154 or JP-A-59-56403, styryl dyes, sensitizing dyes having a gluridyl group described in JP-A-6-295061 or JP The diamino benzene compound described in -A-11-326624.

Among these sensitizing dyes, amino group-containing sensitizing dyes or xanthene dyes are particularly preferred.

(d) photopolymerizable monomer

As the photopolymerizable monomer in the present invention, a compound having one or more ethylenically unsaturated groups (hereinafter referred to as an ethylenic compound) is used. Specifically, these include, for example, esters of aliphatic (poly) hydroxy compounds and unsaturated carboxylic acids, esters of aromatic (poly) hydroxy compounds and unsaturated carboxylic acids, unsaturated carboxylic acids and polyhydric carboxylic acids and aliphatic polyhydrides. Esters obtained from hydroxy compounds, ethylene oxide of aromatic polyhydroxy compounds, esterification products of propylene oxide addition products with unsaturated carboxylic acids, ethylene oxide of aliphatic polyhydroxy compounds, propylene oxide addition products of unsaturated carboxylic acids Esterification products, esters of caprolactone-modified polyhydric alcohols and unsaturated carboxylic acids, reaction products of polyhydric alcohols and polyhydric isocyanates and unsaturated carboxylic acids, styryl terminated compounds, phosphoric acid-containing unsaturated compounds, or polyepoxy and unsaturated carboxylic acids of It may be an addition product.

Of these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are specifically, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, Trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate , Acrylates such as dipentaerythritol hexaacrylate or glycerol acrylate, or the same kind of methacrylates, itaconates, crotonates or maleates.

The ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid may be, for example, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate or pyrogallol triacrylate. have. The esters obtained by esterification of unsaturated carboxylic acids with polyhydric carboxylic acids and polyhydric hydroxy compounds need not necessarily be single substances, and representative embodiments thereof include condensates of (meth) acrylic acid, phthalic acid and ethylene glycol, (meth ) Condensates of acrylic acid, maleic acid and diethylene glycol, condensates of (meth) acrylic acid, terephthalic acid and pentaerythritol, and condensates of (meth) acrylic acid, adipic acid, butane diol and glycerol.

Examples of other ethylenic compounds used in the present invention include acrylamides such as ethylenebisacrylamide; Allyl esters such as diallyl phthalate; And vinyl group-containing compounds such as divinyl phthalate are also useful.

Among the ethylenic compounds, those having a (meth) acryloyl group are preferred, and those having an acryloyl group are more preferred. Such compounds include, for example, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, Dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate.

As a compounding quantity of the said component in the photopolymerizable composition of this invention, per 100 weight part of organic binders (b), a photoinitiator (c) is 0.1-50 weight part, Preferably it is 1-45 weight part, and a photopolymerizable monomer ( d) is usually 0 to 200 parts by weight, preferably 3 to 180 parts by weight. In addition, black material (a) is 30-70 weight% normally in the total solid except a solvent, Preferably it is 35-65 weight%. Further, the sensitizing dye is usually 0 to 30 parts by weight, preferably 0 to 10 parts by weight, per 100 parts by weight of the organic binder (b).

When the photopolymerization initiator is less than the above range, the photopolymerizable composition tends to have low sensitivity and poor working efficiency, and when it exceeds the above range, the film forming function tends to decrease. If a photopolymerizable monomer (ethylenic compound) is less than the said range, crosslinking density will fall and it will have a problem in durability, heat resistance, etc., and when it exceeds this range, developability may fall. If a black material is less than the said range, light-shielding property will fall, and therefore, formation of resin BM which has sufficient optical density tends to become difficult. On the other hand, when it exceeds the said range, there exists a tendency for the sensitivity, resolution, developability, etc. to fall remarkably, and hence image formation tends to become difficult.

The photopolymerizable composition of the present invention is usually a black material (a), an organic binder (b) (epoxy acrylate resin having a carboxyl group), a photopolymerization initiator (c) (oxime ester compound) and, if necessary, photopolymerizable. It is used in the state which melt | dissolved the monomer (d) (ethylenic compound) in a solvent.

The solvent is preferably selected from those capable of dissolving or dispersing the components constituting the composition and having a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120-170 degreeC.

Such solvents are, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol t-butyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol or Glycol monoalkyl ethers such as tripropylene glycol methyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether or diethylene glycol dibutyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, dipropylene glycol monomethyl Glycol alkyl ether acetates such as ether acetate or 3-methyl-3-methoxybutyl acetate;

Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether or dihexyl ether;

Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone or methyl nonyl ketone Such ketones;

Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol or glycerol;

aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene or dodecane;

Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene or bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene or cumene;

Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, Butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxyprop Chain or cyclic esters such as cypionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate or γ-butyrolactone;

Alkoxycarboxylic acids such as 3-methoxypropionic acid or 3-ethoxypropionic acid;

Halogenated hydrocarbons such as butyl chloride or amyl chloride;

Ether ketones such as methoxymethylpentanone; or

Nitrile such as acetonitrile or benzonitrile.

Solvents corresponding to the above are trade name mineral sprit, Varsol # 2, Apco # 18 solvent, Apco thinner, Socal solvent No. 1 and No. 2, Solvesso # 150, Shell TS28 solvent, Carbitol, Ethyl Carbitol, butyl Carbitol, Methyl Cellosolve, Ethyl Cellosolve, Ethyl Cellosolve Acetate, and diglime.

These solvents may be used alone or as mixtures of several kinds. The photopolymerizable composition of the present invention is preferably prepared using such a solvent to have a solid concentration of 5 to 50% by weight, preferably 10 to 30% by weight.

In the present invention, the essential components (a), (b) and (c), and optional component (d) are added as necessary, and a pigment dispersant, an adhesion improving agent, a coatability improving agent, a developability improving agent, and the like are preferably added. can do. In particular, in the composition of the present invention, it is preferable to mix the pigment dispersant because it is important in terms of quality stability to finely disperse the black material and stabilize the dispersed state.

The pigment dispersant is one having affinity for both the black material (a) and the organic binder (b), and may be, for example, a nonionic, cationic or anionic surfactant, or a polymer dispersant. Of these, polymer dispersants are preferred, and polymer dispersants (e) having basic functional groups such as nitrogen-containing heterocycles such as primary, secondary or tertiary amino groups, pyridine, pyrimidine or pyrazine are advantageously used.

Specific examples of the preferred chemical structure of the polymer dispersing agent (e) having a basic functional group include polyisocyanate compounds, compounds having one or two hydroxyl groups in the molecule, and compounds having active hydrogen and tertiary amino groups in the same molecule. The dispersion resin obtained by making a reaction can be mentioned.

The polyisocyanate compound is, for example, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-di Aromatic diisocyanates such as isocyanates or tolidine diisocyanates; Aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate or dimer acid diisocyanate; Alicyclic diisocyanates such as isophorone diisocyanate, 4,4'-methylenebis- (cyclohexyl isocyanate) or ω, ω'-diisocyanate dimethylcyclohexane; Aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate or α, α, α ', α'-tetramethylxylylene diisocyanate; Lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate phenyl Triisocyanates such as methane) or tris (isocyanatephenyl) thiophosphate; Or trimers or water addition products thereof, or polyol addition products thereof. Preferred as polyisocyanates are trimers of organic diisocyanates, most preferred are trimers of tolylene diisocyanates or trimers of isophorone diisocyanates, which can be used alone or in combination.

Processes for the preparation of trimers of isocyanates include, for example, treating the polyisocyanates with suitable trimerization catalysts such as tertiary amines, phosphines, alkoxides, metal oxides or carboxylates to partially trimer the isocyanate groups, After stopping the trimerization by adding a catalyst, unreacted polyisocyanate may be removed by solvent extraction and thin film distillation to obtain a desired isocyanurate group-containing polyisocyanate.

Compounds having one or two hydroxyl groups in the same molecule, for example, polyether glycols, polyester glycols, polycarbonate glycols or polyolefin glycol, or such a hydroxyl group in the terminal of the compound C _{1 -25} alkyl May be alkoxylated, or a mixture of two or more thereof.

The polyether glycols may be polyether diols, polyether ester diols or mixtures of two or more thereof. Polyether diols are those obtained by homopolymerization or copolymerization of alkylene oxides, for example polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol or It may be a mixture of two or more thereof.

Polyether ester diols are those obtained by reacting an ether group-containing diol or a mixture of this with another glycol with dicarboxylic acids or anhydrides thereof, or those obtained by reacting polyester glycols with alkylene oxides, e.g. For example poly (polyoxytetramethylene) adipate. Most preferred as the polyether glycol is an alkoxylated compound is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a hydroxyl group of one of the terminal of the compound to a C _{1 -25} alkyl.

Polyester glycols are dicarboxylic acids (e.g. succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid or phthalic acid) or anhydrides thereof and glycols (e.g. ethylene glycol, diethylene glycol, Triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, Neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentane Diol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5- Aliphatic glycols such as dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol or 1,9-nonane diol, alicyclics such as bishydroxymethylcyclohexane Glycol, xylylene glycol or bismuth Obtained by polycondensation of an aromatic glycol such as hydroxyethoxybenzene or N-alkyldialkanolamine such as N-methyldiethanolamine, for example polyethylene adipate, polybutylene adipate, polyhexamethylene adipate or polyethylene / polypropylene adipate, or a diol or a diol or poly-C _{1 -25 1} polylactone obtained by using an alcohol as an initiator monool lactone, for example, polycaprolactone glycol, a lactone or a polymethyl ballet It may be a mixture of two or more thereof. Most preferred as a polyester glycol, a polycaprolactone obtained used the polycaprolactone glycol or C _{1 -25} alcohol as an initiator.

The polycarbonate glycol may be, for example, poly (1,6-hexylene) carbonate or poly (3-methyl-1,5-pentylene) carbonate, and the polyolefin glycol may be, for example, polybutadiene glycol, hydrogenated poly Butadiene glycol or hydrogenated polyisopropylene glycol. The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is 300 to 10,000, preferably 500 to 6,000, more preferably 1,000 to 4,000.

Now, a compound having an active hydrogen and a tertiary amino group in the same molecule will be described. Active hydrogen, ie, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, may be a hydrogen atom in a functional group such as a hydroxyl group, an amino group or a thiol group, among which a hydrogen atom in an amino group, in particular a primary amino group is preferred. Do. The tertiary amino group is not particularly limited. Tertiary amino group may be an amino group, or a heterocyclic structure, and more specifically to an imidazole ring or a triazole ring having a C _{1 -4} alkyl group;

Examples of the compound having active hydrogen and tertiary amino groups in the same molecule include, for example, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N- Dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N-dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine or N, N-dibutyl-1,4-butanediamine may be mentioned.

Moreover, N containing heterocycle as a tertiary amino group is a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, benzotriazole, for example. N-containing hetero 5-membered rings such as rings, benzoxazole rings, benzothiazole rings or benzothiadiazole rings, or pyridine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, acridine rings or N-containing hetero 6-membered ring such as isoquinoline ring. Preferred as N-containing heterocycles are imidazole rings or triazole rings.

As specific examples of the compound having an imidazole ring and an amino group, for example, 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole and 1- (2-aminoethyl) imidazole may be mentioned. have. As specific examples of the compound having a triazole ring and an amino group, for example, 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H -1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole and 3-amino-1-benzyl-1H-2,4-triazole may be mentioned.

Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole or 3-amino-1,2,4 -Triazole is preferred. The preferred blending ratio of the dispersant material is 10 to 200 parts by weight, preferably 20 to 20, of compounds having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 per 100 parts by weight of the polyisocyanate compound. 190 parts by weight, more preferably 30 to 180 parts by weight, and 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight of the compound having active hydrogen and tertiary amino groups in the same molecule.

The GPC equivalent weight average molecular weight of the polymer dispersing agent (e) having a basic functional group is 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. If the molecular weight is 1,000 or less, the dispersibility and dispersion stability tend to be insufficient, and if it is 200,000 or more, the solubility tends to decrease and the dispersibility tends to be insufficient, and at the same time, control of the reaction will be difficult. The preparation of the polymer dispersant is carried out in accordance with known methods for preparing polyurethane resins. As solvents for the preparation, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone or isophorone, esters such as ethyl acetate, butyl acetate or cellosolve acetate, benzene Hydrocarbons such as toluene, xylene or hexane, some alcohols such as diacetone alcohol, isopropanol, secondary butanol or tert butanol, chlorides such as methylene chloride or chloroform, ethers such as tetrahydrofuran or diethyl ether, or dimethylform Aprotic polar solvents such as amides, N-methylpyrrolidone or dimethyl sulfoxide can be used.

For the production, a urethanization catalyst is usually used. This is for example tin based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate or stannous octoate, iron acetylacetonate or ferric chloride. Iron based catalysts or tertiary amine based catalysts such as triethylamine or triethylenediamine.

It is preferable to control the introduction amount of the compound which has active hydrogen and a tertiary amino group in the same molecule in the range of 1-100 mg KOH / g as amine value after reaction. More preferably, it is in the range of 5-95 mg KOH / g. The amine number is a value expressed in mg of KOH corresponding to the acid value when neutralizing and titrating the basic amino group with an acid. If the amine value is less than or equal to the above range, the dispersing ability tends to be lowered, and if it exceeds the above range, the developability tends to be lowered. In the case where an isocyanate group remains in the polymer dispersant obtained by the above reaction, deactivating the isocyanate group with an alcohol or an amine compound is preferable because it tends to increase the stability over time of the product. In the case of using a polymer dispersant, the proportion is preferably 0.1 to 30% by weight, particularly preferably 0.5 to 25% by weight, with respect to the black material (a).

Next, the manufacturing method of the photopolymerizable composition of this invention is demonstrated. In this invention, it is preferable to disperse | distribute a color material normally using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, or a homogenizer, for example. By forming the color material into fine particles by the dispersion treatment, the coating properties of the resist will be improved. In addition, when using a black material as the color material, the above treatment will contribute to the improvement of the light shielding ability.

Dispersion treatment is preferably carried out in a system using a black material and a solvent or an organic binder having a dispersing function, or in a system further using the pigment dispersant. Particular preference is given to using polymeric dispersants to achieve good dispersion stability over time. In addition, dispersion treatment in a liquid in which all the components to be combined as a resist liquid are mixed at the same time is not preferable because the highly reactive component may cause deformation due to heat generated during dispersion.

In the case of dispersing with a sand grinder, glass beads or zirconia beads having a diameter of 0.1 to 8 mm are preferably used. As dispersion conditions, the temperature is usually 0 ° C to 100 ° C, preferably room temperature to 80 ° C. The dispersion time is arbitrarily adjusted because the appropriate time varies depending on the composition (color material, solvent, dispersant) of the ink, the device size of the sand grinder, and the like. It is a measure of dispersion to control the gloss of the ink so that the 20 ° gloss value of the resist is in the range of 100 to 200. When the resist gloss is low, the dispersion treatment is not sufficient, and in many cases coarse pigment particles remain, which is insufficient in view of developability, adhesion, resolution and the like. In addition, when the dispersion treatment is performed until the gloss value exceeds the above range, a large number of ultra fine particles are formed, and conversely, dispersion stability tends to be impaired.

Subsequently, the ink and resist components obtained by the dispersing treatment are added and mixed with the other components necessary to obtain a uniform solution. In many cases, fine dust is mixed with the photosensitive solution in the manufacturing process, so that the obtained resist photosensitive solution is preferably filtered through, for example, a filter.

Next, the manufacturing method of the color filter using the photopolymerizable composition of this invention is demonstrated.

Hereinafter, the application example of the photopolymerizable composition of this invention is demonstrated.

(I) color filter

First, the photopolymerizable composition of the present invention is coated on a transparent substrate with a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater or a spray, and dried. Subsequently, a photomask is placed on this sample, and image exposure, development, and, if necessary, thermal curing or photocuring are performed to form a light shielding BM image. This operation is repeated for three-color RGB to form a color filter image.

(I-1) Application and drying of the photopolymerizable composition

When the pixel of the color filter is formed using the photopolymerizable composition of the present invention, since it has very high sensitivity and high resolution, for example, an image is exposed and developed without providing a polyvinyl alcohol oxygen barrier layer. Can be formed. The transparent substrate used is a transparent substrate for color filters, and the material thereof is not particularly limited. For example, polyester such as polyethylene terephthalate, polyolefin such as polypropylene or polyethylene, or polycarbonate, polymethyl meta It may be a thermoplastic plastic sheet of acrylate or polysulfone, for example a thermosetting plastic sheet of epoxy resin, polyester resin or poly (meth) acrylic resin, or glass plate. In particular, in view of heat resistance, glass plates or heat resistant plastics are preferably used.

In order to improve physical properties such as adhesion to the surface, a corona discharge treatment, an ozone treatment or a treatment for forming a thin film of a polymer such as a silane coupling agent or a urethane polymer may be first applied to the transparent substrate. The coating method is not particularly limited, and the film thickness of the resin black matrix after application and drying is suitably 0.1 to 2 m, preferably 0.1 to 1.5 m, and more preferably 0.1 to 1 m. In the present application, it is preferable that the color filter of the present invention has an optical density of 3.0 or more per micrometer in thickness in terms of light shielding property. Moreover, it is advantageous that the 20 degree glossiness value of BM is 100-200 as an index of the dispersion state of solid content like a pigment.

(I-2) Exposure and development

For drying, a hot plate, an IR oven or a convection oven may be used, and preferred drying conditions are a drying time of 10 seconds to 60 minutes at 40 to 150 ° C. Further, the light source used for exposure may be, for example, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp or a low pressure mercury lamp, or an argon ion laser, Laser light sources such as YAG lasers, excimer lasers or nitrogen lasers. When using the irradiation light which has only a specific wavelength, an optical filter can be used.

The development treatment is not particularly limited as long as a solvent capable of dissolving the resist film of the unexposed part is used. For example, organic solvents such as acetone, methylene chloride, trichloroethylene or cyclohexanone can be used. However, since many organic solvents cause environmental pollution, are harmful to the human body, and pose a fire hazard, it is preferable to use an alkali developer without such a risk. Such alkaline developers include, for example, inorganic alkali agents such as sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide or potassium hydroxide, or organic alkali agents such as diethanolamine, triethanolamine or tetraalkyl ammonium hydroxide. It may be an aqueous solution. The alkaline developer may contain, if necessary, a low molecular weight compound having a surfactant, a water-soluble organic solvent, a hydroxyl group, or a carboxyl group. In particular, since many surfactants have an effect of improving developability and resolution and a debris reduction effect, it is preferable to add a surfactant.

For example, the surfactant for the developer may be an anionic surfactant having a sodium naphthalene sulfonate group or a sodium benzene sulfonate group, a nonionic surfactant having a polyalkyleneoxy group, or a cationic surfactant having a tetraalkylammonium group. . The development treatment method is not particularly limited, and is usually carried out by immersion development, spray development, brush development, ultrasonic development, and the like at a development temperature of 10 to 50 ° C., preferably 15 to 45 ° C.

(II) liquid crystal display (panel)

The liquid crystal display of the present invention can be manufactured as follows using the color filter. First, an alignment film is formed on a color filter, a spacer is arrange | positioned on this alignment film, and it bonds with an opposing board | substrate, and a liquid crystal cell is formed. Next, a liquid crystal is inject | poured into the formed liquid crystal cell, and it connects to a counter electrode.

As an orientation film, the resin film of polyimide is suitable, for example. Gravure printing or flexographic printing is normally used for formation of an alignment film. The thickness of the alignment film is usually 10 to 100 nm. After hardening an oriented film by thermal baking, it surface-treats by ultraviolet irradiation or a rubbing cloth, and processes it into the surface state which can adjust the inclination of a liquid crystal.

As the spacer, one having a size corresponding to the distance from the opposing substrate is used, and usually 2 to 8 mu m is suitable. By photolithography, the photo spacer PS of a transparent resin film is formed on a color filter substrate, and this can be used instead of a spacer. As the counter substrate, an array substrate is usually used, and in particular, a TFT (thin film transistor) substrate is suitable.

The distance from the opposing substrate depends on the use of the liquid crystal display device, and is usually selected in the range of 2 to 8 µm. After the spacer is bonded to the opposing substrate, portions other than those corresponding to the liquid crystal injection holes are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating to seal the periphery of the liquid crystal cell.

The liquid crystal cell sealed in the periphery is cut into panel units, and the liquid crystal injection port is immersed in the liquid crystal under reduced pressure in the vacuum chamber, and then leaked into the chamber, thereby injecting the liquid crystal into the liquid crystal cell. The degree of reduced pressure in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, Preferably it is 50-90 degreeC. The liquid crystal cell is usually immersed in the liquid crystal after maintaining heating for 10 to 60 minutes at the time of pressure reduction. The liquid crystal injection port of the liquid crystal cell into which a liquid crystal is injected is sealed by hardening of UV curable resin, and a liquid crystal display device (panel) is completed.

The type of liquid crystal is not particularly limited, and the liquid crystal may be a known liquid crystal such as an aromatic, aliphatic or polycyclic compound, and may be any of a lyotropic liquid crystal and a thermotropic liquid crystal. As a thermotropic liquid crystal, a nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, etc. are known, and any of these can be used.

(III) Photo Space

(III-1) Supply Method to Substrate

The resin composition of the present invention is usually supplied onto a substrate in a dissolved or dispersed state in a solvent. Supply can be performed by a conventional method such as spinner method, wire bar method, flow coating method, die coating method, roll coating method or spray coating method. In particular, the die coating method is preferable from a general viewpoint that the amount of the coating liquid used is significantly reduced, and there is no influence of dust to be attached as in the case of the spin coating method, for example, and the generation of foreign matter is suppressed. The application amount is a dry film thickness, usually 0.5 to 10 m, preferably 1 to 8 m, particularly preferably 1 to 5 m. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform across the entire substrate surface. Significant nonuniformity can cause imbalance of the liquid crystal panel. In addition, the resin composition may be supplied in a pattern form by an inkjet method or a printing method.

(III-2) Drying Method

Drying after supplying the resin composition onto the substrate is preferably carried out by a drying method using a hot plate, an IR oven or a convection oven. It is also possible to use a combination of drying under reduced pressure carried out in a vacuum chamber without increasing the temperature. Drying conditions can be arbitrarily selected according to the kind of solvent component, the performance of the dryer to be used, and the like. The drying time is usually within a range of 15 seconds to 5 minutes at a temperature of 40 to 100 ° C, preferably 30 seconds to 3 minutes at a temperature of 50 to 90 ° C, depending on the type of solvent component, the performance of the dryer to be used, and the like. It is selected within the range.

(III-3) Exposure method

Exposure is performed by superposing a negative mask pattern on the coating film of a resin composition, and then irradiating an ultraviolet-ray or a visible light through a mask pattern. Moreover, the scanning exposure method by a laser beam can also be used. In this case, if necessary, exposure is performed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer in order to prevent the sensitivity of the photopolymerizable layer from being deteriorated by oxygen. The light source used for exposure is not specifically limited. The light source may be, for example, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc or a fluorescent lamp, or an argon ion laser, Laser source such as YAG laser, excimer laser, nitrogen laser, helium cadmium laser, blue violet semiconductor laser or near infrared semiconductor laser. When irradiating light with a specific wavelength, an optical filter can be used.

(III-4) Developing method

After the exposure is performed, an image pattern can be formed on the substrate by an aqueous solution containing an alkaline compound and a surfactant or development using an organic solvent. The aqueous solution may further contain organic solvents, buffers, complexing agents, dyes or pigments.

The alkaline compound is, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium sulfate, potassium sulfate, sodium hydrogen phosphate, hydrogen phosphate Inorganic alkaline compounds such as potassium, sodium dihydrogen phosphate, potassium dihydrogen phosphate or ammonium hydroxide, or mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono Or an organic alkaline compound such as diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH) or choline. Such alkaline compounds may be mixtures of two or more thereof.

Surfactants include, for example, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters or monoglyceride alkyl esters, alkylbenzene sulfonates, alkylnaphthalenes Anionic surfactants such as sulfonates, alkyl sulfates, alkyl sulfonates or sulfosuccinates, or amphoteric surfactants such as alkyl betaines or amino acids.

The organic solvent can be, for example, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol or diacetone alcohol. The organic solvent can be used alone or in combination with an aqueous solution.

(III-5) heat curing treatment

It is preferable to give a thermosetting process to the board | substrate after image development. In this case, as the thermosetting treatment conditions, the temperature is selected in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes.

(IV) rib (liquid crystal division orientation projection)

The rib (liquid crystal division orientation projection) means a projection formed on the transparent electrode in order to improve the viewing angle of the liquid crystal display device. By inclining the liquid crystal locally using the slope of the projection, the liquid crystal is divided in multiple directions within one pixel. Hereinafter, the formation method of a rib is explained in full detail.

(IV-1) Coating and Developing Process

The photosensitive composition of the present invention was formed on a transparent substrate having a black matrix and a red, blue, and green color filter, and further having a thickness of 150 nm thick ITO deposited on a normal 0.1-2 mm thick spinner, wire bar, Application is carried out using an application device such as a flow coater, die coater, roll coater or spray. The coating film thickness of a composition is 0.5-5 micrometers normally. After the coating film containing the composition is dried, a photomask is placed on the dry coating film, and then image exposed through the photomask. After the exposure, the unexposed portion that has not been exposed is removed by development to form a pixel. Usually, an image obtained after development is required to have a reproducibility of a thin line having a width of 5 to 20 mu m, and to have a high sharp thin line reproducibility along with the demand of a high quality display. For stable reproduction of high sharp thin lines, the cross-sectional shape of the thin line image after development is a rectangle with a clear contrast of the non-image portion and the image portion in terms of a wide range of development margins such as development time, developer aging and physical stimulation of the development shower. The form is preferred.

(IV-2) heating process

In the present invention, the image after development has a cross-sectional shape that approximates a rectangular shape. In order to obtain the arch shape required for the rib shape, it is usually 150 ° C or higher, preferably 180 ° C or higher, more preferably 200 ° C or higher and usually 400 ° C or lower, preferably 300 ° C or lower, and more preferably 280 ° C or lower. At a temperature of 10 minutes, preferably at least 15 minutes, more preferably at least 20 minutes and usually at most 120 minutes, preferably at most 60 minutes, more preferably at most 40 minutes, By modifying the rectangular cross-sectional shape into an arch shape, ribs having a width of 0.5 to 20 mu m and a height of 0.2 to 5 mu m are formed. Deformation by heating is performed by the contact angle W1 formed by the side surface of the thin line image (rectangular cross-sectional image) and the substrate plane before heating, and the contact angle W2 formed by the side surface of the thin line image after the heat treatment and the substrate plane. ) Is compared by controlling the photosensitive composition and heating conditions arbitrarily so that W1 / W2 is at least 1.2, preferably at least 1.3, more preferably at least 1.5 and usually at most 10, preferably at most 8. If the heating temperature is high or the heating time is long, the strain tends to be more pronounced, while when the heating temperature is low or the heating time is short, the strain tends to be low.

Next, the present invention will be described in more detail with Examples and Comparative Examples. However, it should be understood that the present invention is not limited to the following examples without departing from the object of the present invention.

Preparation Example 1

Preparation of Polymer Dispersant Solution

32 g of tolylene diisocyanate (manufactured by Mitsubishi Chemical Corporation, Mytec GP750A, 50% by weight of resin solids, butyl acetate solution) and 0.02 g of dibutyltin dilaurate as catalyst were used in propylene glycol monomethyl ether acetate (PGMEA). Diluted in g and dissolved. To this, 14.4 g of polyethylene glycol (manufactured by NOF CORPORATION, UNIOX M-1000) having a number-average molecular weight of one terminal and a polypropylene glycol (manufactured by Sanyo Chemical Industries, Ltd., SANNIX PP-) having a number average molecular weight of 1,000 1000) 9.6 g of the mixture was added dropwise while stirring, followed by further reaction at 70 ° C for 3 hours. Subsequently, after adding 1 g of N, N-dimethylamino-1,3-propanediamine to this, it was made to react at 40 degreeC for further 1 hour. The amine titer of the solution containing the polymer dispersant thus obtained was obtained by neutralization titration, and it was confirmed that it was 14 mg KOH / g. In addition, the resin content was obtained by a dry up method (solvent was removed on a hot plate for 30 minutes at 150 ° C., and the resin concentration was calculated from the weight change amount), and it was confirmed that it was 40% by weight.

Preparation Example 2

Preparation of Organic Binder

200 g o-cresol novolac epoxy resin, 200 g acrylic acid, 0.2 g p-methoxyphenol, 0.2 g dodecyltrimethylammonium chloride and 272 g PGMEA were added to the flask with an epoxy equivalent of 200 g / eq and a softening point of 65 ° C. Charged and reacted at the temperature of 100 degreeC for 8 hours (1 equivalent of acrylic acid reacted with 1 equivalent of epoxy group). Furthermore, after adding 42 g of tetrahydrophthalic anhydride to this, it was made to react at 80 degreeC for 3 hours. The reaction solution was reprecipitated in water and dried in vacuo to give a novolak epoxy acrylate resin having a carboxyl group. Neutralization titration with KOH was performed, and the acid value of the resin after that was 50 mg KOH / g.

Dispersion of carbon black

As the solids, coloring carbon black (manufactured by Mitsubishi Chemical Corporation, MA-220) and the polymer dispersant shown in Preparation Example 1 and PGMEA in the proportions of 50 parts by weight and 5 parts by weight, respectively, were added so that the solid content concentration was 50% by weight. The total weight of the dispersion was 50 g. The dispersion was sufficiently stirred with a stirrer to perform premixing.

The dispersion treatment was then carried out at 25 to 45 ° C. for 6 hours by a paint shaker. As beads, 0.5 mmφ zirconia beads were added at the same weight as the dispersion. After the dispersion was completed, the beads and the dispersion were separated by a filter.

Preparation Example 3

Preparation of Oxime Ester Compound C-1

(I) Production of carbazole derivatives (ketones)

3.9 g (20 mmol) of ethyl carbazole were dissolved in 20 mL of dichloromethane, and 2.9 g (22 mmol) of aluminum chloride were added. Under cooling in an ice bath, 4.1 g (22 mmol) of o-methylbenzoyl chloride was added dropwise while maintaining the temperature of the reaction solution at 5 ° C or lower. Stirring was performed while gradually raising the temperature to room temperature over 1 hour, and the reaction was carried out at room temperature for an additional 3 hours. The reaction solution was cooled in an ice bath and 2.9 g (22 mmol) of aluminum chloride was added, followed by 2.3 g (22 mmol) of methacryloyl chloride while cooling in an ice bath. It dripped keeping it as. After stirring was performed while gradually raising the temperature to room temperature over 1 hour, the reaction was performed at room temperature for an additional 3 hours.

The reaction solution was added dropwise to 150 ml of ice water, 100 ml of ethyl acetate was added for extraction, the aqueous layer was extracted with 50 ml of ethyl acetate, and the organic layers were combined and extracted with 150 ml of 10% aqueous sodium carbonate solution. The organic layer was further extracted with 150 mL of water, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off by an evaporator to give an orange-red oil. Purification was carried out by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/1) to give 3.1 g of a pale yellow solid (1) and 0.7 g of a pale yellow solid (2). NMR spectral analysis was carried out on the obtained solid (1) and solid (2) to obtain the following results (shift values).

Solid (1):

7.9-8.8, m, 3 H; 7.4, m, 7 H; 5.9 (1 H,) 5.6, s, 1 H; 5.6, s, 1 H; 4.4 (2H,), 2.4, s, 3H; 2.1, 2.4, d3H, 1.5, t, 3H

Solid (2):

8.6, dd, 1 H; 8.0, dd, 1 H; 7.9, d, 1 H; 7.4, m, 6 H; 4.5, q, 2H; 3.6, d, 2H, 2.6, s, 1H; 2.4, s, 3 H; 2.2, s, 3 H; 1.5, t, 3H

From the above NMR analysis results, the pale yellow solid (1) was identified as 3-methacryloyl-9-ethyl-6- (o-toluoyl) -9H-carbazole. The pale yellow solid (2) was found to be a ketone compound represented by the formula:

(II) Production of Oxime Ester Compounds

The pale yellow solid (2) (0.38 g, 0.001 mol) was dissolved in 5 mL of ethanol, hydroxylamine hydrochloride (0.075 g, 0.00105 mol) and pyridine (0.084 g, 0.00105 mol) were added, followed by 2 hours. It was refluxed. After ethanol was distilled off, water was added to dissolve the inorganic material and then filtered. The filtrate was dissolved in ethyl acetate, dried over magnesium sulfate and evaporated to afford an oxime. The obtained solid was dissolved in 3 ml of THF, acetyl chloride (0.23 g, 0.0022 mol) was added and then stirred. Triethylamine (0.21 g, 0.0023 mol) was added dropwise to the reaction solution at room temperature. Precipitation of the salt was confirmed by dropping triethylamine. After stirring for 2 hours, 20 ml of water were added, followed by extraction with 40 ml of ethyl acetate. The organic layer was washed twice with 20 ml of water, twice with 20 ml of saturated aqueous potassium carbonate solution, and the organic layer was dried over magnesium sulfate and evaporated. Purification was carried out by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/1) to give 0.3 g of a pale yellow solid (3).

On the obtained solid (3), H-NMR spectral analysis was performed under the following conditions to obtain the following results (shift value).

Solvent: In Chloroform (CDCl ₃ )

Frequency: 270 ㎒

Reference compound: (CH ₃ ) ₄ Si

8.5, dd, 1 H; 8.1, dd, 1 H; 7.9, dd, 1 H; 7.4, m, 6 H; 4.4, q, 2 H; 3.6, d, 2H, 2.4, s, 3H; 2.3, s, 3 H; 2.2, s, 3 H; 2.0, s, 3 H; 1.5, t, 3H

From the NMR analysis results, it was confirmed that the pale yellow solid (3) was an oxime ester compound represented by the following formula (photopolymerization initiator C-1 used in Example 1 to be described later):

Preparation Example 4

Preparation of Oxime Ester Compound C-2

C was prepared in the same manner as in the preparation of C-1, except that 3-methacryloyl-9-ethyl-6- (o-toluoyl) -9H-carbazole was used instead of the pale yellow solid (2) in Preparation Example 3. -2 was prepared. NMR shift values were as follows:

8.5, d, 1 H; 8.4, d, 1 H; 8.1, dd, 1 H; 7.9, dd, 1 H; 7.4, m, 6 H; 7.2, d, 1 H; 5.6, s, 1 H; 5.1, s, 1 H; 4.4, q, 2 H; 2.4, s, 3 H; 2.2, s, 3 H; 2.0, s, 3 H; 1.5, t, 3H

Preparation Example 5

Preparation of Oxime Ester Compound C-3

C-3 was prepared in the same manner as the preparation of C-1, except that methacryloyl chloride was changed to crotonyl chloride in Preparation Example 3. NMR shift values were as follows:

8.5, d, 1 H; 8.4, d, 1 H; 8.1, dd, 1 H; 7.9, dd, 1 H; 7.4, m, 6 H; 4.4, q, 2 H; 2.4, s, 3 H; 2.2, s, 3 H; 2.0, s, 3 H; 1.5, t, 3H

Preparation Example 6

Preparation of Oxime Ester Compound C-4

C-4 was prepared by the same method as the preparation of C-1, except for changing the methacryloyl chloride to acetyl chloride in Preparation Example 3 and the acetyl chloride used in the final step to monoethyl succinyl chloride. NMR shift values were as follows:

8.6, d, 1 H; 8.5, d, 1 H; 8.1, dd, 1 H; 8.0, dd, 1 H; 7.9, dd, 1 H; 7.5, m, 6 H; 4.5, q, 2H; 4.2, m, 6 H; 2.9, t, 2 H; 2.8, t, 2 H; 2.7, t, 2 H; 2.6, s, 3 H; 2.5, s, 3 H; 1.5, t, 3 H; 1.3, s, 3H

Preparation Example 7

Preparation of Oxime Ester Compound C-5

C-5 was prepared in the same manner as in the preparation of C-1, except for changing the methacryloyl chloride to acetyl chloride in Preparation Example 3 and the acetyl chloride used in the final step to morpholinyl carbonyl chloride. .

Preparation Example 8

Preparation of Oxime Ester Compound C-8

C-8 was prepared in the same manner as the preparation of C-1, except that methacryloyl chloride was changed to monoethyl succinyl chloride in Preparation Example 3. NMR shift values were as follows:

8.5, d, 1 H; 8.4, d, 1 H; 8.1, dd, 1 H; 7.9, dd, 1 H; 7.4, m, 6 H; 4.4, q, 2 H; 4.1, q, 2H; 3.3, t, 2H; 2.6, s, 3 H; 2.4, s, 3 H; 2.3, s, 3 H; 1.5, t, 3 H; 1.2, d, 3H

Examples 1 to 9 and Comparative Examples 1 to 3

(1) Preparation of Resist Solution

After using each of the carbon black dispersion inks described above, the components (a), (b), (c), (d) and (e), the organic solvent and the surfactant are added as solids in the following blending ratios, and then agitated. Was stirred and dissolved to prepare a black resist photosensitive solution.

(a) black material

50 g of carbon black (manufactured by Mitsubishi Chemical Corporation, MA-220)

(b) organic binder

30 g described in Table 2

(d) photopolymerizable monomer: ethylenic compound

10 g of dipentaerythritol hexaacrylate

(c) photopolymerization initiator

Listed in Table 2

Organic solvent

Propylene Glycol Monomethyl Ether Acetate 300g

(e) 5 g of a polymer dispersant (Preparation Example 1)

100 ppm of surfactant (manufactured by Sumitomo 3M Limited, FC-430)

(2) Evaluation of resist

The black resist photosensitive solution was applied onto a glass substrate (Corning Incorporated, 7059) with a spin coater and dried on a hot plate at 80 ° C. for 1 minute. The film thickness of the resist after drying was measured by a tactile film thickness meter (a-step manufactured by KLA-Tencor Corporation) to confirm that the thickness was 1 m. The sample was then image exposed by varying the exposure dose through a mask with a high pressure mercury lamp. A resist pattern was obtained by spray development using an aqueous sodium carbonate solution having a concentration of 0.8% at a temperature of 25 ° C.

The sensitivity, resolution and light-shielding property were evaluated based on the following criteria, and the results shown in Table 2 were obtained.

1. Sensitivity

This was shown by the appropriate exposure amount (mj / cm <2>) which can form and arrange | position a 20 micrometer mask pattern. That is, a resist with a small exposure amount has high sensitivity because an image can be formed with a small exposure amount.

2. Resolution

At a exposure dose that faithfully reproduces a 20 μm mask pattern, the resolvable resist minimum pattern dimension was observed under a microscope of 200 times magnification.

Minimum pattern dimensions 10 μm or less: ○

Minimum pattern dimensions exceed 10 μm: ×

3. Shading

The optical density (OD) in the image portion was measured by a Macbeth reflection density meter (TR927, manufactured by Gretag Macbeth (formerly Gormor Group)). An OD value is a numerical value which shows light shielding ability, and a high value shows high light shielding property.

4. Scratch resistance

The glass substrate having the obtained image pattern was placed on an untreated glass substrate (manufactured by Corning Incorporated, 7059) such that the image pattern was brought into contact with the untreated glass surface, and subjected to the load shown below, and subjected to friction five times at a speed of 3 cm / sec. I was. After rubbing, the presence or absence of a scratch was visually evaluated based on the following reference | standard.

Load (g / ㎠) scratch evaluation 60 Observed △ 60 Not observed at all ○ 100 Not observed at all ◎

Example 10

A black matrix pattern was obtained in the same manner as in Example 9 except that titanium black (manufactured by Mitsubishi Chemical Corporation, 13M-C) was used instead of carbon black (manufactured by Mitsubishi Chemical Corporation, MA-220) used as the black material. The results are shown in Table 2.

Comparative Example 4

A black matrix pattern was obtained in the same manner as in Comparative Example 3 except that titanium black (manufactured by Mitsubishi Chemical Corporation, 13M-C) was used instead of carbon black (manufactured by Mitsubishi Chemical Corporation, MA-220) used as the black material. The results are shown in Table 2.

Organic binders (b) Photopolymerization initiator (c) Sensitivity definition Scratch resistance Shading Corresponds to Table 1 mj / ㎠ Example 1 Preparation Example 2 C-1 No. 22 25 ○ ◎ 3.5 Example 2 Preparation Example 2 C-2 No. 3 25 ○ ◎ 3.5 Example 3 Preparation Example 2 C-3 No. 4 25 ○ ◎ 3.5 Example 4 Preparation Example 2 C-4 No. 16 30 ○ ○ 3.5 Example 5 Preparation Example 2 C-5 No. 19 30 ○ ○ 3.5 Example 6 Preparation Example 2 C-1 / C-2 Mixing System No. 22, no. 3 25 ○ ◎ 3.5 Example 7 Preparation Example 2 C-7 No. 28 20 ○ ◎ 3.5 Example 8 Preparation Example 2 C-8 No. 29 25 ○ ◎ 3.5 Example 9 Preparation Example 2 C-9 No. 37 20 ○ ◎ 3.5  Example 10 Preparation Example 2 C-9 No. 37 20 ○ ◎ 3.3 Comparative Example 1 Preparation Example 2 Triazine A - 100 ○ △ 3.5 Comparative Example 2 ACA-200M CGI-124 - 150 × △ 3.5 Comparative Example 3 Preparation Example 2 3 types of mixing system - 200 ○ △ 3.5 Comparative Example 4 Preparation Example 2 3 types of mixing system - 150 ○ △ 3.3

In Table 2, the meanings of the symbols are as follows.

ACA-200M: acrylic polymer (manufactured by DAICEL CHEMICAL INDUSTRIES, LTD., ACA-200M)

C-1: Compound No. 22 shown in Table 1

C-2: Compound No. 3 shown in Table 1

C-3: Compound No. 4 shown in Table 1

C-4: Compound No. 16 shown in Table 1

C-5: compound number 19 shown in Table 1

C-7: Compound No. 28 shown in Table 1

C-8: Compound No. 29 shown in Table 1

C-9: compound number 37 shown in Table 1

Triazine A: 4- (m-bromo-p-methoxyphenyl) -2,6-di (trichloromethyl) -s-triazine (5 g)

CGI-124: photopolymerization initiator (manufactured by Ciba Specialty Chemicals K.K., CGI-124) (5 g)

3 type mixing system: 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'- tetraphenylbiimidazole (2 g) + 4,4'-bis (diethylamino) benzo Phenone (1 g) + 2-mercaptobenzothiazole (1 g)

Examples 11 and 12 and Comparative Example 5

Each test solution was applied onto an AN100 glass substrate sputtered with 150 nm thick ITO by a spin coater, and dried at 80 ° C. for 3 minutes on a hot plate to obtain a coating film having a dry film thickness of 1.7 μm. Then, using a 3 kW high-pressure mercury lamp through a fine line width of the pattern mask 15 ㎛ from the coating film side, 25, 50, 100 and 200 mJ / ㎝ ^- was carried out an image exposure under the exposure conditions of ^FIG. Next, using a developing solution containing an aqueous solution containing 1% by weight of potassium carbonate and 4% by weight of a nonionic surfactant ("Emulgen A-60" manufactured by Kao Corporation), a shower was carried out at 23 ° C under a water pressure of 0.25 MPa. After the development was carried out, the development was stopped with pure water, and the substrate was rinsed with a cleaning spray. The shower developing time was adjusted to 10 to 120 seconds to double the time (break time) during which the photosensitive layer was dissolved and removed. Thus, the glass substrate in which the image was formed was heated at 230 degreeC for 30 minutes, and the thin line pattern deformed in arch shape was formed. The cross-sectional shape of the obtained thin line before and after heating was measured by VK9500, the contact angle formed by the board | substrate plane and the thin line image side surface was calculated | required, and the change rate of the contact angle before and behind heating was evaluated by the following method. The results are shown in Table 3.

As is clear from Table 3, Examples 11 and 12 using the photosensitive composition of the present invention show that the deformation rate of the contact angle is high, the arch protrusions are formed satisfactorily, and the formation of liquid crystal split alignment protrusions with good image formation is possible. Turned out.

Evaluation of rate of change of contact angle by heating

The contact angle was obtained by measuring the cross-sectional shape of the thin line before and after heating with VK9500, and formed by the contact angle W1 formed by the side of the thin line image before heating and the substrate plane and the side of the thin line image after heating and the substrate plane. The contact angle W2 was calculated | required, and the change of the contact angle by heating was evaluated from the value of the change rate (W1 / W2) of a contact angle as follows. See FIG. 1.

A: W1 / W2 is 2 or more

B: W1 / W2 is 1.5 or more but less than 2

C: W1 / W2 is 1.2 or more and less than 1.5

D: W1 / W2 is less than 1.2

Image formation

The image obtained by the said exposure and image development process was evaluated as follows.

A: An image with a film thickness of 70% or more of the coating film thickness is formed.

B: An image of a film thickness of less than 70% of the coating film thickness is formed.

C: The photosensitive layer is completely dissolved and no image is formed.

Example 11 Example 12 Comparative Example 5 compound Compounding rate Compounding rate Compounding rate (Parts by weight) (Parts by weight) (Parts by weight) Photosensitive composition Photopolymerizable monomer (d) M-1 12 10.5 21 M-2 2 2 2 Photopolymerization initiator (c) C-9 2 2 0 S-1 0 0 6 S-2 0 0 3 Organic binders (b) P-1 84 85.5 77 Polymer dispersants (e) F-1 0.1 0.1 0.1 menstruum PGMA 500 500 500 Property evaluation P / M ratio (b) parts by weight / (d) parts by weight 6 6.8 3.3 Strain of contact angle by heating A A C Proper sensitivity mJ / cm ^-2 60 60 200 Image formation A A B

In Table 3, the meanings of the symbols are as follows.

M-1: Nippon Kayaku Co., Ltd. Manufacture, dipentaerythritol hexaacrylate (DPHA)

M-2: SHIN-NAKAMURA CHEMICAL CO., LTD. Preparation, bifunctional phosphate "PM-21"

S-1: Ciba Specialty Chemicals K.K. Manufacture, "IRGACURE 907"

S-2: Nippon Kayaku Co., Ltd. Manufacture, 2,4-diethyl thioxanthone

P-1: Alkali-soluble resin of the weight average molecular weight 2,000 and acid value 100, and has a chemical formula shown below.

F-1: DAINIPPON INK AND CHEMICALS, INCORPORATED, Fluorine-based surfactant "F475"

PGMA: Tokyo Kasei Kogyo Co., Ltd. Isopropylene glycol monomethyl ether acetate.

In Table 3, the appropriate sensitivity mJ / cm ⁻² means the minimum exposure amount at which a thin line pattern of 15 μm can be reproduced.

The photopolymerizable composition of this invention and the color filter using the same can be used for a color television, a liquid crystal display element, a solid-state image sensor, and a camera, for example.

Japanese Patent Application No. 2004-046071 (filed February 23, 2004), Japanese Patent Application No. 2004-094927 (filed March 29, 2004) and Japanese Patent Application No. 2004 including the specification, claims, and abstract The entire contents of -183593, filed June 22, 2004, are incorporated herein by reference in their entirety.

Claims (20)

Oxime ester compound represented by the formula (1) or (2):

(In the above formula, R ^1a is optionally substituted C _{2 -25} alkenyl, C _{1 -20} alkyl-heteroaryl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group, C _{1 -20} heteroaryloxy carbonyl alkyl group or a hetero arylthio group, a C _{0 -20} amino group, or a C _{1 -20} represents an amino group, with the proviso that, R ^1a is C _{1 -10,} which can form a ring with R1 ', the linking group may have a substituent An alkylene group,-(CH = CH) _n -,-(C≡C) _n -or a combination thereof (n is an integer from 0 to 3); R ^2a is optionally substituted C _{2 -12} alkanoyl groups, C _{3 -25} noilgi alkenyl, C _{3 -8} cycloalkyl alkanoyl, C _{7 -20} benzoyl group, C _{1 -20} group, C ₂ to _{heteroaryl- 10} alkoxy group or a C _{7 -20} phenoxy represents a carbonyl group; R 1 ′ represents any substituent containing an aromatic ring or a heteroaromatic ring):

(In the above formula, R ^1b is optionally substituted C _{6 -20} phenyl group, C _{1 -20} alkyl, C _{5 -8} cycloalkyl group, C _{2 -20} alkanoyl groups, C _{7 -20} benzoyl group, C _{2 -12} alkoxy group or a phenoxy a carbonyl group, C _{1 -20} amide group, a nitro group, a C _{2 -25} alkenyl, C _{1 -10} alkyl-heteroaryl, C _{3 -20} Alkoxycarbonyl group, a C _{8 -20} phenoxycarbonyl group, a C _{1 -20} heteroaryloxy carbonyl group or a hetero arylthio group, a C _{0 -20} represents an amino group, or a C _{1 -20} amino group, with the proviso that, R ^1b is R1 'and together can form a ring, the linking group which may have a substituent, C _{1 -10} alkylene _{group, - (CH = CH) n} -, - (C≡C) n - or a combination thereof (n Is an integer from 0 to 3); R ^2b is optionally substituted C _{1 -20} heteroaryl group, C _{1 -20} heteroaryl alkanoyl, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl group, C _{3 - 20} heteroaryloxy carbonyl nilal Kano represents a group, or C _{2 -10} amino group; R 1 ′ represents any substituent containing an aromatic ring or a heteroaromatic ring). The compound according to claim 1, wherein in formula (1), R ^1a is a ring which may be substituted with a C _{2 -25} alkenyl, C _{3 -20} alkoxycarbonyl group, a C _{8 -20} phenoxycarbonyl group or C _{1 -20} alkyl, or amino, or R ^1a is R1 ' the formation, and the linking group is C _{1 -10} alkylene group which may have a _{substituent, - (CH = CH) n} -, - (C≡C) n - or a combination thereof (n is an integer of 0 to 3), R ^2a is C _{2 -12} alkanoyl oxime ester compound which may be substituted. The compound according to claim 1, wherein in formula (2), R ^1b is an optionally substituted C _{1 -20} alkyl, R ^2b is optionally substituted C _{1 -20} heteroaryl group, C _{1 -20} heteroaryl alkanoyl, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl group or a C _{2 - An} oxime ester compound which is a ₁₀ aminocarbonyl group. Oxime ester compound represented by the formula (3) or (4):

(In the above formula, R ^1a is optionally substituted C _{2 -25} alkenyl, C _{1 -20} alkyl-heteroaryl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group, C _{1 -20} heteroaryloxy carbonyl represents an alkyl group or a hetero arylthio group, a C _{0 -20} amino group, or a C _{1 -20} amino group, with the proviso that, R ^1a may form a ring together with R ³ or R ^7, in this case, R ^1a and R ³ and / or R ⁷ are bonded to each other to form a divalent or trivalent linking group, the linking group is C _{1 -10} alkylene group which may have a _{substituent, - (CH = CH) n} -, - (C≡C) n - Or a combination thereof (n is an integer from 0 to 3); R ^2a is optionally substituted C _{2 -12} alkanoyl groups, C _{3 -25} noilgi alkenyl, C _{3 -8} cycloalkyl alkanoyl, C _{7 -20} benzoyl group, C _{1 -20} group, C ₂ to _{heteroaryl- 10} alkoxy group or a C _{7 -20} phenoxy represents a carbonyl group; ^{R 3, R 4, R 5} , R 6 and R ⁷ are each independently of each other, a hydrogen atom, a halogen atom, or which may be substituted with a C _{1 -12} alkyl, C _{1 -12} alkoxy group, a cycloalkyl C _{5 -8} alkyl group, C _{6 -20} phenyl, C _{7 -20} benzyl group, C _{7 -20} benzoyl group, C _{2 -12} alkanoyl groups, C _{1 -20} in the heteroaryl group, a C _{3 -20} alkoxy carbonyl nilal alkanoyl group, C _8-20 phenoxycarbonyl nilal alkanoyl group, C _3-20 heteroaryloxy carbonyl nilal alkanoyl group, C _{2 -12} alkoxycarbonyl group or phenoxycarbonyl group, or ^{-OR 8, -SR 9, -SOR 9} , -SO ₂ R ⁹ or NR ¹⁰ R ¹¹ , at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represents -OR ⁸ , -SR ⁹ or -NR ¹⁰ R ¹¹ , wherein R ⁸ is C _{1 -12} alkyl group which may be hydrogen, or substituted, C _{2 -8} alkanoyl, C _{3 -12} alkenyl, C _{3 -20} noilgi alkenyl, C _{6 -20} phenyl, - (CH ₂ CH ₂ O ) _m H (m is an integer of 1 to 20) or C _{3 -15} trialkyl represents a silyl, R ⁹ is Bovine atom or C _{1 -12} alkyl group which may be substituted, C _{2 -8} alkanoyl, C _{3 -12} alkenyl group, C ₆ represents a phenyl group or a C _{3 -20 -15} trialkylsilyl, R ¹⁰ and R ¹¹ are each independently of the other, hydrogen atom or C _{1 -12} alkyl group which may be substituted, C _{2 -4} hydroxyl group, C _{3 -5} alkenyl group or represents a C _6-20 phenyl group, with the proviso that, R ³ to R ⁷ May combine with each other or each of them with R ¹ to form a cyclic structure):

(In the above formula, R ^1b is optionally substituted C _{6 -20} phenyl group, C _{1 -20} alkyl, C _{5 -8} cycloalkyl group, C _{2 -20} alkanoyl groups, C _{7 -20} benzoyl group, C _{2 -12} alkoxy group or a phenoxy a carbonyl group, C _{1 -20} amide group, a nitro group, a C _{2 -25} alkenyl, C _{1 -10} alkyl-heteroaryl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group, C _{1 -20} heteroaryloxy-carbonyl group or a hetero arylthio group, a C _{0 -20} amino group, or represents a C _{1 -20} amino group, with the proviso that, R ^1b may form a ring together with R ³ or R ^7, in this case, R ^1b and a R ³ and / or R ⁷ is a bivalent or trivalent form a linking group, C _{1 -10} alkylene group, which linking group may have a substituent and bonded to each other _{- (CH = CH) n -} , - (C ≡C) _n -or a combination thereof (n is an integer from 0 to 3); R ^2b is optionally substituted C _{1 -20} heteroaryl group, C _{1 -20} heteroaryl alkanoyl, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl group, C _{3 - 20} heteroaryloxy carbonyl nilal alkanoyl group, or C _{2 -10} represents an amino group; R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same as in formula (3)). The compound according to claim 4, wherein in formula (3), R ^1a is optionally substituted C _{2 -25} alkenyl, C _{3 -20} alkoxycarbonyl group, a C _{8 -20} phenoxycarbonyl group or C _{1 -20} alkyl, or amino, or R ^1a is R ³ or R ⁷ form a ring together with, and in this case, R ^1b and R ³ and / or R ⁷ are bonded to each other, and divalent or trivalent form a linkage group, the linking group which may have a substituent, C _{1 -10} alkylene group, - ( CH = CH) _n -,-(C≡C) _n -or a combination thereof (n is an integer from 0 to 3), R ^2a is a C _{2 -12} alkanoyl group which may be substituted, ^{R 3, R 4, R 5} , R 6 and R ⁷ are each independently of each other, C _{1 -12} alkyl group which may be a hydrogen atom, a halogen atom, or a substituted, C _{6 -20} phenyl group, C _{1 -20} heteroaryl Diary or -NR ¹⁰ R ¹¹ , wherein at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represents -NR ¹⁰ R ¹¹ (wherein R ¹⁰ and R ¹¹ are each independently of one another a hydrogen atom, or which may be substituted with a C _{1 -12} alkyl, C _{2 -4} hydroxyl group, C _{3 -5} alkenyl or C _{6 -20} shows a represents a phenyl group), provided that, R ³ to R ⁷ are bound to the standing or Each of which is combined with R ^1a to form a cyclic structure. The compound according to claim 4, wherein in formula (4), R ^1b is an optionally substituted C _{1 -20} alkyl, R ^2b is optionally substituted C _{1 -20} heteroaryl group, C _{1 -20} heteroaryl alkanoyl, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl group or a C _{2 - 10} aminocarbonyl group, ^{R 3, R 4, R 5} , R 6 and R ⁷ are each independently of each other, C _{1 -12} alkyl group which may be a hydrogen atom, a halogen atom, or a substituted, C _{6 -20} phenyl group, C _{1 -20} heteroaryl Diary or —NR ¹⁰ R ¹¹ , wherein at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is —NR ¹⁰ R ¹¹ (wherein R ¹⁰ and R ¹¹ are each independently of one another a hydrogen atom; , or which may be substituted with a C _{1 -12} alkyl, C _{2 -4} hydroxyl group, C _{3 -5} alkenyl or C _{6 -20} shows a represents a phenyl group), provided that, R ³ to R ⁷ are bonded to each other or An oxime ester compound capable of combining with R ^1b to form a cyclic structure. Oxime ester compound represented by any one of formulas (5) to (7):

(In the above formula, R ^1a and R ^2a are the same as in formula (3) as defined in claim 4; R ^3, R ^6, R ⁷ and R ¹² to R ¹⁶ is C _{1 -12} alkyl, C _{2 -12} alkenyl noilgi, C _{6 -20} phenyl, C _{7 -20,} which may be each substituted with a hydrogen atom, a halogen atom, or Benzyl or benzoyl, or —NR ¹⁰ R ¹¹ , provided that R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ may combine with each other to form a cyclic structure):

(In the above formula, R ^1b and R ^2b are the same as in formula (4) as defined in claim 4; R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ are the same as in formula (5)):

(In the above formula, R ^1b is the same as in formula (4) as defined in claim 4; R ² represents R ^2a in formula (3) or R ^2b in formula (4) as defined in claim 4; R ^3, R ^6, R ⁷ and R ¹² to R ¹⁶ is C _{1 -12} alkyl, C _{2 -12} alkenyl noilgi, C _{6 -20} phenyl, C _{7 -20,} which may be each substituted with a hydrogen atom, a halogen atom, or Benzyl or benzoyl, or —NR ¹⁰ R ¹¹ , provided that R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ may be bonded to each other to form a cyclic structure, and R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ is one or more of the at least one selected from the group, and C _{3 -15} tree group consisting alkylsilyl a C _{1 -20} alkyl, heteroaryl, heteroaryl-alkanoyl and heteroaryl which may be substituted Containing). 8. A compound according to claim 7, wherein in formula (5), R ^1a is optionally substituted C _{2 -25} alkenyl, C _{3 -20} alkoxycarbonyl group, a C _{8 -20} phenoxycarbonyl group or C _{1 -20} alkyl, or amino, or R ^1a is R ³ or R ⁷ form a ring together with, and in this case, R ^1a and R ³ and / or R ⁷ are bonded to each other, and divalent or trivalent form a linkage group, the linking group which may have a substituent, C _{1 -10} alkylene group, - ( CH = CH) _n -,-(C≡C) _n- , or a combination thereof (n is an integer from 0 to 3); R ^2a is optionally substituted C _{2 -12} alkanoyl group and; R ^3, R ^6, R ⁷ and R ¹² to R ¹⁶ is C _{1 -12} alkyl, C _{2 -12} alkenyl noilgi, C _{6 -20} phenyl, C _{7 -20,} which may be each substituted with a hydrogen atom, a halogen atom, or Or a benzyl group or a benzoyl group, or -NR ¹⁰ R ¹¹ , provided that R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ are bonded to each other to form a cyclic structure. 8. A compound according to claim 7, wherein in formula (6): R ^1b is an optionally substituted C _{1 -20} alkyl, R ^2b is optionally substituted C _{1 -20} heteroaryl alkanoyl, C _{3 -20} alkoxycarbonyl alkaryl noilgi, C _{8 -20} phenoxycarbonyl nilal alkanoyl group or a C _{2 -10} and the amino group, R ^3, R ^6, R ⁷ and R ¹² to R ¹⁶ is C _{1 -12} alkyl, C _{2 -12} alkenyl noilgi, C _{6 -20} phenyl, C _{7 -20,} which may be each substituted with a hydrogen atom, a halogen atom, or Or a benzyl group or a benzoyl group, or -NR ¹⁰ R ¹¹ , provided that R ³ , R ⁶ , R ⁷ and R ¹² to R ¹⁶ are bonded to each other to form a cyclic structure. Oxime ester compound represented by the formula (8) or (9):

(In the above formula, R ^1a is optionally substituted C _{2 -25} alkenyl, C _{1 -20} alkyl-heteroaryl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group, C _{1 -20} heteroaryloxy carbonyl alkyl group or a hetero arylthio group, an amino group or C _{1 -20 -20 0} C represents the amino group, with the proviso that, R ^1a may form a ring together with Ar _1, and a linking group is C _{1 -10} alkyl which may have a substituent A len group,-(CH = CH) _n -,-(C≡C) _n -or a combination thereof (n is an integer from 0 to 3); R ^2a is the same as in formula (1) as defined in claim 1; Ar ₁ represents an aromatic ring, heteroaromatic ring, condensed aromatic ring or condensed heteroaromatic ring which may have a substituent; p represents an integer from 2 to 5):

(In the above formula, R ^1b is optionally substituted C _{6 -20} phenyl group, C _{1 -20} alkyl, C _{5 -8} cycloalkyl group, C _{2 -20} alkanoyl groups, C _{7 -20} benzoyl group, C _{2 -12} alkoxy group or a phenoxy a carbonyl group, C _{1 -20} amide group, a nitro group, a C _{2 -25} alkenyl, C _{1 -10} alkyl-heteroaryl, C _{3 -20} alkoxycarbonylalkyl group, C _{8 -20} phenoxycarbonyl group, C _{1 -20} heteroaryloxy-carbonyl group or a hetero arylthio group, a C _{-20 0} represents an amino group or C _{1 -20} amino group, with the proviso that, R ^1b may form a ring together with Ar _1, the linking group which may have a substituent C _{1 -10} alkylene _{group, - (CH = CH) n} -, - (C≡C) n - or a combination thereof (n is an integer of 0 to 3); R ^2b is the same as in formula (2) as defined in claim 1; Ar ₁ represents an aromatic ring, heteroaromatic ring, condensed aromatic ring or condensed heteroaromatic ring which may have a substituent; p represents an integer of 2 to 5). The compound according to claim 10, wherein in formula (8), R ^1a is C _{2 -25} alkenyl group which may be substituted, C _{3 -20} alkoxycarbonyl group, a C _{8 -20} phenoxycarbonyl group, or C _{1 -20} represents an amino group, with the proviso that, R ^1a is Ar ₁ It can form a ring with, in this case, R ^1a and Ar ₁ may be bonded to each other to form a divalent or trivalent linking group, the linking group which may have a substituent, C _{1 -10} alkylene group, - (CH = CH ) _n -,-(C≡C) _n -or a combination thereof (n is an integer from 0 to 3), R ^2a is C _{2 -12} alkanoyl oxime ester compound which may be substituted. The compound according to claim 10, wherein in formula (9), R ^1b is an optionally substituted C _{1 -20} alkyl, R ^2b is optionally substituted C _{1 -20} heteroaryl group, C _{1 -20} heteroaryl alkanoyl, C _{3 -20} alkoxy carbonyl nilal alkanoyl groups, C _{8 -20} phenoxycarbonyl nilal alkanoyl group or a C _{2 - An} oxime ester compound which is a ₁₀ aminocarbonyl group. A photopolymerizable composition containing an organic binder (b) and a photopolymerization initiator (c), wherein said component (c) contains the oxime ester compound according to any one of claims 1 to 12. The photopolymerizable composition according to claim 13, wherein the organic binder (b) is an epoxy acrylate resin having a carboxyl group. The photopolymerizable composition according to claim 14, wherein the organic binder (b) is an epoxy acrylate obtained by reacting a (hydro) phthalic anhydride with a reaction product of a novolak epoxy resin and (meth) acrylic acid. The photopolymerizable composition according to any one of claims 13 to 15, further comprising a photopolymerizable monomer (d). The photopolymerizable composition according to any one of claims 13 to 16, further comprising a polymer dispersant (e) containing a basic functional group. The photopolymerizable composition according to any one of claims 13 to 17, further comprising a color material (a). A color filter having an image formed by the photopolymerizable composition according to any one of claims 13 to 18. A liquid crystal display device having an image formed by the photopolymerizable composition according to any one of claims 13 to 18.

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