JP2006036750A - Oxime ester compound, photopolymerizable composition and color filter using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an oxime ester compound useful as a photopolymerization initiator, a photopolymerizable composition containing the same and a highly sensitive photopolymerization initiator. <P>SOLUTION: The oxime ester compound has a specific structure. In particular, in the photopolymerizable composition containing (a) a black color material, (b) an organic binder and (c) the photopolymerization initiator, the oxime ester compound constitutes the component (c). The oxime ester compound can be used as the highly sensitive photopolymerization initiator. The photopolymerizable composition using the same in the form of a thin film is excellent in sensitivity and resolving power and exhibits a high light-blocking effect, so it is capable of forming a high-quality resin black matrix (BM) at a low cost. A color filter using the resin BM is excellent in precision, flatness and durability and is therefore capable of improving the display quality of a liquid crystal device. Moreover, the production process and the color filter itself do not involve any hazardous substance, so the danger to human body is reduced and environmental safety is enhanced. The oxime ester compound can be applied to usage wherein no color material is used, such as a photospacer and a rib (liquid crystal divided-alignment protrusion). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an oxime ester compound useful as a photopolymerization initiator and a photopolymerizable composition containing the oxime ester compound. More specifically, the present invention relates to a photopolymerizable composition for a color filter used in the production of an optical color filter used in a color television, a liquid crystal display element, a solid-state imaging element, a camera, etc. The photopolymerizable composition for a color filter suitable for manufacturing a black matrix (Black Matrix, hereinafter abbreviated as BM) and high accuracy, which is effective for the above-mentioned, has a high light-shielding property but is highly sensitive and has excellent resolution. The present invention relates to a color filter having a highly light-shielding resin BM.

  Further, since the oxime ester-based compound according to the present invention is a highly sensitive photopolymerization initiator, it is not limited to BM, and is a transparent photosensitive material that does not use a color material such as a photo spacer or a rib (liquid crystal dividing alignment protrusion). It can also be used for active compositions and has a wide range of applied technical fields.

  A color filter usually forms a black matrix on the surface of a transparent substrate such as glass or plastic sheet, and then sequentially applies three or more different hues such as red, green and blue in a striped or mosaic shape. It is formed with a color pattern. The pattern size varies depending on the use of the color filter and each color, but is about 5 to 700 μm. Further, the positional accuracy of superposition is several to several tens of μm, and is manufactured by a fine processing technique with high dimensional accuracy.

  Typical methods for producing a color filter include a dyeing method, a printing method, a pigment dispersion method, and an electrodeposition method. Among these, in particular, a pigment dispersion method for forming a color filter image by coating a photopolymerizable composition containing a color material on a transparent substrate and repeating image exposure, development, and curing as necessary is a color filter. It is widely used because it has high accuracy such as pixel position and film thickness, excellent durability such as light resistance and heat resistance, and few defects such as pinholes.

  BMs are generally arranged in a grid, stripe, or mosaic between red, green, and blue color patterns, and thin film transistors (Thin Film Transistors) that improve contrast by suppressing color mixture between colors or leak light. : TFT) to prevent malfunction. For this reason, the BM is required to have high light shielding properties. Conventionally, BM is generally formed by a metal film such as chromium. In this method, a metal such as chromium is vapor-deposited on a transparent substrate, and the chromium layer is etched through a photolithography process. Therefore, a high light-shielding property can be obtained with high accuracy with a thin film thickness. On the other hand, it has a long manufacturing process, low productivity and high cost, and has problems such as environmental problems caused by waste liquid of etching treatment.

  For this reason, a method for forming a low-cost, pollution-free resin BM with a photosensitive resin in which a light-shielding pigment or dye is dispersed has been energetically studied. However, since the resin BM has problems as described later, it has not been put into practical use yet. In the resin BM, in order to develop a light-shielding property (optical density) equivalent to that of a BM made of a metal film such as chromium, it is necessary to increase the content of light-shielding pigments and dyes or to increase the film thickness. There is.

  In the method of increasing the film thickness, the flatness of the RGB colored pixels formed thereon is impaired due to the influence of the unevenness of the BM. For this reason, non-uniformity of the liquid crystal cell gap or disorder of the alignment of the liquid crystal occurs to cause a reduction in display capability. In addition, problems such as disconnection of the transparent electrode ITO (indium tin oxide) film provided on the color filter (breakage of the planar film) occur.

  In addition, in the method of increasing the content of light-shielding pigments and dyes, there is a problem that the sensitivity, developability, resolution, adhesion, etc. of the photosensitive resin (black resist) deteriorate, and only a decrease in productivity. The accuracy and reliability required for the color filter cannot be obtained. That is, since a photosensitive material that can exhibit sensitivity and resolution under conditions of a thin film and high light-shielding properties has not been realized, the practical use of the resin BM is hindered.

  Conventionally, a technique for improving sensitivity and resolution performance is known for a general photosensitive resin or a photosensitive resin having a certain light transmittance such as a colored photosensitive composition for a color filter. For example, a photosensitive composition containing an initiator composed of a binder resin, a polyfunctional acrylic monomer, and a triazine compound is known as a coloring composition for a color filter in which a pigment is dispersed (see Patent Documents 1 to 4). In addition, it is also known that the initiator is bisimidazole in the same composition (see Patent Documents 5 to 6). However, in the case of the compositions disclosed therein, the polymerization inhibition by oxygen occurs when exposed in air. Therefore, practical sensitivity could not be obtained.

  When light blocking capability is required in the entire wavelength region of light as in the case of resin BM, (1) it is extremely difficult to make a difference in crosslink density between the exposed portion and the unexposed portion, and (2) the exposed portion. However, there is a difference in crosslink density with respect to the film thickness direction. That is, even when sufficiently cured on the light-irradiated surface, it does not cure on the base surface. (3) To blend a large amount of black color material insoluble in the developer. This is a hindrance in imparting significant photosensitivity such as a significant decrease in developability.

  In particular, the above phenomena (1) and (2) are contradictory, and as the exposed portion is more cured, the difference in the curing density in the film thickness direction becomes larger, leading to lower resolution. Further, if the difference in cross-linking density between the exposed area / unexposed area and the cured density of the exposed area cannot be made uniform, it becomes difficult to use a developing solution having a strong dissolving power, so that it is difficult to improve developability. Conventionally known photosensitive compositions for forming a resin BM (see, for example, Patent Documents 7 to 8) avoid such a situation, and form a resin BM that can shield light at the same level as a metal BM. Instead, the light was transmitted to some extent to give a photosensitive ability, and the light shielding ability was remarkably low, which was not practical. For this reason, a resin BM having a high light-shielding degree with a thin film has also been proposed due to film shrinkage in the curing process after once forming a resin BM having a high film thickness and low light-shielding properties (see Patent Document 9). However, it is difficult to put it into practical use due to problems such as the complexity of adhesion and the decrease in adhesion due to strain accumulation during film shrinkage. Thus, due to the seemingly contradictory problem of causing a photoreaction under the condition of light shielding, which is inherently opposite to the photoreaction, it has been difficult to realize a practical resin BM.

  Moreover, although the technique which uses a specific oxime ester compound as a photoinitiator is known (refer patent document 10), the initiator (for example, bisimidazole and a triazine type | system | group initiator) currently used by resin BM is known. ) Was simply replaced with the oxime compound, the image characteristics required for the resin BM, that is, sensitivity and resolution could not be improved.

  Highly sensitive photopolymerizable compositions are widely required not only for BM applications having black pigments but also for red, green, and blue color pixel forming compositions, photospacer compositions, and rib compositions. The technical problem has mainly been the selection of the photopolymerization initiator.

Japanese Patent Laid-Open No. 1-152449 JP-A-1-254918 JP-A-2-153353 JP-A-2-804 JP-A-6-75372 JP-A-6-75373 JP-A-6-51499 JP-A-6-3518 JP-A-8-44050 JP 2000-80068 A

  The present invention solves the above-mentioned problems and provides a resist material that can easily form a thin film and a highly light-shielding pattern by a photolithography method and has sufficient sensitivity and resolution. BM can be manufactured with high accuracy and low cost. In addition, a liquid crystal display device using the color filter manufactured in this way is excellent in display capability such as contrast. Further, by making BM resin, the color filter can be improved in image quality and non-polluted.

  In recent years, in order to achieve the “high density” required for color filters, it has been necessary to increase the color material concentration in the colored composition to be used, but on the other hand, the light transmittance of the colored resin composition is lowered. Therefore, in order to maintain and improve the image forming performance, a photopolymerizable material with higher sensitivity has been demanded. The present invention solves the above problems.

  In addition, photo spacers used for the manufacture of liquid crystal display devices, photosensitive compositions for ribs, and photosensitive compositions using photopolymerizable materials in general are also required to be manufactured with high accuracy and low cost. Therefore, there is a demand for a photopolymerizable image-forming material with higher sensitivity, and the present invention solves the above problems.

  As a result of diligent research, the present inventors have combined a specific oxime ester compound having a structure that 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 by using the photopolymerizable composition contained therein.

  Furthermore, the specific oxime ester-based compound is a novel compound in itself and is found to be effective as an excellent photopolymerization initiator regardless of the presence or absence of a coloring material, and has led to the completion of the present invention. It was.

  That is, the gist of the present invention resides in the oxime ester compound represented by the general formula (1) or (2).

（式中、Ｒ^1aは、それぞれ置換されていてもよい炭素数２〜２５のアルケニル基、炭素数１〜２０のヘテロアリールアルキル基、炭素数３〜２０のアルコキシカルボニルアルキル基、炭素数８〜２０のフェノキシカルボニルアルキル基、炭素数１〜２０のヘテロアリールオキシカルボニルアルキル基もしくはヘテロアリールチオアルキル基、炭素数０〜２０のアミノ基、又は炭素数１〜２０のアミノアルキル基を示し、また、Ｒ^1aは、Ｒ１'とともに環を形成してもよく、その連結基は、それぞれ置換基を有していてもよい炭素数１〜１０のアルキレン基、−（ＣＨ＝ＣＨ）_n−、−（Ｃ≡Ｃ）_n−あるいはその組み合わせであり（ｎは０〜３の整数）、Ｒ^2aは、それぞれ置換されていてもよい炭素数２〜１２のアルカノイル基、炭素数３〜２５のアルケノイル基、炭素数３〜８のシクロアルカノイル基、炭素数７〜２０のベンゾイル基、炭素数１〜２０のヘテロアリーロイル基、炭素数２〜１０のアルコキシカルボニル基又は炭素数７〜２０のフェノキシカルボニル基を示し、Ｒ１'は芳香環あるいはヘテロ芳香環を含む任意の置換基を示す。）：

Wherein R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and 8 to 8 carbon atoms. A phenoxycarbonylalkyl group having 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or a heteroarylthioalkyl group, an amino group having 0 to 20 carbon atoms, or an aminoalkyl group having 1 to 20 carbon atoms, R ^1a may form a ring together with R ¹ ′, and the linking group is an alkylene group having 1 to 10 carbon atoms that may have a substituent, — (CH═CH) _n —, — ( C≡C) _n — or a combination thereof (n is an integer of 0 to 3), and R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, 3 to 2 carbon atoms 5 alkenoyl group, C3-C8 cycloalkanoyl group, C7-C20 benzoyl group, C1-C20 heteroaryloyl group, C2-C10 alkoxycarbonyl group, or C7-C20 And R1 ′ represents an optional substituent containing an aromatic ring or a heteroaromatic ring.):

（式中、Ｒ^1bは、それぞれ置換されていてもよい炭素数６〜２０のフェニル基、炭素数１〜２０のアルキル基、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基、炭素数７〜２０のベンゾイル基、炭素数２〜１２のアルコキシカルボニル基もしくはフェノキシカルボニル基、炭素数１〜２０のアミド基、ニトロ基、炭素数２〜２５のアルケニル基、炭素数１〜１０のヘテロアリールアルキル基、炭素数３〜２０のアルコキシカルボニルアルキル基、炭素数８〜２０のフェノキシカルボニルアルキル基、炭素数１〜２０のヘテロアリールオキシカルボニルアルキル基もしくはヘテロアリールチオアルキル基、炭素数０〜２０のアミノ基、又は炭素数１〜２０のアミノアルキル基を示し、またＲ^1bは、Ｒ１'とともに環を形成してもよく、その連結基は、それぞれ置換基を有していてもよい炭素数１〜１０アルキレン基、−（ＣＨ＝ＣＨ）_n−、−（Ｃ≡Ｃ）_n−あるいはその組み合わせであり（ｎは０〜３の整数）、Ｒ^2bは、それぞれ置換されていてもよい炭素数１〜２０のヘテロアリール基、炭素数１〜２０のヘテロアリールアルカノイル基、炭素数３〜２０のアルコキシカルボニルアルカノイル基、炭素数８〜２０のフェノキシカルボニルアルカノイル基、炭素数３〜２０のヘテロアリ−ルオキシキシカルボニルアルカノイル基、又は炭素数２〜１０のアミノカルボニル基を示し、 Ｒ１'は芳香環あるいはヘテロ芳香環を含む任意の置換基を示す。）

(In the formula, R ^1b is a phenyl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl having 2 to 20 carbon atoms, each of which may be substituted. Group, benzoyl group having 7 to 20 carbon atoms, alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, amide group having 1 to 20 carbon atoms, nitro group, alkenyl group having 2 to 25 carbon atoms, 1 to carbon atoms 10 heteroarylalkyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, carbon number Represents an amino group having 0 to 20 or an aminoalkyl group having 1 to 20 carbon atoms, and R ^1b forms a ring together with R 1 ′. The linking group may be an optionally substituted alkylene group having 1 to 10 carbon atoms, — (CH═CH) _n —, — (C≡C) _n —, or a combination thereof ( n is an integer of 0 to 3), and R ^2b is an optionally substituted heteroaryl group having 1 to 20 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms. A phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxyxycarbonylalkanoyl group having 3 to 20 carbon atoms, or an aminocarbonyl group having 2 to 10 carbon atoms, and R1 ′ represents an aromatic ring or a heteroaromatic ring. Any optional substituent is shown.)

Another aspect of the present invention is that, in the general formula (1), R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and carbon. It is a phenoxycarbonylalkyl group having 8 to 20 carbon atoms or an aminoalkyl group having 1 to 20 carbon atoms, or R ^1a may form a ring together with R ¹ ′, and each linking group has a substituent. Or an alkylene group having 1 to 10 carbon atoms, — (CH═CH) _n —, — (C≡C) _n — or a combination thereof (n is an integer of 0 to 3), and R ^2a is substituted. It is an oxime ester compound characterized by being an alkanoyl group having 2 to 12 carbon atoms which may be used.

Another gist of the present invention is that, in the general formula (2), R ^1b is an optionally substituted alkyl group having 1 to 20 carbon atoms, and R ^2b may be substituted. C1-C20 heteroaryl group, C1-C20 heteroarylalkanoyl group, C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, or C2-C10 amino An oxime ester compound characterized by being a carbonyl group.

  Another gist of the present invention resides in the oxime ester compound represented by the general formula (3) or (4).

（式中、Ｒ^1aは、それぞれ置換されていてもよい炭素数２〜２５のアルケニル基、炭素数１〜２０のヘテロアリールアルキル基、炭素数３〜２０のアルコキシカルボニルアルキル基、炭素数８〜２０のフェノキシカルボニルアルキル基、炭素数１〜２０のヘテロアリールオキシカルボニルアルキル基もしくはヘテロアリールチオアルキル基、炭素数０〜２０のアミノ基、又は炭素数１〜２０のアミノアルキル基を示し、また、Ｒ^1aは、Ｒ³あるいはＲ⁷とともに環を形成してもよく、その場合、Ｒ^1aとＲ³あるいは／およびＲ⁷は互いに結合してともに２価あるいは３価の連結基を形成し、その連結基はそれぞれ置換基を有してもよい炭素数１〜１０のアルキレン基、−（ＣＨ＝ＣＨ）_n−、−（Ｃ≡Ｃ）_n−あるいはその組み合わせであり（ｎは０〜３の整数）、Ｒ^2aは、それぞれ置換されていてもよい炭素数２〜１２のアルカノイル基、炭素数３〜２５のアルケノイル基、炭素数３〜８のシクロアルカノイル基、炭素数７〜２０のベンゾイル基、炭素数１〜２０のヘテロアリーロイル基、炭素数２〜１０のアルコキシカルボニル基又は炭素数７〜２０のフェノキシカルボニル基を示し、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、互いに独立して、水素原子、ハロゲン原子、それぞれ置換されていてもよい炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数５〜８のシクロアルキル基、炭素数６〜２０のフェニル基、炭素数７〜２０のベンジル基、炭素数７〜２０のベンゾイル基、炭素数２〜１２のアルカノイル基、炭素数１〜２０のヘテロアリーロイル基、炭素数３〜２０のアルコキシカルボニルアルカノイル基、炭素数８〜２０のフェノキシカルボニルアルカノイル基、炭素数３〜２０のヘテロアリ−ルオキシキシカルボニルアルカノイル基、炭素数２〜１２のアルコキシカルボニル基もしくはフェノキシカルボニル基又は、−ＯＲ⁸、−ＳＲ⁹、−ＳＯＲ⁹、−ＳＯ₂Ｒ⁹もしくは−ＮＲ¹⁰Ｒ¹¹を示し、かつ、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷の少なくとも一つは、−ＯＲ⁸、−ＳＲ⁹又は−ＮＲ¹⁰Ｒ¹¹を示す。ただし、Ｒ⁸は、水素原子、それぞれ置換されていてもよい炭素数１〜１２のアルキル基、炭素数２〜８のアルカノイル基、炭素数３〜１２のアルケニル基、炭素数３〜２０のアルケノイル基、炭素数６〜２０のフェニル基、−（ＣＨ₂ ＣＨ₂Ｏ）_mＨ（ｍは１〜２０の整数）、又は炭素数３〜１５のトリアルキルシリル基を示し、Ｒ⁹は、水素原子、それぞれ置換されていてもよい炭素数１〜１２のアルキル基、炭素数２〜８のアルカノイル基、炭素数３〜１２のアルケニル基、炭素数６〜２０のフェニル基又は炭素数３〜１５のトリアルキルシリル基を示し、Ｒ¹⁰およびＲ¹¹は、互いに独立して水素原子、それぞれ置換されていてもよい炭素数１〜１２のアルキル基、炭素数２〜４のヒドロキシルアルキル基、炭素数３〜５のアルケニル基または炭素数６〜２０のフェニル基を表し、Ｒ³〜Ｒ⁷は互いに結合して、またＲ¹と共に環構造を形成してもよい。）：

Wherein R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and 8 to 8 carbon atoms. A phenoxycarbonylalkyl group having 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or a heteroarylthioalkyl group, an amino group having 0 to 20 carbon atoms, or an aminoalkyl group having 1 to 20 carbon atoms, R ^1a may form a ring with R ³ or R ⁷ , in which case R ^1a and R ³ or / and R ⁷ are bonded together to form a divalent or trivalent linking group, linking groups each substituent alkylene group having 1 to 10 carbon atoms which may have _{a, - (CH = CH) n} -, - (C≡C) n - or a combination thereof ( Is an integer of 0 to 3), R ^2a are each optionally substituted alkanoyl group having 2 to 12 carbon atoms, alkenoyl of 3 to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, 7 carbon atoms Represents a benzoyl group having 20 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or a phenoxycarbonyl group having 7 to 20 carbon atoms, and R ³ , R ⁴ , R ⁵ , R ⁶ And R ⁷ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. , A phenyl group having 6 to 20 carbon atoms, a benzyl group having 7 to 20 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, and a carbon number 3 20 alkoxycarbonyl alkanoyl group, phenoxycarbonyl alkanoyl group having 8 to 20 carbon atoms, heteroaryl having 3 to 20 carbon atoms - Luo Kishikishi carbonyl alkanoyl group, or an alkoxycarbonyl group or a phenoxycarbonyl group having 2 to 12 carbon atoms, -OR ⁸ , -SR ⁹ , -SOR ⁹ , -SO ₂ R ⁹ or -NR ¹⁰ R ¹¹ , and at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is -OR ⁸ ,- SR ⁹ or —NR ¹⁰ R ¹¹ , wherein R ⁸ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, or 3 to 12 carbon atoms. alkenyl group, alkenoyl group having 3 to 20 carbon atoms, a phenyl group having 6 to 20 carbon _{atoms, - (CH 2 CH 2 O} ) m H (m is an integer of 1 to 20), or 3 carbon 15 represents a trialkylsilyl group, and R ⁹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, A phenyl group having 6 to 20 carbon atoms or a trialkylsilyl group having 3 to 15 carbon atoms, wherein R ¹⁰ and R ¹¹ are each independently a hydrogen atom, and an optionally substituted alkyl having 1 to 12 carbon atoms; Represents a hydroxyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or a phenyl group having 6 to 20 carbon atoms, wherein R ^{3 to} R ⁷ are bonded to each other and have a ring structure together with R ^1. You may form. ):

（式中、Ｒ^1bは、それぞれ置換されていてもよい炭素数６〜２０のフェニル基、炭素数１〜２０のアルキル基、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基、炭素数７〜２０のベンゾイル基、炭素数２〜１２のアルコキシカルボニル基もしくはフェノキシカルボニル基、炭素数１〜２０のアミド基、ニトロ基、炭素数２〜２５のアルケニル基、炭素数１〜１０のヘテロアリールアルキル基、炭素数３〜２０のアルコキシカルボニルアルキル基、炭素数８〜２０のフェノキシカルボニルアルキル基、炭素数１〜２０のヘテロアリールオキシカルボニルアルキル基もしくはヘテロアリールチオアルキル基、炭素数０〜２０のアミノ基、又は炭素数１〜２０のアミノアルキル基を示し、またＲ^1bは、Ｒ³あるいはＲ⁷とともに環を形成してもよく、その場合、Ｒ^1bとＲ³あるいは／およびＲ⁷は互いに結合してともに２価あるいは３価の連結基を形成し、その連結基はそれぞれ置換基を有してもよい炭素数１〜１０のアルキレン基、−（ＣＨ＝ＣＨ）_n−、−（Ｃ≡Ｃ）_n−あるいはその組み合わせであり（ｎは０〜３の整数）、 Ｒ^2bは、それぞれ置換されていてもよい炭素数１〜２０のヘテロアリール基、炭素数１〜２０のヘテロアリールアルカノイル基、炭素数３〜２０のアルコキシカルボニルアルカノイル基、炭素数８〜２０のフェノキシカルボニルアルカノイル基、炭素数３〜２０のヘテロアリ−ルオキシキシカルボニルアルカノイル基、又は炭素数２〜１０のアミノカルボニル基を示し、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は前記一般式（３）におけると同義である。）

(In the formula, R ^1b is an optionally substituted phenyl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl having 2 to 20 carbon atoms. Group, benzoyl group having 7 to 20 carbon atoms, alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, amide group having 1 to 20 carbon atoms, nitro group, alkenyl group having 2 to 25 carbon atoms, 1 to carbon atoms 10 heteroarylalkyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, carbon number Represents an amino group having 0 to 20 or an aminoalkyl group having 1 to 20 carbon atoms, and R ^1b is together with R ³ or R ⁷ In this case, R ^1b and R ³ or / and R ⁷ may be bonded to each other to form a divalent or trivalent linking group, each of which has a substituent. Or an alkylene group having 1 to 10 carbon atoms, — (CH═CH) _n —, — (C≡C) _n — or a combination thereof (n is an integer of 0 to 3), and R ^2b is each substituted. C1-20 heteroaryl group, C1-20 heteroarylalkanoyl group, C3-20 alkoxycarbonylalkanoyl group, C8-20 phenoxycarbonylalkanoyl group, C3 20 of heteroaryl - Luo Kishikishi carbonyl alkanoyl group, or an amino carbonyl group having 2 to 10 carbon atoms, synonymous with ^{R 3, R 4, R 5} , R 6 and R ⁷ are definitive in the general formula (3) A.)

Another aspect of the present invention is that, in the general formula (3), R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and carbon. It is a phenoxycarbonylalkyl group having 8 to 20 carbon atoms or an aminoalkyl group having 1 to 20 carbon atoms, or R ^1a may form a ring together with R ³ or R ⁷ , in which case R ^1b and R ³ Alternatively, and / or R ⁷ are bonded to each other to form a divalent or trivalent linking group, and each of the linking groups has a C 1-10 alkylene group that 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 an optionally substituted alkanoyl group having 2 to 12 carbon atoms, and R ^{3 , R 4, R 5, R} 6 and R ^7, Independently you are, a hydrogen atom, a halogen atom, each optionally substituted alkyl group having 1 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, heteroarylene acryloyl group or -NR 1 to 20 carbon atoms ¹⁰ R ¹¹ , and at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represents —NR ¹⁰ R ¹¹ (provided that R ¹⁰ and R ¹¹ are each independently hydrogen An atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a hydroxyl alkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or a phenyl group having 6 to 20 carbon atoms), R ^{3 to} R ⁷ are bonded to each other and may form a ring structure together with R ^1a .

Another gist of the present invention is that, in the general formula (4), R ^1b is an optionally substituted alkyl group having 1 to 20 carbon atoms, and R ^2b may be substituted. C1-C20 heteroaryl group, C1-C20 heteroaryl alkanoyl group, C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, or C2-C10 amino R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or a carbon number. A phenyl group having 6 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms or —NR ¹⁰ R ¹¹ , and at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is —NR ¹⁰ indicates R ¹¹ (However, R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a hydroxyl alkyl group having 2 to 4 carbon atoms, or a 3 to 5 carbon atoms. An alkenyl group or a phenyl group having 6 to 20 carbon atoms), R ^{3 to} R ⁷ are bonded to each other and may form a ring structure together with R ^1b , which is an oxime ester compound.

  Another gist of the present invention resides in an oxime ester compound represented by any one of the general formulas (5) to (7).

（式中、Ｒ^1a、Ｒ^2aは、請求項４に記載の前記一般式（３）におけると同義であり、 Ｒ³、Ｒ⁶、Ｒ⁷、Ｒ¹²〜Ｒ¹⁶は、水素原子、ハロゲン原子、それぞれ置換されていてもよい炭素数１〜１２のアルキル基、炭素数２〜１２のアルケノイル基、炭素数６〜２０のフェニル基、炭素数７〜２０のベンジル基もしくはベンゾイル基、又は−ＮＲ¹⁰Ｒ¹¹であり、Ｒ³、Ｒ⁶、Ｒ⁷、Ｒ¹²〜Ｒ¹⁶は互いに結合して環構造を形成してもよい。 ）

(In the formula, R ^1a and R ^2a have the same meaning as in the general formula (3) according to claim 4, and R ³ , R ⁶ , R ⁷ , and R ^{12 to} R ¹⁶ are a hydrogen atom and a halogen atom. , An optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, a benzyl group or benzoyl group having 7 to 20 carbon atoms, or -NR ¹⁰ R ¹¹ , and R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁶ may be bonded to each other to form a ring structure.

（式中、Ｒ^1b、Ｒ^2bは、前記一般式（４）におけると同義であり、Ｒ³、Ｒ⁶、Ｒ⁷、Ｒ¹²〜Ｒ¹⁶は、前記一般式（５）におけると同義である。 ）

(In the formula, R ^1b and R ^2b have the same meaning as in the general formula (4), and R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁶ have the same meaning as in the general formula (5). )

（式中、Ｒ^1aは、それぞれ前記の一般式（４）におけると同義であり、Ｒ^2bは、前記の一般式（３）におけるＲ^2a及び一般式（４）におけるＲ^2bを示し、 Ｒ³、Ｒ⁶、Ｒ⁷、Ｒ¹²〜Ｒ¹⁶は、水素原子、ハロゲン原子、それぞれ置換されていてもよい炭素数１〜１２のアルキル基、炭素数２〜１２のアルケノイル基、炭素数６〜２０のフェニル基、炭素数７〜２０のベンジル基もしくはベンゾイル基、又は−ＮＲ¹⁰Ｒ¹¹であり、Ｒ³、Ｒ⁶、Ｒ⁷、Ｒ¹²〜Ｒ¹⁶は互いに結合して環構造を形成してもよく、且つＲ³、Ｒ⁶、Ｒ⁷、Ｒ¹²〜Ｒ¹⁶のうち少なくとも一つがそれぞれ置換されていてもよい炭素数１〜２０のヘテロアリールアルキル基、ヘテロアリールアルカノイル基もしくはヘテロアリーロイル基及び炭素数３〜１５のトリアルキルシリル基からなる群より選ばれる少なくとも１種を含む。）

(Wherein, R ^1a has the same meaning as in the general formula respectively (4), R ^2b represents an R ^2b in R ^2a and formula (4) in the above general formula (3), R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁶ are each a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, or 6 to 20 carbon atoms. A phenyl group, a benzyl group having 7 to 20 carbon atoms or a benzoyl group, or —NR ¹⁰ R ¹¹ , wherein R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ are bonded to each other to form a ring structure. And a heteroarylalkyl group, a heteroarylalkanoyl group or a heteroaryloyl group having 1 to 20 carbon atoms, wherein at least one of R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁶ may be substituted. And trialkyl having 3 to 15 carbon atoms Containing at least one selected from the group consisting of Lil group.)

Another gist of the present invention is that in general formula (5), R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and a carbon number. It is an 8-20 phenoxycarbonylalkyl group or an aminoalkyl group having 1-20 carbon atoms, or R ^1a may form a ring together with R ³ or R ⁷ , in which case R ^1a and R ³ or / And R ⁷ are bonded to each other to form a divalent or trivalent linking group, each of which is a 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 an optionally substituted alkanoyl group having 2 to 12 carbon atoms, R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ are hydrogen atoms A C 1-12 alkyl group, a C 2-12 alkenoyl group, a C 6-20 phenyl group, a C 7-20 benzyl group or a benzoyl group, each of which may be substituted. Or NR ¹⁰ R ¹¹ , and R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ may be bonded to each other to form a ring structure.

Another gist of the present invention is that, in General Formula (6), R ^1b is an optionally substituted alkyl group having 1 to 20 carbon atoms, and R ^2b is an optionally substituted carbon. A heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, or an aminocarbonyl group having 2 to 10 carbon atoms, R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁶ are each a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, It is a benzyl group or benzoyl group having 7 to 20 carbon atoms, or —NR ¹⁰ R ¹¹ , and R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ may be bonded to each other to form a ring structure. Features It resides in the oxime ester compound.

  Moreover, the other summary of this invention exists in the oxime ester type compound shown by General formula (8) or (9).

（式中、Ｒ^1aは、それぞれ置換されていてもよい炭素数２〜２５のアルケニル基、炭素数１〜２０のヘテロアリールアルキル基、炭素数３〜２０のアルコキシカルボニルアルキル基、炭素数８〜２０のフェノキシカルボニルアルキル基、炭素数１〜２０のヘテロアリールオキシカルボニルアルキル基もしくはヘテロアリールチオアルキル基、炭素数０〜２０のアミノ基、又は炭素数１〜２０のアミノアルキル基を示し、また、Ｒ^1aは、Ａｒ₁とともに環を形成してもよく、その連結基は、それぞれ置換基を有していてもよい炭素数１〜１０のアルキレン基、−（ＣＨ＝ＣＨ）_n−、−（Ｃ≡Ｃ）_n−あるいはその組み合わせであり（ｎは０〜３の整数）、Ｒ^2aは、請求項１に記載の一般式（１）におけると同義であり、Ａｒ₁は、置換基を有していてもよい芳香環、ヘテロ芳香環、縮合芳香環又は縮合ヘテロ芳香環を表し、ｐは、２〜５の整数を表す。）：

Wherein R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and 8 to 8 carbon atoms. A phenoxycarbonylalkyl group having 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or a heteroarylthioalkyl group, an amino group having 0 to 20 carbon atoms, or an aminoalkyl group having 1 to 20 carbon atoms, R ^1a may form a ring together with Ar ₁ , and each of the linking groups thereof may have a substituent, an alkylene group having 1 to 10 carbon atoms, — (CH═CH) _n —, — ( C≡C) _n — or a combination thereof (n is an integer of 0 to 3), R ^2a has the same meaning as in the general formula (1) according to claim 1, and Ar ₁ has a substituent. Shi Represents an aromatic ring, a heteroaromatic ring, a condensed aromatic ring or a condensed heteroaromatic ring which may be present, and p represents an integer of 2 to 5):

（式中、Ｒ^1bは、それぞれ置換されていてもよい炭素数６〜２０のフェニル基、炭素数１〜２０のアルキル基、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基、炭素数７〜２０のベンゾイル基、炭素数２〜１２のアルコキシカルボニル基もしくはフェノキシカルボニル基、炭素数１〜２０のアミド基、ニトロ基、炭素数２〜２５のアルケニル基、炭素数１〜１０のヘテロアリールアルキル基、炭素数３〜２０のアルコキシカルボニルアルキル基、炭素数８〜２０のフェノキシカルボニルアルキル基、炭素数１〜２０のヘテロアリールオキシカルボニルアルキル基もしくはヘテロアリールチオアルキル基、炭素数０〜２０のアミノ基、又は炭素数１〜２０のアミノアルキル基を示し、またＲ^1bは、Ａｒ₁とともに環を形成してもよく、その連結基は、それぞれ置換基を有していてもよい炭素数１〜１０アルキレン基、−（ＣＨ＝ＣＨ）_n−、−（Ｃ≡Ｃ）_n−あるいはその組み合わせであり（ｎは０〜３の整数）、Ｒ^2bは、請求項１に記載の一般式（２）におけると同義であり、Ａｒ₁は、置換基を有していてもよい芳香環、ヘテロ芳香環、縮合芳香環又は縮合ヘテロ芳香環を表し、ｐは、２〜５の整数を表す。）

(In the formula, R ^1b is an optionally substituted phenyl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl having 2 to 20 carbon atoms. Group, benzoyl group having 7 to 20 carbon atoms, alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, amide group having 1 to 20 carbon atoms, nitro group, alkenyl group having 2 to 25 carbon atoms, 1 to carbon atoms 10 heteroarylalkyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, carbon number 0-20 amino group, or an amino alkyl group having 1 to 20 carbon atoms, also R ^1b is, form a ring with Ar ₁ At best, the linkage is respectively substituent may number 1 to 10 alkylene carbon atoms which may have _{a, - (CH = CH) n} -, - (C≡C) n - or a combination thereof ( n is an integer of 0 to 3), R ^2b has the same meaning as in general formula (2) according to claim 1, Ar ₁ is an aromatic ring, heteroaromatic ring optionally having a substituent, Represents a condensed aromatic ring or a condensed heteroaromatic ring, and p represents an integer of 2 to 5.)

Another gist of the present invention is that in general formula (8), R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and a carbon number. An phenoxycarbonylalkyl group having 8 to 20 carbon atoms or an aminoalkyl group having 1 to 20 carbon atoms, and R ^1a may form a ring together with Ar ₁ , in which case R ^1a and Ar ₁ are bonded to each other; Together, a divalent or trivalent linking group is formed, and each of the linking groups is an alkylene group having 1 to 10 carbon atoms which may have a substituent,-(CH = CH) _n -,-( C≡C) _n — or a combination thereof (n is an integer of 0 to 3), and R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, Exist.

Another gist of the present invention is that, in General Formula (9), R ^1b is an optionally substituted alkyl group having 1 to 20 carbon atoms, and R ^2b is an optionally substituted carbon. A heteroaryl group having 1 to 20 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, or an aminocarbonyl having 2 to 10 carbon atoms It exists in the oxime ester type compound characterized by being a group.

  Another gist of the present invention is a photopolymerizable composition containing (b) an organic binder and (c) a photopolymerization initiator, wherein (c) is the oxime ester compound. In the photopolymerizable composition.

  Moreover, the other summary of this invention exists in the photopolymerizable composition in any one of the said which is (b) the organic binder is the epoxy acrylate resin which has a carboxyl group.

  Another gist of the present invention is (b) an epoxy acrylate obtained by reacting (hydro) phthalic anhydride with a reaction product of a novolac type epoxy resin and (meth) acrylic acid. The photopolymerizable composition according to any one of the above.

  Another gist of the present invention resides in the photopolymerizable composition according to any one of the above, wherein the photopolymerizable composition further contains (d) a photopolymerizable monomer.

  Another gist of the present invention is that the photopolymerizable composition further comprises (e) a polymer dispersant having a basic functional group. It exists in things.

  Another gist of the present invention resides in any of the above photopolymerizable compositions, wherein the photopolymerizable composition further contains (a) a coloring material.

  Further, another gist of the present invention resides in a color filter having an image formed by any of the photopolymerizable compositions described above.

  Another gist of the present invention resides in a liquid crystal display device having an image formed by any of the photopolymerizable compositions described above.

  The oxime ester compound of the present invention can be used as a novel and highly sensitive photopolymerization initiator. By combining this with an organic binder and a coloring material, a photopolymerizable composition useful for color filter applications can be constituted. Particularly when used in combination with a black color material, the photopolymerizable composition is excellent in sensitivity and resolution while being highly light-shielding in a thin film, so that a high-quality resin BM is formed at low cost. Can do. Since the color filter using the resin BM of the present invention is excellent in accuracy, flatness and durability, the display quality of the liquid crystal element can be improved. In addition, since the manufacturing process and the color filter itself do not contain harmful substances, the danger to the human body is reduced and the environmental safety is improved. Furthermore, the present invention is not limited to BM use, and can be used for transparent photosensitive compositions that do not use color materials such as photo spacers and ribs (liquid crystal division alignment protrusions), and the application technical fields are wide.

(A) Coloring material Coloring material is not an essential component in the practice of the present invention, but is used in combination in many applications. Here, the coloring material means a colorant for the photosensitive composition. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like. As the pigment, pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene and perylene, various inorganic pigments can be used. It is. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. Terms such as “CI Pigment Red 2” mentioned below mean the color index (CI).

  Examples of red pigments include C.I. 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, 17 , 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, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. 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, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.

  Examples of yellow pigments include C.I. 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, 17 174, 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, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. 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, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. 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, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

  As the black color material, a single black color material or a black color material obtained by mixing red, green, blue, or the like can be used. These black color materials can be appropriately selected from inorganic or organic pigments and dyes, and can be used alone or in combination.

  Examples of the single black color material include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black. Among these, carbon black and titanium black are particularly preferable from the viewpoints of light shielding rate and image characteristics. Examples of commercially available carbon black include the following brands.

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

  Made by Degussa: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, Special BlackS, 350c, p

  Manufactured by Cabot Corporation: Monarch 460, Monarch 430, Monarch 280, Monarch 120, Monarch 800, Monarch 4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACK PEARLS480, PEARLS480, etc.

  Made by Colombian Carbon: Raven11, Raven15, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890H, Raven1000, Raven1020, Raven1040 and the like.

  Next, the black color material by mixing is demonstrated. Specific examples of the color material used as a base for mixing include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 (50240), Erioglaucine X (42080), no. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen 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), etc. (The numbers in parentheses above mean the color index (CI)).

  Further, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  The carbon black may be used in combination with other black or colored inorganic or organic pigments. Other pigments naturally have a light shielding property or image characteristic lower than that of carbon black, so the mixing ratio is naturally limited.

  Titanium black is produced by heating a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No. Sho 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), etc. is not.

Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.
(B) Organic Binder When the photopolymerizable composition is constituted in the present invention, (b) an organic binder is used. The organic binder is not particularly limited, but an epoxy acrylate resin having a carboxyl group is particularly preferably used.

  In the epoxy acrylate resin, an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to the epoxy resin, and a polybasic acid anhydride is further reacted. Is synthesized. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin is a raw material, and “acrylate” is a representative example. It is named like this according to common usage.

  As the raw material epoxy resin, (o, m, p-) cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, represented by the following formula The epoxy resin etc. which can be used can be used suitably (refer patent 2878486).

  The molecular weight of an epoxy resin is 200-200000 normally as a weight average molecular weight measured by GPC, Preferably it is the range of 300-100000. If the molecular weight is less than the above range, there are many cases where problems occur in the film-forming property. Conversely, resins exceeding the above range are prone to gelation during the addition reaction of α, β-unsaturated monocarboxylic acid, and are difficult to produce. There is a risk of becoming.

  Examples of the α, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid and the like, preferably acrylic acid and methacrylic acid, and particularly acrylic acid is highly reactive. Therefore, it is preferable. The α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion includes acrylic acid-2-succinoyloxyethyl, acrylic acid-2-malenoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, Acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexahydrophthalo Yloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like. Preferred are acrylic acid-2-malenoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate, and particularly acrylic acid-2-maleic acid. Noyloxyethyl is preferred.

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

  The amount of α, β-unsaturated monocarboxylic acid or ester thereof used is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1, relative to 1 equivalent of the epoxy group of the raw material epoxy resin. Equivalent range. If the amount of α, β-unsaturated monocarboxylic acid or ester thereof used is small, the amount of unsaturated groups introduced is insufficient, and the subsequent reaction with the polybasic acid anhydride becomes insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, if the amount used is large, α, β-unsaturated monocarboxylic acid or ester thereof remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  The polybasic acid anhydride to be further added to the epoxy resin to which the α, β-unsaturated carboxylic acid or ester thereof is added includes maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetra Carboxylic acid dianhydride and the like, preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, Biphenyltetracarboxylic dianhydride Particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride.

  A known method can also be used for the addition reaction of polybasic acid anhydride, and it can be obtained by continuing the reaction under the same conditions as in the addition reaction of 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 resulting epoxy acrylate resin is in the range of 10 to 150 mgKOH / g, more preferably 20 to 140 mgKOH / g. When the resin acid value is below the above range, the alkali developability is poor, and when the resin acid value exceeds the above range, the curing performance tends to be inferior.

  (B) In addition to the epoxy acrylate resin having a carboxyl group, the following resins can also be used as the organic binder. In addition, some of the resins described below partially overlap with those belonging to the epoxy acrylate resin, and are not classified as different substances.

  That is, a homopolymer or copolymer such as (meth) acrylic acid, (meth) acrylic ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, or a carboxyl group Preferable examples include a vinyl-containing resin, polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, and acetyl cellulose. Among these, from the viewpoint of alkali developability and image formability, the epoxy acrylate resin having a carboxyl group and the carboxyl group-containing vinyl resin are preferable, and the epoxy acrylate resin having a carboxyl group is more preferable.

  As the carboxyl group-containing vinyl resin, for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and other unsaturated carboxylic acids, styrene, α-methylstyrene , 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-dimethyl Aminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl And copolymers with vinyl compounds such as (meth) acrylamide and vinyl acetate.

  Among the above copolymers, a styrene- (meth) acrylate- (meth) acrylic acid copolymer is preferable, and 3-30 mol% styrene, 10-70 mol% (meth) acrylate, 10 (meth) acrylic acid. A copolymer composed of ˜60 mol% is more preferred, and a copolymer composed of 5-25 mol% styrene, 20-60 mol% (meth) acrylate, and 15-55 mol% (meth) acrylic acid is particularly preferred. These carboxyl group-containing vinyl resins have an acid value of 30 to 250 mg-KOH / g, preferably 50 to 200 mg-KOH / g, and more preferably 70 to 150 mg-KOH / g.

  Furthermore, as the carboxyl group-containing vinyl resin, those having an ethylenically unsaturated bond in the side chain are suitable. For example, allyl glycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl is added to the carboxyl group-containing polymer. (Meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, etc. Saturated compound, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1.0] dec-2 Yl] An alicyclic epoxy group-containing unsaturated compound such as oxymethyl (meth) acrylate is obtained by reacting 5 to 90 mol%, preferably about 30 to 70 mol% of the carboxyl group of the carboxyl group-containing polymer. Reaction products and allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, N, N-diallyl A compound having two or more unsaturated groups such as (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate , Vinyl crotonate, vinyl (meth) acrylamide The ratio of the compound having two or more kinds of unsaturated groups such as, and unsaturated carboxylic acid such as (meth) acrylic acid, or further unsaturated carboxylic acid ester to the whole compound having the former unsaturated group Examples include reaction products obtained by copolymerization so as to be about 10 to 90 mol%, preferably about 30 to 80 mol%.

  In addition, when used for forming the liquid crystal split alignment protrusions, in particular, when the weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) measurement is an epoxy acrylate resin having a carboxyl group, it is usually 1,000 or more. , Preferably 1,500 or more, usually 30,000 or less, preferably 20,000 or less, more preferably 10,000 or less, particularly preferably 5,000 or less. In the case of a carboxyl group-containing vinyl resin, it is usually 1,000 or more, preferably 1500 or more, more preferably 2000 or more, and usually 100,000 or less, preferably 50,000,000 or less, more preferably 20,000 or less, Especially preferably, it is 10,000 or less. When the organic binder in the above range is contained, deformation of the photopolymerizable composition upon heating is large, and therefore, an arch-shaped protrusion that is a good shape of the liquid crystal split alignment protrusion is formed, which is preferable.

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

（式中、符号の意味は前記の一般式（１）で定義したものと同一である。）

(In the formula, the meanings of the symbols are the same as those defined in the general formula (1).)

In general formula (1), R ^1a is preferably an optionally substituted alkenyl group having 2 to 25 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, or a phenoxycarbonylalkyl having 8 to 20 carbon atoms. A group or an aminoalkyl group having 1 to 20 carbon atoms, and R ^1a may form a ring together with R ¹ ′, and the linking group may have a substituent, each having 1 to 1 carbon atoms. 10 alkylene group, — (CH═CH) _n —, — (C≡C) _n — or a combination thereof (n is an integer of 0 to 3), and R ^2a has 2 carbon atoms which may be substituted. R12 'shows the arbitrary substituents containing an aromatic ring or a heteroaromatic ring.

（式中、符号の意味は前記の一般式（２）で定義したものと同一である。）

(In the formula, the meanings of the symbols are the same as those defined in the general formula (2).)

In general formula (2), Preferably, R ^<1b > shows a C1-C20 alkyl group, R ^<2b> is the C1-C20 heteroaryl group each substituted, C3-C3, respectively. 20 represents an alkoxycarbonylalkanoyl group, 8 to 20 phenoxycarbonylalkanoyl group or 2 to 10 aminocarbonyl group, and R1 ′ represents an optional substituent containing an aromatic ring or a heteroaromatic ring.

  Among the oxime ester compounds represented by the general formula (1) or (2), preferred compounds are those represented by the general formula (3) or (4).

（式中、符号の意味は前記の一般式（３）で定義したものと同一である。）

(In the formula, the meanings of the symbols are the same as those defined in the general formula (3).)

In general formula (3), R ^1a is preferably an optionally substituted alkenyl group having 2 to 25 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, or a phenoxycarbonylalkyl having 8 to 20 carbon atoms. R ^1a represents a group or an aminoalkyl group having 1 to 20 carbon atoms, and R ^1a may form a ring together with R ³ or R ⁷ , in which case R ¹ and R ³ or / and R ⁷ are bonded to each other. Together form a divalent or trivalent linking group, each of which may have a substituent, an alkylene group having 1 to 10 carbon atoms, — (CH═CH) _n —, — (C≡C). ) _N -or a combination thereof (n is an integer of 0 to 3), R ^2a represents an optionally substituted alkanoyl group having 2 to 12 carbon atoms, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ^7, independently of one another, a hydrogen atom, c Gen atoms, each optionally substituted alkyl group having 1 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, indicates heteroarylene acryloyl group or -NR ¹⁰ R ¹¹ having 1 to 20 carbon atoms, and, R ^At least one of ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represents —NR ¹⁰ R ¹¹ . R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a hydroxyl alkyl group having 2 to 4 carbon atoms, or an alkenyl group having 3 to 5 carbon atoms. Or a C6-C20 phenyl group is represented, R < ³ > -R < ⁷ > may couple | bond together and may form a ring structure with R < ¹ >.

（式中、符号の意味は前記の一般式（４）で定義したものと同一である。）

(In the formula, the meanings of the symbols are the same as those defined in the general formula (4)).

In general formula (4), R ^1b is preferably an ^optionally substituted alkyl group having 1 to 20 carbon atoms, and R ^2b is an optionally substituted heteroaryl group having 1 to 20 carbon atoms. A heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, or an aminocarbonyl group having 2 to 10 carbon atoms, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, or a carbon number. 1 to 20 heteroarylloyl group or —NR ¹⁰ R ¹¹ , and at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represents —NR ¹⁰ R ¹¹ (where R ¹⁰ and R ¹¹ Are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a hydroxyl alkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or 6 to 20 carbon atoms. R ^{3 to} R ⁷ may be bonded to each other and may form a ring structure together with R ^1b .

  Further preferred oxime ester compounds are compounds represented by any one of the following general formulas (5) to (7).

（式中、符号の意味は前記の一般式（５）で定義したものと同一である。）

(In the formula, the meanings of the symbols are the same as those defined in the general formula (5)).

Preferably, R ^1a is an optionally substituted alkenyl group having 2 to 15 carbon atoms, a heteroarylalkyl group having 1 to 10 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, or 8 to 20 carbon atoms. Phenoxycarbonylalkyl group, heteroarylthioalkyl group having 1 to 15 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, dialkylaminoalkyl group having 1 to 15 carbon atoms, N-acyloxy-N having 3 to 15 carbon atoms An acylaminoalkyl group, or an alkylene group having 1 to 15 carbon atoms, which R ^1a and R ³ or / and R ⁷ may be bonded to each other and may have a substituent, — (CH═CH) _n -Or a combination thereof.

More preferably, the alkenyl group having 2 to 12 carbon atoms, the alkoxycarbonylalkyl group having 3 to 12 carbon atoms, the phenoxycarbonylalkyl group having 8 to 20 carbon atoms, and the heteroaryl having 1 to 10 carbon atoms, each of which may be substituted. A ruthioalkyl group, an amino group having 2 to 8 carbon atoms, or an alkylene group having 1 to 10 carbon atoms that R ^1a and R ³ or / and R ⁷ may be bonded to each other, This is a case where-(CH = CH) _n -or a combination thereof is formed. In the above, n is an integer of 0 to 3, but 1 or 2 is preferable.

Preferably, R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 12 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, and a benzoyl group having 7 to 15 carbon atoms. , A heteroarylloyl group having 1 to 15 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms, a dialkylaminocarbonyl group having 3 to 12 carbon atoms, or phenyl having 7 to 15 carbon atoms An aminocarbonyl group is shown.

Preferably, R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 alkenyl groups, C2-C12 alkenoyl groups, C5-C8 cycloalkyl groups, C6-C12 phenyl groups, C3-C20 heteroaryl groups, C7-C12 Benzoyl group, C2-C12 alkanoyl group, C3-C20 heteroaryloyl group, C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, C3-C20 A heteroaryloxyxycarbonylalkanoyl group, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, carbon A heteroaryloxyoxycarbonylalkyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, or —OR ⁸ or —NR ¹⁰ R ¹¹ , and R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁵ may be bonded to each other and may form a ring structure with R ^1a .

Preferably, R ¹⁶ is an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, and a cycloalkyl group having 5 to 8 carbon atoms. A phenyl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a benzyl group having 7 to 12 carbon atoms, a benzoyl group having 7 to 12 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, and a carbon number Heteroarylloyl group having 3 to 20 carbon atoms, alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, heteroaryloxyoxycarbonylalkyl group having 3 to 20 carbon atoms, 2 to 12 carbon atoms An alkoxycarbonyl group or phenoxycarbonyl group, a trialkylsilyl group having 3 to 15 carbon atoms, or a hydroxylalkyl group having 2 to 4 carbon atoms. It is. Here, R < ³ >, R < ⁶ >, R < ⁷ >, R < ¹² > -R < ¹⁶ > may combine with each other and form a ring structure with R ^<1a> .

R ⁸ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, or an alkenoyl having 3 to 20 carbon atoms. group, a phenyl group having 6 to 12 carbon _{atoms, - (CH 2 CH 2 O} ) m H (m is an integer of 1 to 20, preferably 1 to 5) or shows a trialkylsilyl group having from 3 to 15 carbon atoms, R ⁹ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, or a phenyl group having 6 to 12 carbon atoms. R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a hydroxyl alkyl group having 2 to 4 carbon atoms, or an alkenyl group having 3 to 5 carbon atoms. Or 6-20 carbon atoms Represents a phenyl group.

（式中、符号の意味は前記の一般式（６）で定義したものと同一である。）

(In the formula, the meanings of the symbols are the same as those defined in the general formula (6)).

Preferably, R ^1b is an optionally substituted phenyl group having 6 to 15 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl group having 2 to 15 carbon atoms. A benzoyl group having 7 to 15 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms or a phenoxycarbonyl group having 7 to 12 carbon atoms, an amide group having 1 to 15 carbon atoms, a nitro group, and an alkenyl group having 2 to 15 carbon atoms , A C1-C10 heteroarylalkyl group, a C3-C20 alkoxycarbonylalkyl group, a C1-C15 heteroarylthioalkyl group, a C2-C12 dialkylamino group, a C1-C15 A dialkylaminoalkyl group of the above, an N-acyloxy-N-acylaminoalkyl group having 3 to 15 carbon atoms, or R ^1a and R ³ or / and R ⁷ are This is a case where they are bonded to each other to form an alkylene group having 1 to 15 carbon atoms which may have a substituent, — (CH═CH) _n — or a combination thereof.

More preferably, each optionally substituted phenyl group having 6 to 15 carbon atoms, alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, alkanoyl group having 2 to 12 carbon atoms, carbon number 7-12 benzoyl group, C2-C12 alkoxycarbonyl group or C7-C12 phenoxycarbonyl group, C1-C10 amide group, nitro group, C2-C12 alkenyl group, carbon number An alkoxycarbonylalkyl group having 3 to 12 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroarylthioalkyl group having 1 to 10 carbon atoms, an amino group having 2 to 8 carbon atoms, R ^1a and R ³ or / And R ⁷ may be bonded to each other and may have a substituent, each having 1 to 10 carbon atoms, — (CH═CH) _n — or a combination thereof This is a case of forming a gutter. In the above, n is an integer of 0 to 3, but 1 or 2 is preferable.

Preferably, R ^2a is an optionally substituted heteroaryl group having 1 to 15 carbon atoms, a heteroarylalkanoyl group having 1 to 15 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 15 carbon atoms, or 8 to 8 carbon atoms. A phenoxycarbonylalkanoyl group having 15 carbon atoms, a heteroaryloxyoxycarbonylalkanoyl group having 3 to 15 carbon atoms, and an aminocarbonyl group having 2 to 10 carbon atoms. Preferred R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁵ are the same as the preferred ranges of R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁵ in the general formula (6).

（式中、Ｒ^1aは、それぞれ前記の一般式（４）におけると同義であり、Ｒ^2bは、前記の一般式（３）におけるＲ^2a及び一般式（４）におけるＲ^2bを示し、Ｒ³、Ｒ⁶、Ｒ⁷、Ｒ¹²〜Ｒ¹⁶は、水素原子、ハロゲン原子、それぞれ置換されていてもよい炭素数１〜１２のアルキル基、炭素数２〜１２のアルケノイル基、炭素数６〜２０のフェニル基、炭素数７〜２０のベンジル基もしくはベンゾイル基、又は−ＮＲ¹⁰Ｒ¹¹であり、Ｒ³、Ｒ⁶、Ｒ⁷、Ｒ¹²〜Ｒ¹⁶は互いに結合して環構造を形成してもよく、且つＲ³、Ｒ⁶、Ｒ⁷、Ｒ¹²〜Ｒ¹⁶のうち少なくとも一つがそれぞれ置換されていてもよい炭素数１〜２０のヘテロアリールアルキル基、ヘテロアリールアルカノイル基もしくはヘテロアリーロイル基及び炭素数３〜１５のトリアルキルシリル基からなる群より選ばれる少なくとも１種を含む。）

(Wherein, R ^1a has the same meaning as in the general formula respectively (4), R ^2b represents an R ^2b in R ^2a and formula (4) in the above general formula (3), R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ are each a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, or 6 to 20 carbon atoms. A phenyl group, a C 7-20 benzyl group or benzoyl group, or —NR ¹⁰ R ¹¹ , wherein R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ are bonded to each other to form a ring structure. And a heteroarylalkyl group having 1 to 20 carbon atoms, a heteroarylalkanoyl group or a heteroaryloyl group in which at least one of R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁶ may be substituted. And a trialkyl group having 3 to 15 carbon atoms. Including at least one selected from the group consisting of ryl groups.)

In the chemical formulas representing the oxime ester compound of the present invention, R ^1a , R ^1a , R ^2a , R ^2b , R ^{2 to} R ¹⁶ may each independently represent a fluorine atom, Halogen atoms such as chlorine atom, bromine atom and iodine atom; hydroxyl group; nitro group; cyano group; any organic group and the like. Examples of the arbitrary organic group include methyl group, ethyl group and n-propyl group. , Isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, t-amyl group, n-hexyl group, n-heptyl group, n-octyl group, t-octyl group, etc. 18 linear or branched alkyl groups; C 3-18 cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group; vinyl group, propeni A linear or branched alkenyl group having 2 to 18 carbon atoms, such as a ruthenium group or a hexenyl group; a cycloalkenyl group having 3 to 18 carbon atoms, such as a cyclopentenyl group or a cyclohexenyl group; a methoxy group, an ethoxy group, or an n-propoxy group , Isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, amyloxy group, t-amyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, t-octyloxy A linear or branched alkoxy group having 1 to 18 carbon atoms such as a group; methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, s-butylthio group, t-butylthio group, amylthio group, 1 carbon atom such as t-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, t-octylthio group 18 linear or branched alkylthio groups; aryl groups having 6 to 18 carbon atoms such as phenyl, tolyl, xylyl and mesityl groups; aralkyl groups having 7 to 18 carbon atoms such as benzyl and phenethyl groups; vinyloxy groups A linear or branched alkenyloxy group having 2 to 18 carbon atoms such as a propenyloxy group or a hexenyloxy group; a linear or branched alkenylthio group having 2 to 18 carbon atoms such as a vinylthio group, a propenylthio group or a hexenylthio group acylamino group represented by -NHCOR ^21;; amino group represented by -NR ¹⁹ R ^20; acyloxy group represented by -OCOR ^18; carboxyl group; an acyl group represented by -COR ^17; group -NHCOOR ²² A carbamate group represented by —CONR ²³ R ²⁴ ; a carboxylic acid ester group represented by —COOR ²⁵ ; Sulfomoyl group represented by SO ₃ NR ²⁶ R ²⁷ ; Sulfonate group represented by —SO ₃ R ²⁸ ; 2-thienyl group, 2-pyridyl group, furyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl Groups, morpholino groups, pyrrolidinyl groups, saturated or unsaturated heterocyclic groups such as tetrahydrothiophene dioxide groups, and trialkylsilyl groups such as trimethylsilyl groups.

In addition, examples of the substituent of the present invention include a substituent such as ═N—OC (═O) R ² . As such compounds, R ^1a and R ^1b are substituted with ═N—OC (═O) R ² , an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and 2 carbon atoms. It may be a -20 alkanoyl group, a benzoyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, or an amide group having 1 to 20 carbon atoms.

  In the above, a plurality of substituents may be bonded to each other to form a ring, and the formed ring may be a saturated or unsaturated aromatic ring or heterocyclic ring, and each ring further has a substituent. And the substituent may further form a ring.

R ^{17 to} R ²⁸ each represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. These positional relationships are not particularly limited, and when they have a plurality of substituents, they may be the same or different.

  As mentioned above, although the compound shown by General formula (5)-(7) was explained in full detail, it is as follows when a preferable compound is put together in the combination of each substituent.

In General Formula (5), R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, or carbon. R ^1a may form a ring together with R ³ or R ⁷ , in which case R ^1a and R ³ or / and R ⁷ are bonded to each other to form 2 A trivalent or trivalent linking group, each of which may have a substituent, an alkylene group having 1 to 10 carbon atoms, — (CH═CH) _n —, — (C≡C) _n — Or a combination thereof (n is an integer of 0 to 3), R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ is a hydrogen atom, a halogen atom, An optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, a benzyl group or a benzoyl group having 7 to 20 carbon atoms, or —NR ¹⁰ R ¹¹ , a compound in which R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁶ may be bonded to each other to form a ring structure.

In General Formula (6), R ^1b is an optionally substituted alkyl group having 1 to 20 carbon atoms, and R ^2b is an optionally substituted heteroarylalkanoyl group having 1 to 20 carbon atoms, An alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms or an aminocarbonyl group having 2 to 10 carbon atoms, and R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ A hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, a benzyl group having 7 to 20 carbon atoms, or benzoyl Or a compound represented by —NR ¹⁰ R ¹¹ , wherein R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ may be bonded to each other to form a ring structure.

In General Formula (7), R ^1b is an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, or 8 to 8 carbon atoms. 20 phenoxycarbonylalkyl groups or aminoalkyl groups having 1 to 20 carbon atoms, or R ^1a may form a ring together with R ³ or R ⁷ , in which case R ^1a and R ³ or / and R ⁷ are bonded to each other to form a divalent or trivalent linking group, and each of the linking groups may have a substituent, an alkylene group having 1 to 10 carbon atoms, — (CH═CH) _n —, -(C≡C) _n- , or a combination thereof (n is an integer of 0 to 3), and R ² is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, or 1 to 20 carbon atoms. Heteroarylalkanoyl group , An alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, or an aminocarbonyl group having 2 to 10 carbon atoms, and R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ are , A hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, a benzyl group having 7 to 20 carbon atoms, or A benzoyl group, or —NR ¹⁰ R ¹¹ , R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ may be bonded to each other to form a ring structure, and R ³ , R ⁶ , R ⁷ , at least one of the respective optionally substituted good having 1 to 20 carbon atoms heteroarylalkyl group, the heteroaryl alkanoyl group or heteroarylene acryloyl group and having 3 to 15 carbon atoms bets of R ¹² to R ¹⁶ A compound containing at least one selected from the group consisting of a realkylsilyl group.

  In addition, a preferable oxime ester compound is a compound represented by the following general formula (8) or (9).

（式中、符号の意味は前記一般式（８）で定義したものと同一である。）

(In the formula, the meaning of the symbols is the same as defined in the general formula (8).)

In the general formula (8), R ^1a is preferably an optionally substituted alkenyl group having 2 to 25 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, or a phenoxycarbonylalkyl having 8 to 20 carbon atoms. Group or a C1-C20 aminoalkyl group is shown. R ^1a may form a ring together with Ar ₁ , in which case R ^1a and Ar ₁ are bonded together to form a divalent or trivalent linking group, and each linking group is substituted. An alkylene group having 1 to 10 carbon atoms which may have a group, — (CH═CH) _n —, — (C≡C) _n — or a combination thereof (n is an integer of 0 to 3), R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms.

（式中、符号の意味は前記一般式（９）で定義したものと同一である。）

(In the formula, the meanings of the symbols are the same as those defined in the general formula (9).)

In the general formula (9), preferably, R ^1b is an optionally substituted alkyl group having 1 to 20 carbon atoms, and R ^2b is an optionally substituted heteroaryl having 1 to 20 carbon atoms. Group, a C1-C20 heteroarylalkanoyl group, a C3-C20 alkoxycarbonylalkanoyl group, a C8-C20 phenoxycarbonylalkanoyl group, or a C2-C10 aminocarbonyl group.

Ar ₁ is a part necessary for the compound of the present invention to absorb light, and is preferably used as long as it is a compound having absorption at 200 nm or more, preferably 200 to 500 nm, more preferably 250 to 500 nm. It is done. Specifically, Ar ₁ is an aromatic ring composed of a benzene ring, a phenanthrene ring, an azulene ring, a fluorene ring, an acenaphthylene ring, an indene ring and a condensed ring thereof, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, A thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazane ring, a triazole ring, a pyran ring, a thiadizole ring, an oxadiazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a condensed ring thereof, Further examples include condensed rings composed of aromatic and heterocyclic rings such as acridine ring, phenanthridine ring, xanthene ring, carbazole ring, phenazine ring, phenothiazine ring, phenoxazine ring, and benzothiazole ring.

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

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

  Moreover, although the said oxime ester type compound can be used independently as a photoinitiator of this invention, it can also use together with another photoinitiator and can anticipate the high sensitivity by combined use. For example, the following compounds can be mentioned.

  2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine, -Trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5-[[beta]-(2'-benzofuryl) vinyl] -1,3,4-oxadi Azole, 2-trichloromethyl-5- [β- (2 '-(6 "benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl Halomethylated oxadiazole derivatives such as ru-1,3,4-oxadiazole, 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4, 5-bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenyl Imidazole dimers, imidazole derivatives such as (4'-methoxyphenyl) -4,5-diphenylimidazole dimer, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2 -Methylanthraquinone, 2-ethylanthraquinone, 2-t-butyl Anthraquinone derivatives such as luanthraquinone and 1-chloroanthraquinone, benzanthrone derivatives, benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, etc. Benzophenone derivatives, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (P-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1 Acetophenone derivatives such as propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2, Thioxanthone derivatives such as 4-diethylthioxanthone and 2,4-diisopropylthioxanthone, benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate, 9-phenylacridine, 9- (p-methoxyphenyl) Acridine derivatives such as acridine, phenazine derivatives such as 9,10-dimethylbenzphenazine, bis-cyclopentadienyl-Ti-dichloride, bis-cyclopentadienyl-Ti-bis-phenyl, bis-cycl Pentadienyl-Ti-bis- (2,3,4,5,6-pentafluorophen-1-yl), bis-cyclopentadienyl-Ti-bis- (2,3,5,6-tetrafluoropheny- 1-yl), bis-cyclopentadienyl-Ti-bis- (2,4,6-trifluorophen-1-yl), bis-cyclopentadienyl-Ti-2,6-difluorophenyl- 1-yl, bis-cyclopentadienyl-Ti-2,4-di-fluorophen-1-yl, bis-methylcyclopentadienyl-Ti-bis- (2,3,4,5,6-penta Fluorophen-1-yl), bis-methylcyclopentadienyl-Ti-bis- (2,6-di-fluorophen-1-yl), bis-cyclopentadienyl-Ti-2,6-di- Fluoro-3- (pill- - yl) - titanocene derivatives of 1-yl and the like, and the like.

  In addition to the initiator component, a sensitizing dye can be further added to the photopolymerizable composition of the present invention. In order to cause a photopolymerization reaction under high light shielding, it is preferable to add a sensitizing dye. Examples of such a sensitizing dye include a coumarin compound having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and a 3-ketocoumarin compound described in JP-A 63-221110. Xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, pyromethene dyes described in JP-A-6-19240, JP-A-47-2528, JP-A-54-155292. (P-dialkylaminobenzylidene) ketone and styryl dye described in JP-A-56-166154 and JP-A-59-56403, and a julolidyl group described in JP-A-6-295061. Examples thereof include sensitizing dyes and diaminobenzene compounds described in JP-A No. 11-326624.

  Of these sensitizing dyes, amino group-containing sensitizing dyes and xanthene dyes are particularly preferable.

(D) Photopolymerizable monomer As the photopolymerizable monomer of the present invention, a compound having one or more ethylenically unsaturated groups (hereinafter referred to as an ethylenic compound) is used. Specifically, an ester of an aliphatic (poly) hydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic (poly) hydroxy compound and an unsaturated carboxylic acid, an unsaturated carboxylic acid, a polyvalent carboxylic acid, and an aliphatic poly Esters obtained by hydroxy compounds, ethylene oxide of aromatic polyhydroxy compounds, esterification reaction products of propylene oxide adducts and unsaturated carboxylic acids, ethylene oxides of aliphatic polyhydroxy compounds, propylene oxide adducts and unsaturated carboxylic acids Esterification reaction product, ester of caprolactone-modified polyhydric alcohol and unsaturated carboxylic acid, reaction product of polyhydric alcohol, polyisocyanate and unsaturated carboxylic acid, styryl-terminated compound, phosphoric acid unsaturated compound, polyepoxy And an adduct of carboxylic acid with unsaturated carboxylic acid.

  Among these, specific examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, trimethylol propane tri Acrylate esters such as acrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. Methacrylic acid with the acrylate of the exemplified compound replaced with methacrylate Ether, similarly itaconic acid ester instead itaconate, maleic acid esters, and the like was replaced with crotonic acid ester or maleate was replaced crotonate.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but typical examples include (meth) acrylic acid, phthalic acid and ethylene. Condensate of glycol, condensate of (meth) acrylic acid, maleic acid and diethylene glycol, condensate of (meth) acrylic acid, terephthalic acid and pentaerythritol, condensate of (meth) acrylic acid, adipic acid, butanediol and glycerin Etc.

  Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate.

  Among the ethylenic compounds listed above, preferred are those having a (meth) acryloyl group, more preferably an acryloyl group. Such compounds include trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. Is mentioned.

  The blending amount of the photopolymerizable composition of the present invention described above is usually 0.1 to 50 parts by weight, preferably 1 to 45 parts of (c) photopolymerization initiator with respect to 100 parts by weight of (b) organic binder. Part by weight, (d) the photopolymerizable monomer is usually 0 to 200 parts by weight, preferably 3 to 180 parts by weight. Moreover, (a) black color material is 30 to 70 weight% normally in the total solid content except a solvent, Preferably it is 35 to 65 weight%. Further, the sensitizing dye is usually 0 to 30 parts by weight, preferably 0 to 10 parts by weight with respect to 100 parts by weight of the (b) organic binder.

  If the photopolymerization initiator is less than the above range, the sensitivity becomes low and the working efficiency is poor, and if it exceeds the above range, the coating film forming function is liable to be adversely affected. If the photopolymerizable monomer (ethylenic compound) is less than the above, problems such as durability and heat resistance due to a decrease in crosslink density are likely to occur, and if the above range is exceeded, developability may be degraded. There is. If the black color material is less than the above range, the light shielding property is lowered, and it becomes difficult to form a resin BM having a sufficient optical density. On the other hand, if the above range is exceeded, the sensitivity, resolution, developability and the like are drastically lowered, making it difficult to form an image.

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

  As the solvent, it is preferable to select a solvent that can dissolve or disperse each component constituting the composition and has a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120-170 ° C.

Examples of such a solvent include 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. Glycol mono, such as ether, diethylene glycol monoethyl ether, methoxymethyl pentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether Alkyl ethers;
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, 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 ether acetate, 3- Glycol alkyl ether acetates such as methyl-3-methoxybutyl acetate;
Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as 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, methyl nonyl ketone;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, 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 Rate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxy Linear or cyclic esters such as propyl propionate, butyl 3-methoxypropionate, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Examples thereof include nitriles such as acetonitrile and benzonitrile.

  Solvents corresponding to the above include mineral spirit, Valsol # 2, Apco # 18 Solvent, Apco Thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, diglyme and other commercial products.

  These solvents can be used alone or in combination. The photopolymerizable composition of the present invention is desirably prepared using these solvents so that the solid content concentration is in the range of 5 to 50% by weight, preferably 10 to 30% by weight.

  In the present invention, an optional component (d) is added to these essential components (a), (b) and (c) as necessary, but in addition to these, a pigment dispersant, an adhesion improver, a coatability improver, a development An improver or the like can be suitably added. In particular, in the composition of the present invention, since it is important for quality stability to finely disperse the black color material and stabilize the dispersion state, it is desirable to incorporate a pigment dispersant.

  The pigment dispersant has affinity for both (a) the black color material and (b) the organic binder, and examples thereof include surfactants such as nonions, cations and anions, and polymer dispersants. Among these, a polymer dispersant is preferable, and in particular, a polymer dispersant having a basic functional group (e) such as a primary, secondary, or tertiary amino group, a nitrogen-containing heterocycle such as pyridine, pyrimidine, and pyrazine. Advantageously used.

  (E) If the chemical structure preferable as a polymer dispersant having a basic functional group is specifically exemplified, for example, a polyisocyanate compound, a compound having one or two hydroxyl groups in the molecule, and an activity in the same molecule Examples thereof include a dispersion resin obtained by reacting hydrogen with a compound having a tertiary amino group.

  Examples of the polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as tilxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate Examples thereof include triisocyanates such as isocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate, which may be used alone or in combination.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

  Examples of compounds having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms. And mixtures of two or more of these.

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and the like. The mixture of 2 or more types of these is mentioned.

  Polyether ester diols include those obtained by reacting a mixture of an ether group-containing diol or other glycol with a dicarboxylic acid or an anhydride thereof, or reacting a polyester glycol with an alkylene oxide, such as poly ( And polyoxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (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-pentanediol, 1,6-hexanediol, 2-methyl-2,4 -Pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, Obtained by polycondensation with N-alkyldialkanolamine such as N-methyldiethanolamine), such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, or the diols or carbon Number 1-25 Polylactone diol or polylactone monool obtained by using a monovalent alcohol as an initiator, for example, polycaprolactone glycol, poly methyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone starting with an alcohol having 1 to 25 carbon atoms.

  Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned. 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, and more preferably 1,000 to 4,000.

  A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described. Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. A hydrogen atom of an amino group is preferred. The tertiary amino group is not particularly limited. Moreover, as a tertiary amino group, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring or a triazole ring is mentioned.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include 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, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, the tertiary amino group is an N-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include N-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring, N-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, and isoquinoline ring. Preferred as these N-containing heterocycles are an imidazole ring or a triazole ring.

  Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Further, specific examples of the compound having a triazole ring and an amino group include 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, 3-amino-1-benzyl-1H-2,4-triazole and the like.

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

  (E) The weight average molecular weight in terms of GPC of the polymer dispersant having a basic functional group is 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. It is. When the molecular weight is 1,000 or less, the dispersibility and dispersion stability are poor, and when it is 200,000 or more, the solubility is lowered and the dispersibility is poor, and at the same time, the reaction is difficult to control. The polymer dispersant is produced according to a known method for producing a polyurethane resin.

  As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.

  In the above production, a urethanization reaction catalyst is usually used. For example, tin such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stanas octoate, iron such as iron acetylacetonate and ferric chloride, tertiary amine such as triethylamine and triethylenediamine, etc. Can be mentioned.

  The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is less than the above range, the dispersing ability tends to decrease, and when it exceeds the above range, the developability tends to decrease. In addition, when an isocyanate group remains in a polymer dispersing agent by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time increases. In addition, when using a polymer dispersing agent, 0.1 to 30 weight% is preferable with respect to (a) black color material, and 0.5 to 25 weight% is especially preferable.

  Next, the manufacturing method of the photopolymerizable composition of this invention is demonstrated. In the present invention, it is preferable to disperse the normal color material in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the color material is finely divided by the dispersion treatment, the coating characteristics of the resist are improved. Moreover, when a black color material is used as a color material, it contributes to the improvement of light-shielding capability.

  In the dispersion treatment, the treatment is preferably carried out in a system in which a black color material and a solvent or an organic binder having a dispersion function or the above-described pigment dispersant are further used in combination. In particular, it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time. Dispersion treatment with a solution in which all components to be blended as a resist solution are mixed at the same time is not preferable because a highly reactive component may be denatured 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. The conditions for the dispersion are usually that the temperature is from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the ink (coloring material, solvent, dispersant) and the size of the sand grinder. The standard of dispersion is to control the gloss of the ink so that the 20-degree 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 rough pigment particles often remain, which is insufficient in terms 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 ultrafine particles are generated, and the dispersion stability tends to be impaired.

  Next, the ink obtained by the above dispersion treatment and the above-mentioned other components necessary as a resist component are added and mixed to obtain a uniform solution. In the manufacturing process, fine dust is often mixed with the photosensitive solution. Therefore, the obtained resist photosensitive solution is preferably filtered through a filter or the like. Then, the manufacturing method of the color filter using the photopolymerizable composition of this invention is demonstrated.

  Hereinafter, application examples of the photopolymerizable composition of the present invention will be described.

[1] 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 then dried. A photomask is placed on the surface, and a light-shielding BM image is formed through image exposure, development, and heat curing or photocuring as necessary through the photomask, and this operation is repeated for each of the three RGB colors. To form.

[1-1] Application and Drying of Photopolymerizable Composition In addition, when forming a pixel of a color filter using the photopolymerizable composition of the present invention, it has very high sensitivity and high resolution. An image can be formed by exposure and development without providing an oxygen barrier layer such as alcohol. The transparent substrate used here is a transparent substrate for a color filter, and its material is not particularly limited. For example, polyester such as polyethylene terephthalate, polypropylene, polyolefin such as polyethylene, polycarbonate, polymethyl methacrylate, A thermoplastic plastic sheet such as polysulfone, an epoxy resin, a polyester resin, a thermosetting plastic sheet such as poly (meth) acrylic resin, or various glass plates can be used. In particular, a glass plate and a heat resistant plastic are preferably used from the viewpoint of heat resistance.

  In order to improve physical properties such as surface adhesion, such a transparent substrate can be previously subjected to corona discharge treatment, ozone treatment, thin film treatment of various polymers such as silane coupling agents and urethane polymers, and the like. . The coating method is not particularly limited, but the thickness of the resin black matrix after coating and drying is 0.1 to 2 μm, preferably 0.1 to 1.5 μm, more preferably 0.1 to 1 μm. Good. The color filter of the present invention preferably has an optical density of 3.0 or more at a film thickness of 1 μm from the viewpoint of light shielding properties. Further, it is advantageous that the 20 degree gloss value of BM is 100 to 200 as an indicator of the dispersion state of solid components such as pigments.

[1-2] Exposure and development In drying, a hot plate, an IR oven, a convection oven, or the like can be used. Preferred drying conditions are 40 to 150 ° C., and the drying time is in the range of 10 seconds to 60 minutes. The light source used for exposure is, for example, 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, or the like, an argon ion laser, a YAG laser, an excimer laser, Examples include a laser light source such as a nitrogen laser. An optical filter can also be used when only the wavelength of specific irradiation light is used.

  The development treatment is not particularly limited as long as it is a solvent capable of dissolving the resist film in the unexposed area. For example, an organic solvent such as acetone, methylene chloride, trichlene, and cyclohexanone can be used. However, since many organic solvents have environmental pollution, harmfulness to human body, fire risk, etc., it is preferable to use an alkaline developer without such danger. Examples of such an alkali developer include inorganic alkali agents such as sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, or diethanolamine, triethanolamine, tetraalkylammonium hydroxide salt, etc. And an aqueous solution containing an organic alkali agent. If necessary, the alkaline developer may contain a surfactant, a water-soluble organic solvent, a low molecular compound having a hydroxyl group or a carboxyl group, and the like. In particular, it is preferable to add a surfactant since many surfactants have an improving effect on developability, resolution, and background stains.

  For example, as a surfactant for a developer, an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, a cation having a tetraalkylammonium group Can be mentioned. Although there is no restriction | limiting in particular about the image development processing method, Usually, it is carried out by methods, such as immersion image development, spray image development, brush image development, ultrasonic wave development, at 10-50 degreeC, Preferably it is 15-45 degreeC.

[2] Liquid crystal display device (panel)
The liquid crystal display device 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 disposed on the alignment film, and then a liquid crystal cell is formed by being bonded to a counter substrate. Next, liquid crystal is injected into the formed liquid crystal cell and connected to the counter electrode to complete.

  The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method or a flexographic printing method is usually employed, and the thickness of the alignment film is usually 10 to 100 nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state capable of adjusting the tilt of the liquid crystal.

  A spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film is formed on the color filter substrate by photolithography, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

  The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After bonding to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then the pressure is reduced in the vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. To do. The degree of vacuum 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 warming holding at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. In the liquid crystal cell into which the liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.

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

[3] Photospacer [3-1] Supplying Method to Substrate The resin composition of the present invention is usually supplied onto the substrate in a state dissolved or dispersed in a solvent. As the supply method, a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering to the spin coating method, and the generation of foreign matter is suppressed. To preferred. The coating amount is usually in the range of 0.5 to 10 μm, preferably 1 to 8 μm, particularly preferably 1 to 5 μm as a dry film thickness. It is also important that the dry film thickness or the height of the finally formed spacer is uniform across the entire substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel. Further, it may be supplied in a pattern by an inkjet method or a printing method.

[3-2] Drying method The drying after supplying the resin composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature. Drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer used, and the like. The drying time is usually selected within a range of 15 seconds to 5 minutes at a temperature of 40 to 100 ° C., preferably 50 to 90 ° C., depending on the type of solvent component, the performance of the dryer used, and the like. It is selected in the range of 30 seconds to 3 minutes.

[3-3] Exposure Method Exposure is performed by superimposing a negative mask pattern on the coating film of the resin composition and irradiating an ultraviolet or visible light source through the mask pattern. Further, a scanning exposure method using a laser beam may be used. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said exposure is not specifically limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, Examples include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

[3-4] Development Method After performing the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution containing an alkaline compound and a surfactant or an organic solvent. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), co The organic alkaline compound such emissions and the like. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.

[3-5] Thermosetting treatment The substrate after development is preferably subjected to thermosetting treatment. The thermosetting treatment conditions in this case are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes.

[4] Ribs (Liquid crystal alignment protrusions)
Ribs (liquid crystal split alignment protrusions) are protrusions formed on a transparent electrode in order to improve the viewing angle of a liquid crystal display device, and the liquid crystal is locally tilted using the slope of the protrusions within one pixel. The liquid crystal is divided into multiple directions. Hereinafter, a method for forming the rib will be described in detail.

[4-1] Application and development process A black matrix and red, blue, and green color filters are provided, and a 150-nm thick ITO is vapor-deposited thereon. The photosensitive composition is applied using an application device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, or a spray. The coating film thickness of the composition is usually 0.5 to 5 μm. After the coating film made of the composition is dried, a photomask is placed on the dried coating film, and image exposure is performed through the photomask. After exposure, an unexposed uncured portion is removed by development to form a pixel. Usually, an image obtained after development is required to have a fine line reproducibility with a width of 5 to 20 μm, and there is a tendency that a finer fine line reproducibility is required due to a demand for a high-quality display. In order to stably reproduce high-definition fine lines, the cross-sectional shape of the fine line image after development is a rectangular shape with a clear contrast between the non-image and the image area, such as development time, developer aging, physical stimulation of the development shower, etc. A wide development margin is preferable.

[4-2] Heating Process In the present invention, the developed image has a cross-sectional shape close to a rectangular shape. In order to obtain an arched shape necessary for the rib shape, it is usually 150 ° C. or higher, preferably 180 ° C. or higher, more preferably 200 ° C. or higher, usually 400 ° C. or lower, preferably 300 ° C. or lower, more preferably 280 ° C. In the following, a heat treatment is performed for 10 minutes or more, preferably 15 minutes or more, more preferably 20 minutes or more, usually 120 minutes or less, preferably 60 minutes or less, more preferably 40 minutes or less, and a rectangular cross section. The shape is deformed into an arch shape to form ribs having a width of 0.5 to 20 μm and a height of 0.2 to 5 μm. As the range of deformation during heating, the photosensitive composition and heating conditions are appropriately adjusted, and the contact angle (W1) formed from the side surface of the thin line image (rectangular image cross-sectional shape) before heating and the substrate plane is the above heat treatment. When the contact angle (W2) formed from the side surface of the subsequent thin line image and the substrate plane is compared, W1 / W2 is 1.2 or more, preferably 1.3 or more, more preferably 1.5 or more, usually 10 or less. , Preferably 8 or less. The higher the heating temperature or the longer the heating time, the higher the deformation rate. Conversely, the lower the heating temperature or the shorter the heating time, the lower the deformation rate.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated still in detail, this invention is not limited to a following example, unless the summary is exceeded.

Synthesis Example 1 (Preparation of polymer dispersant solution)
32 g of tolylene diisocyanate trimer (Mitsubishi Chemical Co., Ltd., Mytec GP750A, resin solid content 50 wt%, butyl acetate solution) and 0.02 g of dibutyltin dilaurate as a catalyst were diluted with 47 g of propylene glycol monomethyl ether acetate (PGMEA) Dissolved. While stirring, 14.4 g of polyethylene glycol (manufactured by NOF Corporation, UNIOX M-1000) having a methoxy group at one end and polypropylene glycol having a number average molecular weight of 1,000. After adding 9.6 g of a mixture with Sanyo Chemical Industries, Ltd. (SANNICS PP-1000), the mixture was further reacted at 70 ° C. for 3 hours. Next, 1 g of N, N-dimethylamino-1,3-propanediamine was added, and the mixture was further reacted at 40 ° C. for 1 hour. The amine value of the solution containing the polymer dispersant thus obtained was determined by neutralization titration to be 14 mg KOH / g. The resin content was 40% by weight as determined by the dry-up method (at 150 ° C. for 30 minutes, the solvent was removed on a hot plate and the resin concentration was calculated from the amount of change in weight).

Synthesis Example 2 (Synthesis of organic binder)
200 g / eq of epoxy equivalent, 200 g of o-cresol novolak epoxy resin having a softening point of 65 ° C., 72 g of acrylic acid, 0.2 g of p-methoxyphenol, 0.2 g of dodecyltrimethylammonium chloride, and 272 g of PGMEA were charged in a flask at a temperature of 100 ° C. The reaction was continued for 1 hour (1 equivalent of acrylic acid reacted with 1 equivalent of epoxy group). Further, 42 g of tetrahydrophthalic anhydride was added and reacted at 80 ° C. for 3 hours. This reaction solution was re-precipitated in water and vacuum-dried to obtain a novolak epoxy acrylate resin having a carboxyl group. When neutralization titration with KOH was performed, the acid value of the resin was 50 mgKOH / g.

(Dispersion of carbon black)
Carbon black for color (Mitsubishi Chemical Co., Ltd., MA-220) 50 parts by weight, the polymer dispersant shown in Synthesis Example-1 as a solid content at a ratio of 5 parts by weight, and the solid content concentration becomes 50% by weight Carbon black, polymer dispersant solution and PGMEA were added as described above. The total weight of the dispersion was 50 g. This was thoroughly stirred with a stirrer and premixed.

  Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As beads, 0.5 mmφ zirconia beads were used, and the same weight as the dispersion was added. After the completion of dispersion, the beads and the dispersion were separated by a filter.

Synthesis Example 3 (Synthesis of oxime ester compound C-1)
[1] Production of carbazole derivative (ketone) 3.9 g (20 mmol) of ethylcarbazole was dissolved in 20 ml of dichloromethane, and 2.9 g (22 mmol) of aluminum chloride was added thereto. While cooling in an ice bath, 4.1 g (22 mmol) of o-methylbenzoyl chloride was added dropwise while keeping the reaction solution at 5 ° C or lower. The mixture was stirred while gradually raising to room temperature over 1 hour, and then reacted at room temperature for another 3 hours. Further, the reaction solution was cooled in an ice bath, and after adding 2.9 g (22 mmol) of aluminum chloride, 2.3 g (22 mmol) of methacrylic acid chloride was kept at 5 ° C. or lower while cooling in the ice bath. While dripping. The mixture was stirred while gradually raising to room temperature over 1 hour, and then reacted at room temperature for another 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 further extracted with 50 ml of ethyl acetate, and the organic layers were combined and extracted with 150 ml of 10% aqueous sodium carbonate solution. Further, the organic layer was extracted with 150 ml of water, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off with an evaporator to obtain an orange-red oil. It was generated by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/1) to obtain 3.1 g of pale yellow solid (1) and 0.7 g of pale yellow solid (2). About the obtained solid (1) and solid (2), NMR spectrum analysis was performed and the following result (shift value) was obtained.
Solid (1); 7.9-8.8, m, 3H; 7.4, m, 7H; 5.9 (1H,) 5.6, s, 1H; 5.6, s, 1H; 4.4 (2H,), 2.4, s, 3H; 2.1, 2.4, d3H, 1.5, t, 3H
Solid (2); 8.6, dd, 1H; 8.0, dd, 1H; 7.9, d, 1H; 7.4, m, 6H; 4.5, q, 2H; 3.6, d, 2H, 2.6, s, 1H; 2.4, s , 3H; 2.2, s, 3H; 1.5, t, 3H
From the 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 confirmed to be a ketone compound represented by the following formula.

[2] Production of Oxime Ester Compound 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), pyridine (0.084 g, 0.00105 mol) was added and refluxed for 2 hours. After distilling off ethanol, water was added to dissolve the inorganic substance, followed by filtration. The filtrate was dissolved in ethyl acetate, dried over magnesium sulfate, and evaporated to obtain an oxime form. The obtained solid was dissolved in 3 ml of THF, and acetyl chloride (0.23 g, 0.0022 mol) was added and stirred. Triethylamine (0.21 g, 0.0023 mol) was added dropwise to the reaction solution at room temperature. Sedimentation was observed as the salt was added. After stirring for 2 hours, 20 ml of water was added and extracted with 40 ml of ethyl acetate. The organic layer was washed twice with 20 ml of water and twice with 20 ml of a saturated aqueous potassium carbonate solution. The organic layer was dried over magnesium sulfate and then evaporated. Purification was performed by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/1) to obtain 0.3 g of a pale yellow solid (3).

The obtained solid (3) was subjected to H-NMR spectrum analysis under the following conditions to obtain the following results (shift value).
・ Solvent: Deuterated chloroform (CDCl ₃ )
・ Frequency: 270 MHz
Reference compound: (CH ₃ ) ₄ Si
8.5, dd, 1H; 8.1, dd, 1H; 7.9, dd, 1H; 7.4, m, 6H; 4.4, q, 2H; 3.6, d, 2H, 2.4, s, 3H; 2.3, s, 3H; 2.2, s, 3H; 2.0, s, 3H; 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 described later).

Synthesis Example 4 (Synthesis of oxime ester compound C-2)
In Synthesis Example-3, the same procedure as in the synthesis of C-1 except that 3-methacryloyl-9-ethyl-6- (o-toluoyl) -9H-carbazole was used instead of the pale yellow solid (2). C-2 was synthesized. NMR shift values were as follows.
8.5, d, 1H; 8.4, d, 1H; 8.1, dd, 1H; 7.9, dd, 1H; 7.4, m, 6H; 7.2, d, 1H; 5.6, s, 1H; 5.1, s, 1H; 4.4, q, 2H; 2.4, s, 3H; 2.2, s, 3H; 2.0, s, 3H; 1.5, t, 3H

Synthesis Example 5 (Synthesis of oxime ester compound C-3)
In Synthesis Example-3, C-3 was synthesized in the same manner as the synthesis of C-1, except that methacrylic acid chloride was changed to crotonic acid chloride. NMR shift values were as follows.
8.5, d, 1H; 8.4, d, 1H; 8.1, dd, 1H; 7.9, dd, 1H; 7.4, m, 6H; 4.4, q, 2H; 2.4, s, 3H; 2.2, s, 3H; 2.0, s, 3H; 1.5, t, 3H

Synthesis Example 6 (Synthesis of oxime ester compound C-4)
In Synthesis Example-3, C-4 was synthesized in the same manner as in C-1, except that methacrylic acid chloride was changed to acetyl chloride and acetyl chloride used in the final step was changed to succinic acid monoethyl chloride. NMR shift values were as follows.
8.5, d, 1H; 8.5, d, 1H; 8.1, dd, 1H; 8.0, dd, 1H; 7.9, dd, 1H; 7.5, m, 6H; 4.5, q, 2H; 4.2, m, 6H; 2.9, t, 2H; 2.8, t, 2H; 2.7, t, 2H; 2.6, s, 3H; 2.5, s, 3H; 1.5, t, 3H; 1.3, s, 3H

Synthesis Example 7 (Synthesis of oxime ester compound C-5)
In Synthesis Example-3, C-5 was synthesized in the same manner as the synthesis of C-1, except that methacrylic acid chloride was changed to acetyl chloride and acetyl chloride used in the final step was changed to morpholinylcarbonyl chloride.

Synthesis Example-8 (Synthesis of oxime ester compound C-8)
In Synthesis Example-3, C-8 was synthesized in the same manner as the synthesis of C-1, except that methacrylic acid chloride was changed to succinic acid monoethyl chloride. NMR shift values were as follows.
8.5, d, 1H; 8.4, d, 1H; 8.1, dd, 1H; 7.9, dd, 1H; 7.4, m, 6H; 4.4, q, 2H; 4.1, q, 2H; 3.3, t, 2H; 2.6, s, 3H; 2.4, s, 3H; 2.3, s, 3H; 1.5, t, 3H; 1.2, d, 3H

[Examples 1 to 9 and Comparative Examples 1 to 3]
(1) Preparation of resist solution Each component (a), (b), (c), (d), (e), organic so as to have the following mixing ratio as a solid content using the carbon black dispersion ink described above A solvent and a surfactant were added, and the mixture was stirred and dissolved with a stirrer to prepare a black resist photosensitive solution.

(A) Black color material Carbon black (manufactured by Mitsubishi Chemical Corporation, MA-220) 50 g
(B) Organic binder (described in Table 2) 30 g
(D) Photopolymerizable monomer: ethylenic compound dipentaerythritol hexaacrylate 10 g
(C) Photopolymerization initiator (described in Table 2)
300g organic solvent propylene glycol monomethyl ether acetate
(E) Polymer dispersant (Synthesis Example 1) 5 g
Surfactant (Sumitomo 3M, FC-430) 100ppm

(2) Evaluation of resist A black resist photosensitive solution was applied to a glass substrate (Corning Corp., 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 with a stylus type film thickness meter (manufactured by Tencor, α-step) and found to be 1 μm. Next, this sample was image-exposed through a mask while changing the exposure amount with a high-pressure mercury lamp. A resist pattern was obtained by spray development using a sodium carbonate aqueous solution having a temperature of 25 ° C. and a concentration of 0.8%.

The sensitivity, resolution, and light shielding properties were evaluated according to the following criteria, and the results shown in Table 2 were obtained.
1. Sensitivity A 20 μm mask pattern was displayed with an appropriate exposure amount (mj / cm ² ) that can be formed according to dimensions. That is, a resist with a small exposure amount has high sensitivity because an image can be formed with a low exposure amount.
2. Resolution The minimum resist pattern size that can be resolved at an exposure amount that faithfully reproduces a 20 μm mask pattern was observed with a microscope at a magnification of 200 times.
Minimum pattern dimension is 10μm or less: ○
Minimum pattern dimension exceeds 10 μm: ×

3. Light-shielding property The optical density (OD) of the image area was measured with a Macbeth reflection densitometer (TR927, manufactured by Kolmorgun). The OD value is a numerical value indicating the light shielding ability, and the larger the numerical value, the higher the light shielding property.
4). Scratch resistance A glass substrate having the obtained image pattern was placed on an untreated glass substrate (Corning Corp., 7059) so that the image pattern was in contact with the untreated glass surface, and the load shown below was applied. However, it was rubbed 5 times at a speed of 3 cm / sec. After twisting, the presence or absence of scratches was visually evaluated according to the following criteria with the naked eye.
Load g / cm ² Scratch evaluation
60 accepted △
60 Not recognized at all ○
100 Not recognized at all ◎

[Example 10]
In Example 9, it was the same as Example 9 except that titanium black (Mitsubishi Materials Corporation, 13M-C) was used instead of carbon black (Mitsubishi Chemical Corporation, MA-220) used as a black color material. Processing was performed to obtain a black matrix pattern. The results are shown in Table 2.

[Comparative Example 4]
Comparative Example 3 was the same as Comparative Example 3 except that titanium black (Mitsubishi Materials Corporation, 13M-C) was used instead of carbon black (Mitsubishi Chemical Corporation, MA-220) used as a black color material. Processing was performed to obtain a black matrix pattern. The results are shown in Table 2.

尚、表２中、記号の意味は次の通りである。
ＡＣＡ−２００Ｍ：アクリルポリマー（ダイセル化学工業社製、ＡＣＡ−２００Ｍ）
Ｃ−１：表１記載のＮｏ．２２の化合物

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: No. in Table 1 22 compounds

Ｃ−２：表１記載のＮｏ．３の化合物

C-2: No. described in Table 1. 3 compounds

Ｃ−３：表１記載のＮｏ．４の化合物

C-3: No. in Table 1 4 compounds

Ｃ−４：表１記載のＮｏ．１６の化合物

C-4: No. in Table 1 16 compounds

Ｃ−５：表１記載のＮｏ．１９の化合物

C-5: No. in Table 1 19 compounds

Ｃ−７：表１記載のＮｏ．２８の化合物

C-7: No. in Table 1 28 compounds

Ｃ−８：表１記載のＮｏ．２９の化合物

C-8: No. in Table 1 29 compounds

Ｃ−９：表１記載のＮｏ．３７の化合物

C-9: No. in Table 1 37 compounds

トリアジンＡ：４−（ｍ−ブロモ−ｐ−メトキシフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン（５ｇ）

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

ＣＧＩ−１２４：: 光重合開始剤（チバ・スペシャルティーケミカル社製、ＣＧＩ−１２４）（５ｇ）

CGI-124 :: Photopolymerization initiator (CGI-124, manufactured by Ciba Specialty Chemicals) (5 g)

３種混合系：２，２'−ビス（ｏ−クロロフェニル）−４，４'，５，５'−テトラフェニルビイミダゾール（２ｇ）＋４，４'−ビス（ジエチルアミノ）ベンゾフェノン（１ｇ）＋ ２−メルカプトベンゾチアゾール（１ｇ）

Three kinds of mixed systems: 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (2 g) + 4,4′-bis (diethylamino) benzophenone (1 g) + 2− Mercaptobenzothiazole (1g)

[Examples 11 to 12] and [Comparative Example 5]
Each test solution was applied onto an AN100 glass substrate sputtered with 150 nm ITO by a spin coater, and dried on a hot plate at 80 ° C. for 3 minutes to obtain a coating film having a dry film thickness of 1.7 μm. Thereafter, image exposure was performed from the coating film side through various fine exposure conditions of 25, 50, 100, and 200 mJ / cm ⁻² using 3 kW high-pressure mercury through a fine line pattern mask having a width of 15 μm. Next, a developer comprising 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) was used, and the water pressure was 0.25 megapascals at 23 ° C. After shower development, development was stopped with pure water and rinsed with a water spray. The shower development time was adjusted between 10 and 120 seconds, and was twice as long as the photosensitive layer was dissolved and removed (break time). The glass substrate thus imaged was heated at 230 ° C. for 30 minutes to form a thin line pattern deformed into an arch shape. The obtained cross-sectional shape of the thin wire before and after heating was measured with VK9500, the contact angle between the substrate plane and the side surface of the thin wire image was determined, and the change rate of the contact angle before and after heating was evaluated by the following method. The results are shown in Table 3.

As is apparent from Table 3, Examples 11 and 12 using the photosensitive composition of the present invention have a high contact angle deformation rate, good arch-like protrusions, and image formation. It was found that it is possible to form a liquid crystal split alignment protrusion.
<Evaluation of rate of change of contact angle by heating>
The cross-sectional shape of the thin line before and after heating is measured with VK9500, the contact angle is obtained, and the contact angle (W1) formed from the side surface and substrate plane of the pre-heating thin line image and the side surface and substrate plane of the thin line image after heating are formed. The contact angle (W2) to be obtained was determined, and the change in the contact angle due to heating was evaluated as follows from the value of the contact angle change rate (W1 / W2). See FIG.

A: W1 / W2 is 2 or more B: W1 / W2 is 1.5 or more and 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>
Images obtained by the above exposure and development processes were evaluated as follows.
A: An image having a film thickness of 70% or more with respect to the coating film thickness was formed.
B: An image having a film thickness of less than 70% with respect to the coating film thickness was formed.
C: The photosensitive layer was completely dissolved and no image was formed.

In Table 3, the meanings of the symbols are as follows.
M-1: Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate (DPHA)
M-2: Shin-Nakamura Science Co., Ltd. bifunctional phosphate "PM-21"
S-1: “Irgacure 907” manufactured by Ciba Specialty Chemicals
S-2: Nippon Kayaku Co., Ltd., 2,4-diethylthioxanthone P-1: Alkali-soluble resin having a weight average molecular weight of 2000 and an acid value of 100. The structural formula is shown in [Chemical Formula 47].
・ F-1: Fluorosurfactant “F475” manufactured by Dainippon Ink & Chemicals, Inc.
PGMA: manufactured by Tokyo Chemical Industry Co., Ltd., isopropylene glycol monomethyl ether acetate In Table 3, aptitude sensitivity mJ / cm ^-2 refers to the minimum exposure that can reproduce a fine line pattern of 15 μm.

  The photopolymerizable composition of the present invention and a color filter using the same can be used for color televisions, liquid crystal display elements, solid-state image sensors, cameras, and the like.

It is a figure which shows typically the state of the change of the contact angle by heating.

Explanation of symbols

W1: Contact angle formed from the side surface of the pre-heating thin line image and the substrate plane W2: Contact angle formed from the side surface of the thin line image after heating and the substrate plane

Claims (20)

An oxime ester compound represented by the general formula (1) or (2).

Wherein R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and 8 to 8 carbon atoms. A phenoxycarbonylalkyl group having 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or a heteroarylthioalkyl group, an amino group having 0 to 20 carbon atoms, or an aminoalkyl group having 1 to 20 carbon atoms, R ^1a may form a ring together with R ¹ ′, and the linking group is an alkylene group having 1 to 10 carbon atoms that may have a substituent, — (CH═CH) _n —, — ( C [identical to] C) _n - or a combination thereof (n is an integer of 0 to 3), R ^2a are each optionally substituted alkanoyl group having 2 to 12 carbon atoms, 3 carbon 5 alkenoyl group, C3-C8 cycloalkanoyl group, C7-C20 benzoyl group, C1-C20 heteroaryloyl group, C2-C10 alkoxycarbonyl group, or C7-C20 And R1 ′ represents an optional substituent containing an aromatic ring or a heteroaromatic ring.):

(In the formula, R ^1b is an optionally substituted phenyl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl having 2 to 20 carbon atoms. Group, benzoyl group having 7 to 20 carbon atoms, alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, amide group having 1 to 20 carbon atoms, nitro group, alkenyl group having 2 to 25 carbon atoms, 1 to carbon atoms 10 heteroarylalkyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, carbon number 0-20 amino group, or an amino alkyl group having 1 to 20 carbon atoms, also R ^1b is, form a ring with R1 ' At best, the linkage is respectively substituent may number 1 to 10 alkylene carbon atoms which may have _{a, - (CH = CH) n} -, - (C≡C) n - or a combination thereof ( n is an integer of 0 to 3), and R ^2b is an optionally substituted heteroaryl group having 1 to 20 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms. A phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxyoxycarbonylalkanoyl group having 3 to 20 carbon atoms, or an aminocarbonyl group having 2 to 10 carbon atoms, and R1 ′ represents an aromatic ring or a heteroaromatic ring. Any optional substituents are included.) In general formula (1) of Claim 1, R ^<1a> is respectively C2-C25 alkenyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 which may be substituted, respectively. It is a phenoxycarbonylalkyl group or an aminoalkyl group having 1 to 20 carbon atoms, or R ^1a may form a ring together with R ¹ ′, and each of the linking groups may have a substituent. An alkylene group of 1 to 10,-(CH = CH) _n -,-(C≡C) _n -or a combination thereof (n is an integer of 0 to 3), and R ^2a may be substituted. An oxime ester compound having an alkanoyl group having 2 to 12 carbon atoms. In General formula (2) of Claim 1, R ^<1b > is a C1-C20 alkyl group which may be substituted, R ^<2b > is C1-C20 which may be respectively substituted. A heteroaryl alkanoyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, or an aminocarbonyl group having 2 to 10 carbon atoms. An oxime ester compound characterized by An oxime ester compound represented by the general formula (3) or (4).

Wherein R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and 8 to 8 carbon atoms. A phenoxycarbonylalkyl group having 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or a heteroarylthioalkyl group, an amino group having 0 to 20 carbon atoms, or an aminoalkyl group having 1 to 20 carbon atoms, R ^1a may form a ring with R ³ or R ⁷ , in which case R ^1a and R ³ or / and R ⁷ are bonded together to form a divalent or trivalent linking group, linking groups each substituent alkylene group having 1 to 10 carbon atoms which may have _{a, - (CH = CH) n} -, - (C≡C) n - or a combination thereof ( Is an integer of 0 to 3), R ^2a are each optionally substituted alkanoyl group having 2 to 12 carbon atoms, alkenoyl of 3 to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, 7 carbon atoms Represents a benzoyl group having 20 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or a phenoxycarbonyl group having 7 to 20 carbon atoms, and R ³ , R ⁴ , R ⁵ , R ⁶ And R ⁷ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. , A phenyl group having 6 to 20 carbon atoms, a benzyl group having 7 to 20 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, and a carbon number 3 20 alkoxycarbonyl alkanoyl group, phenoxycarbonyl alkanoyl group having 8 to 20 carbon atoms, heteroaryl having 3 to 20 carbon atoms - Luo Kishikishi carbonyl alkanoyl group, or an alkoxycarbonyl group or a phenoxycarbonyl group having 2 to 12 carbon atoms, -OR ⁸ , -SR ⁹ , -SOR ⁹ , -SO ₂ R ⁹ or -NR ¹⁰ R ¹¹ , and at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is -OR ⁸ ,- SR ⁹ or —NR ¹⁰ R ¹¹ , wherein R ⁸ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, or 3 to 12 carbon atoms. alkenyl group, alkenoyl group having 3 to 20 carbon atoms, a phenyl group having 6 to 20 carbon _{atoms, - (CH 2 CH 2 O} ) m H (m is an integer of 1 to 20), or 3 carbon 15 represents a trialkylsilyl group, and R ⁹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, A phenyl group having 6 to 20 carbon atoms or a trialkylsilyl group having 3 to 15 carbon atoms, wherein R ¹⁰ and R ¹¹ are each independently a hydrogen atom, and an optionally substituted alkyl having 1 to 12 carbon atoms; Represents a hydroxyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or a phenyl group having 6 to 20 carbon atoms, wherein R ^{3 to} R ⁷ are bonded to each other and have a ring structure together with R ^1. You may form. ):

(In the formula, R ^1b is an optionally substituted phenyl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl having 2 to 20 carbon atoms. Group, benzoyl group having 7 to 20 carbon atoms, alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, amide group having 1 to 20 carbon atoms, nitro group, alkenyl group having 2 to 25 carbon atoms, 1 to carbon atoms 10 heteroarylalkyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, carbon number 0-20 amino group, or an amino alkyl group having 1 to 20 carbon atoms, also R ^1b are both with R ³ or R ⁷ It may form a ring, in which case, by combining R ^1b and R ³ or / and R ⁷ together together form a divalent or trivalent linking group, have their respective linking group substituent Or an alkylene group having 1 to 10 carbon atoms, — (CH═CH) _n —, — (C≡C) _n — or a combination thereof (n is an integer of 0 to 3), and each R ^2b is substituted. C1-20 heteroaryl group, C1-20 heteroarylalkanoyl group, C3-20 alkoxycarbonylalkanoyl group, C8-20 phenoxycarbonylalkanoyl group, C3 20 of heteroaryl - Luo Kishikishi carbonyl alkanoyl group, or an amino carbonyl group having 2 to 10 carbon ^{atoms, R 3, R 4, R} 5, R 6 and R ⁷ are synonymous der as in the general formula (3) .) In general formula (3) of Claim 4, R ^<1a> is respectively C2-C25 alkenyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 which may be substituted, respectively. It is a phenoxycarbonylalkyl group or an aminoalkyl group having 1 to 20 carbon atoms, or R ^1a may form a ring together with R ³ or R ⁷ , in which case R ^1b and R ³ or / and R ⁷ Are bonded to each other to form a divalent or trivalent linking group, each of which may have a substituent, an alkylene group having 1 to 10 carbon atoms, — (CH═CH) _n —, — (C≡C) _n -or a combination thereof (n is an integer of 0 to 3), R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently of each other , A hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, or —NR ¹⁰ R ¹¹ , And at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represents —NR ¹⁰ R ¹¹ (provided that R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a hydrogen atom. An alkyl group having 1 to 12 carbon atoms, a hydroxyl alkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or a phenyl group having 6 to 20 carbon atoms), R ^{3 to} R ⁷ may be An oxime ester-based compound which is bonded to each other and may form a ring structure with R ^1a . In general formula (4) of Claim 4, R ^<1b > is a C1-C20 alkyl group which may be substituted, R ^<2b > is C1-C20 which may be respectively substituted. A heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, or an aminocarbonyl group having 2 to 10 carbon atoms, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or phenyl having 6 to 20 carbon atoms. group, a heteroarylene acryloyl group or -NR ¹⁰ R ¹¹ having 1 to 20 carbon atoms, and at least one of ^{R 3, R 4, R 5} , R 6 and R ⁷ represents an -NR ¹⁰ R ¹¹ (However, R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a hydroxyl alkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or a carbon number An oxime ester compound, wherein R ^{3 to} R ⁷ may be bonded to each other and may form a ring structure with R ^1b . An oxime ester compound represented by any one of the general formulas (5) to (7).

(In the formula, R ^1a and R ^2a have the same meaning as in the general formula (3) according to claim 4, and R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁶ are a hydrogen atom, a halogen atom, Each optionally substituted alkyl group having 1 to 12 carbon atoms, alkenoyl group having 2 to 12 carbon atoms, phenyl group having 6 to 20 carbon atoms, benzyl group or benzoyl group having 7 to 20 carbon atoms, or -NR ¹⁰ R ¹¹ and R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁶ may be bonded to each other to form a ring structure.

(In the formula, R ^1b and R ^2b have the same ^{meanings as} in the general formula (4) described in claim 4, and R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁶ are the same as those in the general formula (5). Is synonymous with

(Wherein, R ^1b has the same meaning as in the general formula (4) according to claim 4, R ² is in the R ^2a and formula in the formula of claim 4 (3) (4) R ^2b represents R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁶ are a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, and an alkenoyl having 2 to 12 carbon atoms. Group, a phenyl group having 6 to 20 carbon atoms, a benzyl group or benzoyl group having 7 to 20 carbon atoms, or —NR ¹⁰ R ¹¹ , and R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ are bonded to each other. A heteroarylalkyl group having 1 to 20 carbon atoms, which may form a ring structure, and at least one of R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ may be substituted. An alkanoyl group or a heteroaryloyl group and a C 3-15 Containing at least one selected from the group consisting of alkyl silyl group.) In general formula (5) of Claim 7, R ^<1a> is respectively C2-C25 alkenyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 which may be substituted, respectively. It is a phenoxycarbonylalkyl group or an aminoalkyl group having 1 to 20 carbon atoms, or R ^1a may form a ring together with R ³ or R ⁷ , in which case R ^1a and R ³ or / and R ⁷ are They are bonded to each other to form a divalent or trivalent linking group, and each of the linking groups may have a substituent, an alkylene group having 1 to 10 carbon atoms,-(CH = CH) _n -,-( C≡C) _n- or a combination thereof (n is an integer of 0 to 3), R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ are a hydrogen atom, halogen Each having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, a benzyl group or benzoyl group having 7 to 20 carbon atoms, or An oxime ester compound, which is —NR ¹⁰ R ¹¹ , wherein R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ may be bonded to each other to form a ring structure. In General formula (6) of Claim 7, R ^<1b > is a C1-C20 alkyl group which may be substituted, and R ^<2b > is C1-C20 which may be respectively substituted. A heteroarylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms or an aminocarbonyl group having 2 to 10 carbon atoms, and R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ are each a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms. 20 benzyl or benzoyl group, or an ^{-NR 10 R 11, R 3,} R 6, R 7, R 12 ~R 16 is an oxime, characterized in that it may be bonded together to form a ring structure Ester-based compounds. An oxime ester compound represented by the general formula (8) or (9).

Wherein R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and 8 to 8 carbon atoms. A phenoxycarbonylalkyl group having 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or a heteroarylthioalkyl group, an amino group having 0 to 20 carbon atoms, or an aminoalkyl group having 1 to 20 carbon atoms; R ^1a may form a ring together with Ar ₁ , and the linking group is an alkylene group having 1 to 10 carbon atoms that may have a substituent, — (CH═CH) _n —, — ( C [identical to] C) _n - or a combination thereof (n is an integer of 0 to 3), R ^2a is the same meaning as in formula (1) according to claim 1, Ar ₁ may have a substituent Aromatic ring optionally heteroaromatic ring represents a fused aromatic ring or a fused heteroaromatic ring, p is represents an integer of from 2 to 5).:

(In the formula, R ^1b is an optionally substituted phenyl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl having 2 to 20 carbon atoms. Group, benzoyl group having 7 to 20 carbon atoms, alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, amide group having 1 to 20 carbon atoms, nitro group, alkenyl group having 2 to 25 carbon atoms, 1 to carbon atoms 10 heteroarylalkyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, carbon number 0-20 amino group, or an amino alkyl group having 1 to 20 carbon atoms, also R ^1b is, form a ring with Ar ₁ At best, the linkage is respectively substituent may number 1 to 10 alkylene carbon atoms which may have _{a, - (CH = CH) n} -, - (C≡C) n - or a combination thereof ( n is an integer of 0 to 3), R ^2b has the same meaning as in general formula (2) according to claim 1, and Ar ₁ is an aromatic ring, heteroaromatic ring, which may have a substituent, Represents a condensed aromatic ring or a condensed heteroaromatic ring, and p represents an integer of 2 to 5.) In general formula (8) of Claim 10, R ^<1a> is respectively substituted C2-C25 alkenyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20, A phenoxycarbonylalkyl group or an aminoalkyl group having 1 to 20 carbon atoms, and R ^1a may form a ring together with Ar ₁ , in which case R ^1a and Ar ₁ are bonded to each other to form 2 A trivalent or trivalent linking group, each of which may have a substituent, an alkylene group having 1 to 10 carbon atoms, — (CH═CH) _n —, — (C≡C) _n -or a combination thereof (n is an integer of 0 to 3), and R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms. In General formula (9) of Claim 10, R ^<1b> is a C1-C20 alkyl group which may be substituted, R ^<2b > is C1-C20 which may be respectively substituted. A heteroaryl alkanoyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, or an aminocarbonyl group having 2 to 10 carbon atoms. An oxime ester compound characterized by   It is a photopolymerizable composition containing (b) an organic binder and (c) a photopolymerization initiator, and (c) contains the oxime ester compound according to any one of claims 1 to 12. The photopolymerizable composition characterized by the above-mentioned.   (B) The photopolymerizable composition according to claim 13, wherein the organic binder is an epoxy acrylate resin having a carboxyl group.   15. The photopolymerizable material according to claim 14, wherein the organic binder is an epoxy acrylate obtained by reacting a reaction product of a novolac type epoxy resin and (meth) acrylic acid with (hydro) phthalic anhydride. Composition.   The photopolymerizable composition according to any one of claims 13 to 15, wherein the photopolymerizable composition further contains (d) a photopolymerizable monomer.   The photopolymerizable composition according to any one of claims 13 to 16, wherein the photopolymerizable composition further contains (e) a polymer dispersant having a basic functional group.   The photopolymerizable composition according to any one of claims 13 to 17, wherein the photopolymerizable composition further contains (a) a coloring material.   A color filter comprising an image formed by the photopolymerizable composition according to claim 13. A liquid crystal display device comprising an image formed by the photopolymerizable composition according to claim 13.

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