JP2007072035A - Photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition capable of forming a black matrix pattern having good linearity, less liable to peel and ensuring less residue. <P>SOLUTION: An acyloxime ester compound represented by formula (1) is used as a photopolymerization initiator in the photosensitive composition. In the general formula (1), Ar is made to a bulky group containing a carbazole skeleton. In the general formula, R<SB>1</SB>represents a 1-5C lower alkyl group; A represents a group selected from a 1-20C alkyl group, a 1-4C haloalkyl group, a phenyl group, CN and NO<SB>2</SB>; and Ar represents a group having carbazole or a substitution product thereof, or a benzoyl group which may have a substituent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive composition for forming a black matrix of a liquid crystal display panel.

  In a display body such as a liquid crystal display, a liquid crystal layer is sandwiched between two substrates, a pair of electrodes is arranged opposite to each of the two substrates, and the liquid crystal layer faces the inside of one substrate. Then, a color filter layer composed of pixels such as red (R), green (G), blue (B), and black is disposed. The black pixels play a role of preventing color mixture of different colors and hiding the electrode pattern, and are usually arranged in a matrix so as to partition the R, G, and B pixels. It is said.

  Generally, the color filter is formed by a lithography method. Specifically, a coating solution of a composition in which a colorant such as an organic pigment, dye or carbon black is uniformly dispersed or dissolved in a photosensitive resin component is applied on a substrate and dried, and then a color filter is formed. Exposure according to the pattern of each color to be performed is performed. Subsequently, the pixel pattern obtained by developing this with an alkali developer or the like is subjected to heat treatment to give mechanical strength as a permanent film. By repeating this process for each color of R, G, and B, a color filter layer is formed.

  As a black matrix for a color filter, a conventionally deposited chromium thin film patterned by a lithography method has been used. This black matrix made of a chromium thin film has high dimensional accuracy and high reliability. However, in order to form a chromium thin film, a vacuum film forming process such as vapor deposition and sputtering is required as described above. Increasing the size of the substrate is accompanied by an increase in opportunities, and it has been difficult to respond to the increase in size of the substrate.

  Also, as a chromium thin film, a resin film formed from a photocurable composition in which a black colorant is dispersed has been used in the same manner as other color filters because of environmental problems (Patent Literature). 1). As black colorants for these black matrix materials, carbon black, titanium black and the like are known, and carbon black is most commonly used.

Patent Document 1 contains a compound containing at least one ethylenically unsaturated double bond capable of addition polymerization, a photopolymerization initiator, a metal oxide, and the like, and is substantially free of halogen atoms. A composition is disclosed. This composition can provide a color filter having excellent heat resistance and high electrical insulation resistance by substantially removing halogen atoms.
Japanese Patent Laid-Open No. 11-84125

  However, in order to impart high light shielding properties to the black matrix, the content of the light shielding material must be increased. For this reason, the optical density increases, and light does not reach the deep part of the film during exposure, and photocuring (photosensitive reaction) may not sufficiently proceed. As a result, the development margin becomes narrow, the linearity of the pattern becomes low, the pattern peels off from the substrate, and a residue may be generated on the substrate.

  Further, when a color filter is produced, depending on the colored photosensitive resin used, if a heat treatment is performed in a baking furnace after exposure and development, a sublimate may be generated from the colored pattern. If this sublimate is mixed in the colored pattern as a foreign substance, it may cause a product defect.

  In view of the above problems, an object of the present invention is to provide a photosensitive composition that can form a black matrix pattern that has good linearity in a color filter of a liquid crystal display, hardly peels off, and has little residue. .

  The present inventors can form a black matrix pattern having good linearity, being difficult to peel off, and having little residue by using an acyloxime ester compound as a photopolymerization initiator of the photosensitive composition. It has been found that a photosensitive composition can be provided.

  More specifically, the present invention provides the following.

[式中、Ｒ_１は、炭素数１以上５以下の低級アルキル基を表し、Ａは、炭化水素基、−ＣＮ、−ＮＯ_２より選択される基を表し、Ａｒはカルバゾールまたはその置換体を有する基、置換基を有してもよいベンゾイル基のいずれかを表す。] (1) A photopolymerization compound, a photopolymerization initiator, and a colorant, and a photosensitizer containing an acyloxime ester compound represented by the following general formula (1) as the photopolymerization initiator. Sex composition.

[Wherein, R ₁ represents a lower alkyl group having 1 to 5 carbon atoms, A represents a group selected from a hydrocarbon group, —CN, and —NO ₂ , and Ar represents carbazole or a substituent thereof. Or a benzoyl group which may have a substituent. ]

According to the invention of (1), the initiation efficiency of the photopolymerization initiator can be improved by setting the photopolymerization initiator to the above-described structure, in particular, R ₁ is a lower alkyl group having 1 to 5 carbon atoms. . Therefore, the photopolymerizable compound can be efficiently activated by a small amount of light to be cured, and the sensitivity of the photosensitive composition to light can be increased. As a result, it is possible to provide a black matrix pattern with high linearity and less occurrence of peeling and residue.

[式中、Ｂは、同一または異なっていてもよい、水素原子、ハロゲン原子、炭素数１から１２のアルキル基、フェニル基、Ｃ_６Ｈ_５Ｓ−、より選択される基を表し、ｋは０から５の整数である。
Ｇは、同一または異なっていてもよい、水素原子、ハロゲン原子、炭素数１から２０のアルキル基、炭素数１から２０のアルコキシ基、炭素数３から２０のシクロアルキル基、−ＯＲ_２、−ＮＲ_３Ｒ_４より選択される基を表し、ｍは０から５の整数である。
ここで、Ｒ_２は、炭素数１から２０のアルキル基（炭素原子の一部がヘテロ原子で置換されていてもよい）、又は、炭素数３から２０のシクロアルキル基（炭素原子の一部がヘテロ原子で置換されていてもよい）を表し、
Ｒ_３、Ｒ_４は、同一または異なっていてもよい、炭素数１から２０のアルキル基、炭素数２から２０のアルコキシカルボニル基を示し、あるいはＲ_３とＲ_４とが一緒になって炭素数３から２０の環を形成してもよく、環を形成した場合、炭素原子の一部がヘテロ原子で置換されていてもよい。
Ｄは同一または異なっていてもよい、水素原子、ハロゲン原子、炭素数１から２０であってヘテロ原子を含んでもよい炭化水素系基、より選択される基を表し、ｎは０から３の整数である。
Ｅは、水素原子、ハロゲン原子、炭素数１から１２のアルキル基、フェニル基より選択される基を表す。] (2) The photosensitive composition according to (1), wherein Ar is a group represented by the following general formula (2) or (3).

[In the formula, B represents the same or different hydrogen atom, halogen atom, alkyl group having 1 to 12 carbon atoms, phenyl group, C ₆ H ₅ S—, and k is a group selected from It is an integer from 0 to 5.
G may be the same or different, hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, -OR ₂ ,- It represents a group selected from NR ₃ R ₄ , and m is an integer of 0 to 5.
Here, R ₂ represents an alkyl group having 1 to 20 carbon atoms (a part of carbon atoms may be substituted with a heteroatom) or a cycloalkyl group having 3 to 20 carbon atoms (a part of carbon atoms). May be substituted with a heteroatom)
R ₃ and R ₄ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms or an alkoxycarbonyl group having 2 to 20 carbon atoms, or R ₃ and R ₄ together represent a carbon number. 3 to 20 rings may be formed, and in the case of forming a ring, some of the carbon atoms may be substituted with heteroatoms.
D represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms and optionally containing a hetero atom, which may be the same or different, and n is an integer of 0 to 3 It is.
E represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a phenyl group. ]

  According to the invention of (2), the sensitivity to light can be further improved by using Ar as benzoyl. Furthermore, as shown in the above general formula (3), when a carbazole ring having a benzene ring substituted at the 3-position of the benzene ring and further having several substituents is used, the sensitivity to light is further improved. At the same time, the heat resistance can be improved.

(3) The photosensitive composition according to (1) or (2), wherein R ₁ is a methyl group or an ethyl group.

According to the invention of (3), the sensitivity to light can be further improved by using R ₁ as a methyl group or an ethyl group. Therefore, the photopolymerization initiator can be cured by being efficiently activated by a small amount of light. As a result, it is possible to provide a black matrix pattern with higher linearity and less occurrence of peeling and residue. Moreover, since the structure of the photopolymerization initiator according to the present invention can be made simpler, the manufacturing process can be simplified.

［式中、Ａは炭化水素基、−ＣＮ、−ＮＯ_２より選択される基を表し、Ｇは、同一または異なっていてもよい、水素原子、ハロゲン原子、炭素数１から２０のアルキル基、炭素数１から２０のアルコキシ基、炭素数３から２０のシクロアルキル基、−ＯＲ_２、−ＮＲ_３Ｒ_４より選択される基を表し、ｍは０から５の整数である。
ここで、Ｒ_２は、炭素数１から２０のアルキル基（炭素原子の一部がヘテロ原子で置換されていてもよい）、又は、炭素数３から２０のシクロアルキル基（炭素原子の一部がヘテロ原子で置換されていてもよい）を表し、
Ｒ_３、Ｒ_４は、同一または異なっていてもよい、炭素数１から２０のアルキル基、炭素数２から２０のアルコキシカルボニル基を示し、あるいはＲ_３とＲ_４とが一緒になって炭素数３から２０の環を形成していてもよく、環を形成した場合、炭素原子の一部がヘテロ原子で置換されていてもよい。］ (4) The photosensitive composition according to any one of (1) to (3), wherein the compound represented by the general formula (1) is a compound represented by the following general formula (4).

[Wherein, A represents a hydrocarbon group, a group selected from —CN, —NO ₂ , and G represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, which may be the same or different, This represents a group selected from an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, —OR ₂ , and —NR ₃ R ₄ , and m is an integer of 0 to 5.
Here, R ₂ represents an alkyl group having 1 to 20 carbon atoms (a part of carbon atoms may be substituted with a heteroatom) or a cycloalkyl group having 3 to 20 carbon atoms (a part of carbon atoms). May be substituted with a heteroatom)
R ₃ and R ₄ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms or an alkoxycarbonyl group having 2 to 20 carbon atoms, or R ₃ and R ₄ together represent a carbon number. 3 to 20 rings may be formed, and when the ring is formed, a part of carbon atoms may be substituted with a heteroatom. ]

  According to the invention of (4), the photopolymerization initiator having the structure of the general formula (4) has high heat resistance, higher linearity, and less occurrence of peeling and residue. A photosensitive composition capable of forming a pattern can be provided.

(5) The photopolymerization initiator is any one of (1) to (4), which is a mixture of a compound represented by the general formula (1) and a compound represented by the following general formula (5). Photosensitive composition.

  According to the invention of (5), by containing the above-mentioned compound as a photopolymerization initiator, it can be efficiently activated by a very small amount of light. This is because the compounds having different electron band spectra coexist so that the photopolymerization initiator broadens the net wavelength range of light having high sensitivity, or at least two kinds of compounds interact. Accordingly, the combined use of the photopolymerization initiator according to the invention described in (1) to (4) and the compound represented by the general formula (5) further increases the sensitivity and development margin of the photosensitive composition, thereby increasing the black matrix. It becomes easier to make the pattern into a good shape with high linearity and less peeling and residue.

  (6) The photosensitive composition according to any one of (1) to (5), wherein the photopolymerization initiator further contains mercaptobenzimidazole.

  According to the invention of (6), similar to the invention described in (5), by using it in combination, it is possible to provide a black matrix pattern with higher linearity and less occurrence of peeling and residue. Further, since mercaptobenzimidazole also acts as an antioxidant, it can be more reliably prevented from peeling off and generating residues by further adding it as a photopolymerization initiator.

  (7) The photosensitive composition according to any one of (1) to (6), wherein the photopolymerizable compound is a compound having at least one ethylenic double bond in the molecule.

  According to the invention of (7), by using a photopolymerizable compound having an ethylenic double bond in the molecule as the photopolymerizable compound, the absorption density of the photosensitive composition is increased in a wide wavelength region, It can be activated even with a very small amount of light. As a result, it is possible to easily form a good black matrix pattern having high light shielding properties, high linearity, and no peeling or residue.

  The “compound having at least one ethylenic double bond in the molecule” includes monomers, oligomers, prepolymers and the like, and it is preferable to select and use at least one of these.

  (8) The photosensitive composition according to any one of (1) to (7), wherein the photopolymerizable compound is an acrylic resin.

  According to the invention of (8), the weather resistance and chemical resistance of the photosensitive composition can be enhanced by using the photopolymerizable compound as an acrylic resin. Here, as the “acrylic resin”, acrylic acid, methacrylic acid and derivatives thereof such as acrylamide and acrylonitrile can be used.

  (9) The photosensitive composition according to any one of (1) to (8), wherein the photopolymerizable compound is a resin having a cardo structure in the molecule.

  According to the invention of (9), the heat resistance and chemical resistance of the photosensitive composition can be improved by using a photopolymerizable compound as a resin having a cardo structure in the molecule.

  (10) The photosensitive composition according to any one of (1) to (9), wherein the colorant includes carbon black.

  According to the invention of (10), by using carbon black as the colorant, a black matrix pattern having a thin film and high light shielding properties can be provided.

  (11) The photosensitive composition according to any one of (1) to (10), which is used as a black resist constituting a black matrix constituting a liquid crystal display.

  According to the present invention, by using a photopolymerization initiator excellent in sensitivity to light, it is possible to easily form a black matrix pattern on a substrate with excellent linearity, no peeling or residue, and excellent display contrast. it can. In addition, a black matrix pattern with high sensitivity, excellent development margin, and high resolution can be provided even with a highly light-shielding resist.

  Hereinafter, the present invention will be specifically described.

  The photosensitive composition according to the present invention contains a photopolymerizable compound, a photopolymerization initiator, and a colorant.

[式中、Ｒ_１は、炭素数１以上５以下の低級アルキル基を表し、Ａは、炭化水素基、−ＣＮ、−ＮＯ_２より選択される基を表し、Ａｒはカルバゾールまたはその置換体を有する基、置換基を有してもよいベンゾイル基のいずれかを表す。] [Photopolymerization initiator]
A “photopolymerization initiator” is a component of a photocurable composition, and refers to a compound that polymerizes the composition by irradiation with ultraviolet rays, electron beams, or the like to polymerize the composition. In the present invention, a compound represented by the following general formula (1) can be used as a photopolymerization initiator.

[Wherein, R ₁ represents a lower alkyl group having 1 to 5 carbon atoms, A represents a group selected from a hydrocarbon group, —CN, and —NO ₂ , and Ar represents carbazole or a substituent thereof. Or a benzoyl group which may have a substituent. ]

R ₁ represents a lower alkyl group having 1 to 5 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, and a pentyl group. Among these, it is preferable to use a methyl group or an ethyl group.

Examples of A include a group selected from a hydrocarbon group, —CN, and —NO ₂ . Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, and a phenyl group. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tertiary butyl group, amyl group, isoamyl group, Linear or branched saturated hydrocarbon group such as triamyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, isononyl group, decyl group, isodecyl group In addition, as described above, it is preferable to use a methyl group having 1 carbon atom.

  Examples of the haloalkyl group having 1 to 4 carbon atoms include a monofluoromethyl group, a difluoromethyl group, and a trifluoromethyl group.

  Ar is either carbazole or a group having a substituent thereof, or a benzoyl group which may have a substituent. Among them, carbazole or a group having a substituent thereof is preferably used. More preferably, the 3-position of the benzene ring is substituted with a benzoyl group having a substituent G.

[式中、Ｂは、同一または異なっていてもよい、水素原子、ハロゲン原子、炭素数１から１２のアルキル基、フェニル基、Ｃ_６Ｈ_５Ｓ−、より選択される基を表し、ｋは０から５の整数である。] Specific examples of the benzoyl group which may have a substituent include those represented by the following general formula (2).

[In the formula, B represents the same or different hydrogen atom, halogen atom, alkyl group having 1 to 12 carbon atoms, phenyl group, C ₆ H ₅ S—, and k is a group selected from It is an integer from 0 to 5. ]

Among them, B represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, and C ₆ H ₅ S—, which may be the same or different. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tertiary butyl group, amyl group, isoamyl group, Linear or branched saturated hydrocarbon group such as triamyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, isononyl group, decyl group, isodecyl group Is mentioned. Furthermore, k is an integer from 0 to 5.

［式中、Ｇは、同一または異なっていてもよい、水素原子、ハロゲン原子、炭素数１から２０のアルキル基、炭素数１から２０のアルコキシ基、炭素数３から２０のシクロアルキル基、−ＯＲ_２、−ＮＲ_３Ｒ_４より選択される基を表し、ｍは０から５の整数である。
ここで、Ｒ_２は、炭素数１から２０のアルキル基（炭素原子の一部がヘテロ原子で置換されていてもよい）、又は、炭素数３から２０のシクロアルキル基（炭素原子の一部がヘテロ原子で置換されていてもよい）を表し、
Ｒ_３、Ｒ_４は、同一または異なっていてもよい、炭素数１から２０のアルキル基、炭素数２から２０のアルコキシカルボニル基を示し、あるいはＲ_３とＲ_４とが一緒になって炭素数３から２０の環を形成してもよく、環を形成した場合、炭素原子の一部がヘテロ原子で置換されていてもよい。
Ｄは同一または異なっていてもよい、水素原子、ハロゲン原子、炭素数１から２０であってヘテロ原子を含んでもよい炭化水素系基、より選択される基を表し、ｎは０から３の整数である。
Ｅは、水素原子、ハロゲン原子、炭素数１から１２のアルキル基、フェニル基より選択される基を表す。] Specific examples of the group having a carbazole substituent and the group having a benzoyl group structure which may have a substituent include a structure represented by the general formula (3).

[In the formula, G may be the same or different, hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms,- It represents a group selected from OR ₂ and —NR ₃ R ₄ , and m is an integer of 0 to 5.
Here, R ₂ represents an alkyl group having 1 to 20 carbon atoms (a part of carbon atoms may be substituted with a heteroatom) or a cycloalkyl group having 3 to 20 carbon atoms (a part of carbon atoms). May be substituted with a heteroatom)
R ₃ and R ₄ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms or an alkoxycarbonyl group having 2 to 20 carbon atoms, or R ₃ and R ₄ together represent a carbon number. 3 to 20 rings may be formed, and in the case of forming a ring, some of the carbon atoms may be substituted with heteroatoms.
D represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms and optionally containing a hetero atom, which may be the same or different, and n is an integer of 0 to 3 It is.
E represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a phenyl group. ]

G may be the same or different, hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, -OR ₂ ,- Of these, NR ₃ R ₄ , of which a group having 3 or more carbon atoms is preferably used. This is because by making G a bulky structure, it is possible to suppress generation of sublimates during exposure and to reduce film slippage.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tertiary butyl group, amyl group, isoamyl group, Linear or branched saturated hydrocarbon groups such as triamyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, isononyl group, decyl group, isodecyl group Is mentioned.

  Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, an isopropoxy group, and an isobutoxy group.

  Furthermore, examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclohexyl group, and a cyclohexyl group. M is an integer from 0 to 5.

R ₂ of —OR ₂ is an alkyl group having 1 to 20 carbon atoms (a part of the carbon atoms may be substituted with a hetero atom or an ester bond), or C 3 to 20 In which a part of the carbon atoms is substituted with a heteroatom, or may be substituted with an ester bond.

  As the alkyl group, as described above, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tertiary butyl group, amyl group, isoamyl group, tertiary amyl group, Examples thereof include straight-chain or branched saturated hydrocarbon groups such as hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, isononyl group, decyl group and isodecyl group. These alkyl groups may contain an oxy group, a thio group, a dithio group, an imino group, a nitrino group, a hydrazo group, an azo group, and the like.

  Furthermore, examples of the cycloalkyl group include a cyclopropyl group, a cyclohexyl group, and a cyclohexyl group. As described above, these cycloalkyl groups may also contain an oxy group, a thio group, a dithio group, an imino group, a nitrino group, a hydrazo group, an azo group, and the like. Note that these groups may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or the like.

  Furthermore, in consideration of solubility in a solvent, a part of the carbon atoms of the alkyl group and cycloalkyl group are particularly preferably substituted with an ether bond or an ester bond. The ether bond and ester bond are preferably contained in the alkyl group and cycloalkyl group in an amount of 1 to 6, more preferably 2 to 4. As the solvent at this time, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, ethers, ketones and esters are preferable, and propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are more preferable. .

In addition, R ₄ and R ₅ in —NR ₄ R ₅ may be the same or different, and are an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, or R ₄ and R _5. Together, they may form a ring having 3 to 20 carbon atoms. As the alkyl group, as described above, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tertiary butyl group, amyl group, isoamyl group, tertiary amyl group, Examples thereof include saturated hydrocarbon groups such as a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a tertiary octyl group, a nonyl group, an isononyl group, a decyl group, and an isodecyl group.

  The alkoxycarbonyl group is a straight chain such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a tert-butoxycarbonyl group, or a cyclohexyloxycarbonyl group, A branched or cyclic group is mentioned.

Examples of the case where R ₄ and R ₅ together form a ring include a piperidine ring, a piperazine ring, a morpholine ring, and a thiomorpholine ring. Note that these rings may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or the like.

  D represents a halogen atom, which may be the same or different, or a hydrocarbon group which has 1 to 20 carbon atoms and may contain a hetero atom. Examples thereof include hydrocarbon groups having 1 to 20 carbon atoms including oxy group, thio group, dithio group, imino group, nitrino group, hydrazo group, azo group and the like. In addition, this hydrocarbon group may contain an unsaturated bond and may form a ring.

  E represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group. Among them, it is preferable to use an alkyl group. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an amyl group, and an isoamyl group. Linear or branched saturated carbonization such as tertiary amyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, isononyl group, decyl group, isodecyl group A hydrogen group is mentioned. As described above, it is preferable to use an ethyl group having 2 carbon atoms.

［式中、Ａは炭化水素基、−ＣＮ、−ＮＯ_２より選択される基を表し、Ｇは、同一または異なっていてもよい、水素原子、ハロゲン原子、炭素数１から２０のアルキル基、炭素数１から２０のアルコキシ基、炭素数３から２０のシクロアルキル基、−ＯＲ_２、−ＮＲ_３Ｒ_４より選択される基を表し、ｍは０から５の整数である。
ここで、Ｒ_２は、炭素数１から２０のアルキル基（炭素原子の一部がヘテロ原子で置換されていてもよい）、又は、炭素数３から２０のシクロアルキル基（炭素原子の一部がヘテロ原子で置換されていてもよい）を表し、
Ｒ_３、Ｒ_４は、同一または異なっていてもよい、炭素数１から２０のアルキル基、炭素数２から２０のアルコキシカルボニル基を示し、あるいはＲ_３とＲ_４とが一緒になって炭素数３から２０の環を形成していてもよく、環を形成した場合、炭素原子の一部がヘテロ原子で置換されていてもよい。］ The compound having such a structure is preferably a compound represented by the general formula (4). By having both carbazole and benzoyl skeletons, sensitivity to light is improved. Furthermore, heat resistance improves by having a carbazole skeleton.

[Wherein, A represents a hydrocarbon group, a group selected from —CN, —NO ₂ , and G represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, which may be the same or different, This represents a group selected from an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, —OR ₂ , and —NR ₃ R ₄ , and m is an integer of 0 to 5.
Here, R ₂ represents an alkyl group having 1 to 20 carbon atoms (a part of carbon atoms may be substituted with a heteroatom) or a cycloalkyl group having 3 to 20 carbon atoms (a part of carbon atoms). May be substituted with a heteroatom)
R ₃ and R ₄ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms or an alkoxycarbonyl group having 2 to 20 carbon atoms, or R ₃ and R ₄ together represent a carbon number. 3 to 20 rings may be formed, and when the ring is formed, a part of carbon atoms may be substituted with a heteroatom. ]

More specifically, the following general formula (6) wherein A is a methyl group, Ar is a group represented by the general formula (3), G is a methyl group, n of D is 0, and E is an ethyl group It is more preferable to use the compound shown by these.

  When using the said compound as a photoinitiator, it is 1 mass part to 150 mass parts with respect to a total of 100 mass parts of a photopolymerizable compound, Preferably it is 5 mass parts to 100 mass parts, More preferably, it is 10 mass parts to 50 mass parts. It is contained in the range of parts by mass. When the content is 150 parts by mass or less, sufficient heat resistance and chemical resistance can be obtained, and when the content is 1 part by mass or more, the coating film forming ability is improved and photocuring failure is prevented. can do.

  Moreover, you may use a photoinitiator combining the compound shown by the said General formula (1), and another compound (photoinitiator) several types. Examples of such compounds include acetophenone such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, benzophenone, Benzophenones such as 2-chlorobenzophenone and p, p′-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether, benzyldimethyl ketal, thioxanthene, Sulfur compounds such as 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2- Anthraquinones such as ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2- Thiol compounds such as mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, and imidazolyl compounds such as 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer And triazine compounds such as p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4, -Bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino- 2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- Triazine compounds having a halomethyl group such as (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-benzyl-2-dimethylamino And aminoketone compounds such as -1- (4-morpholinophenyl) -butan-1-one.

Among these compounds, it is preferable to use mercaptobenzimidazole or a triazine compound, but it is more preferable to use a compound represented by the following general formula (5). This is because the sensitivity to light can be further improved by using this compound in combination.

  When using the said compound together with the compound shown by General formula (1) as a photoinitiator, it is 1 mass part to 150 mass parts with respect to a total of 100 mass parts of a photopolymerizable compound, Preferably it is 5 mass parts To 100 parts by mass, more preferably 10 to 50 parts by mass. When the content is 150 parts by mass or less, sufficient heat resistance and chemical resistance can be obtained, and when the content is 1 part by mass or more, the film forming ability is improved and photocuring failure is prevented. Can do.

  When a compound represented by the general formula (1) and a compound other than the compound represented by the general formula (1) (particularly the general formula (5) and mercaptobenzimidazole) are used in combination, the mass ratio is from 10:90. 90:10 is preferable, and 50:50 to 70:30 is particularly preferable. Since the compounding ratio of the compound represented by the general formula (1) and the compound other than the compound represented by the general formula (1) is within the above-described range, the two compounds effectively interact with each other. The sensitivity of the composition and the development margin can be further improved.

As an example of the method for producing a photopolymerization initiator according to the present invention, the following synthesis scheme may be mentioned. This synthesis scheme is a synthesis example in which n of D is 0. Here, in the formula, R ₁ corresponds to A in the present invention, and R ₂ corresponds to a phenyl group containing G in the present invention. Further, R ₃ corresponds to R ₁ in the present invention, and R corresponds to E in the present invention.

[Photopolymerizable compound]
“Photopolymerizable compound” refers to a substance that polymerizes and cures upon irradiation with light such as ultraviolet rays. As the photopolymerizable compound, a compound having an ethylenic double bond is preferable. Specifically, acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl acrylate, 2 -Hydroxyethyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, acrylic acid amide, methacrylic acid amide, acrylonitrile, methacrylonitrile , Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl Acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol Diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylo Propane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1 Monomers, oligomers such as 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardoepoxy diacrylate; polyester prepolymers obtained by condensing polyhydric alcohols with monobasic acids or polybasic acids Polyester (meth) acrylate and polyol obtained by reacting (meth) acrylic acid Polyurethane (meth) acrylate obtained by reacting a group with two isocyanate groups and then reacting with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin , Phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy Examples thereof include an epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as a resin with (meth) acrylic acid. Further, a resin obtained by reacting the epoxy (meth) acrylate resin with a polybasic acid anhydride can be used.

  Among these, it is preferable to use a resin having a cardo structure in the molecule. Since the resin having a cardo structure has high heat resistance and chemical resistance, the heat resistance and chemical resistance of the photosensitive composition can be improved by using it as a photopolymerizable compound. Specifically, it is preferable to use a resin represented by the following general formula (7).

式中、Ｘは、下記一般式（８）で示される基である。

In the formula, X is a group represented by the following general formula (8).

  Wherein Y is maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, It is a residue obtained by removing a carboxylic anhydride group (—CO—O—CO—) from a dicarboxylic anhydride such as glutaric anhydride.

  In the formula, Z represents two carboxylic acids from tetracarboxylic dianhydrides such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, etc. It is a residue excluding an anhydride group.

  The said photopolymerizable compound is contained in 60 mass parts to 99.9 mass parts with respect to a total of 100 mass parts of a photoinitiator. When the content is less than 60 parts by mass, sufficient heat resistance and chemical resistance cannot be expected, and by setting the content to 99.9 parts by mass or less, the coating film forming ability can be improved and photocuring failure can be prevented.

[Colorant]
The “colorant” refers to a component that is contained as one of the photosensitive resin components and colors on the substrate. For example, a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colorists), specifically, a color index (CI) number as shown below. What is attached can be mentioned.

  C. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185;

C. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same and only the numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

  C. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 79, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;

C. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same and only the numbers are described), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37;
C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28;
C. I. Pigment Black 1 and Pigment Black 7.
Carbon black is also preferred as the black pigment.

  Since the photosensitive composition according to the present invention has high sensitivity, it is particularly suitable for forming a black matrix. That is, a light-shielding agent such as carbon black can be preferably used as the colorant. Specifically, carbon black or a carbon black dispersion liquid dispersed with an acrylic dispersion liquid may be used. In addition, examples include metal oxides such as titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, composite oxides, metal sulfides, metal sulfates, inorganic pigments such as metal sulfates, and the like. It is done. Among these colorants, it is more preferable to use carbon black having light shielding properties.

As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, but it is particularly preferable to use channel black having excellent light shielding properties. Resin-coated carbon black may also be used.

  Since this resin-coated carbon black has lower conductivity than carbon black without resin coating, there is less current leakage when used as a color filter for liquid crystal displays, etc., and a highly reliable display with low power consumption is formed. it can.

  An organic pigment may be further added as an auxiliary pigment for carbon black. This is because the organic pigment can eliminate the redness of the carbon black by appropriately selecting and adding an organic pigment that exhibits a complementary color of the inorganic pigment. Examples thereof include phthalocyanine pigments, azo pigments, basic dye lake pigments, and the like.

  The organic pigment is preferably used in the range of 10 to 80 parts by mass, more preferably in the range of 20 to 40 parts by mass with respect to 100 parts by mass of the sum of the inorganic pigment and the organic pigment. preferable. As the inorganic pigment and the organic pigment, a solution in which a dispersant is used and dispersed at an appropriate concentration can be used.

As the dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant.

[Composition of photosensitive composition]
In the photosensitive composition according to the present invention, the photopolymerizable compound, the photopolymerization initiator, and the colorant are combined in 100 parts by mass, the photopolymerizable compound is contained in an amount of 20 to 60 parts by mass, and the photopolymerization initiator is added. It is preferable to contain 0.5 to 30 parts by mass and a colorant in the range of 10 to 70 parts by mass. When the colorant is 10 parts by mass or more, the light shielding performance of the formed black pattern can be sufficiently obtained. Further, when the colorant is 70 parts by mass or less, curing failure can be suppressed when a light beam having a predetermined wavelength is irradiated.

  In the above composition ratio, the colorant may be only an inorganic pigment such as carbon black or titanium black, but may contain an auxiliary pigment.

  The concentration of the colorant is such that when a black matrix is formed using the photosensitive composition according to the present invention as described later, an OD (Optical Density) value of 3 μm per 1 μm of film thickness of the photosensitive composition. It is preferable to adjust so that it may become 5 or more. If the OD value per film thickness of 1 μm of the photosensitive composition is 3.5 or more, sufficient display contrast can be obtained when used for a black matrix of a liquid crystal display.

  Moreover, when forming a black matrix pattern using the photosensitive composition which concerns on this invention, as mentioned later, the photosensitive composition of this invention is apply | coated and dried on a board | substrate, and a film | membrane is formed. In order to improve the coating property and the physical properties after photocuring at this time, in addition to the above components, a polymer binder may be further contained as a binder. What is necessary is just to select a binder suitably according to the improvement objectives, such as compatibility, film formation property, developability, and adhesiveness.

  The thickness of the black matrix pattern formed on the substrate can usually be set within the range of 0.5 μm to 10.0 μm, preferably 0.2 μm to 5.0 μm, more preferably 0.2 μm to 3 μm. 0.0 μm.

Further, the photosensitive composition according to the present invention may contain a solvent for dilution, a thermal polymerization inhibitor, an antifoaming agent, a surfactant and the like.

  Here, examples of the solvent that can be added to the photosensitive composition include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl Ether, propylene glycol mono-n-butyl ether, dipropylene glycol (Poly) alkylene glycol mono, such as coal monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Alkyl ethers: (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate acetate Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate Alkyl lactates such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Lopionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, Other esters such as i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; aroma such as toluene, xylene Group hydrocarbons; amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the like. These solvents can be used alone or in combination of two or more.

  Among them, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and 3-methoxybutyl acetate are photopolymerizable compounds and photopolymerization starts. It is preferable because propylene glycol monomethyl ether acetate, cyclohexanone, and 3-methoxybutyl acetate are particularly preferable because it exhibits excellent solubility in the agent and can improve dispersibility of insoluble components such as black pigments. A solvent can be used in 50 mass parts-500 mass parts with respect to a total of 100 mass parts of a photopolymerizable compound, a photoinitiator, and a light shielding material.

  Moreover, hydroquinone, hydroquinone monoethyl ether, etc. can be used as a thermal polymerization inhibitor. In addition, silicone-based and fluorine-based compounds can be used as antifoaming agents, and various known thermal polymerization inhibitors such as anionic, cationic, and nonionic surfactants can be used as surfactants.

  As a manufacturing method of the photosensitive composition concerning this invention, it is obtained by mixing the above-mentioned photopolymerizable compound, a photoinitiator, a coloring agent, and these all with a stirrer. In addition, you may filter using a filter so that the obtained mixture may become uniform.

<Method for forming color filter>
Hereinafter, the example of the method of forming a color filter using the photosensitive composition concerning this invention is demonstrated.

[Formation of black matrix (black colored layer)]
First, a photosensitive composition (including a black colorant) is applied onto a substrate, such as a contact transfer type coating device such as a roll coater, reverse coater, or bar coater, a spinner (rotary coating device), or a non-contact type such as a curtain flow coater. Apply using an applicator. As the substrate, a substrate having optical transparency is used. In the present embodiment, it is assumed that a glass substrate having a thickness of 0.5 mm to 1.1 mm is used.

  In order to improve the adhesion between the glass substrate and the photosensitive composition, a silane coupling agent may be applied on the glass substrate in advance. Alternatively, a silane coupling agent may be added during the preparation of the photosensitive composition.

  After this photosensitive composition is applied, it is dried to remove the solvent. The drying method is not particularly limited. For example, (1) a method of drying on a hot plate at a temperature of 80 ° C. to 120 ° C., preferably 90 ° C. to 100 ° C. for 60 seconds to 120 seconds, (2) several hours at room temperature Any of the following methods may be used: (3) a method of removing the solvent by placing it in a warm air heater or an infrared heater for several tens of minutes to several hours.

Next, exposure is performed partially by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. Energy dose to be irradiated may differ depending on the composition of the photosensitive composition, for example, about 2000 mJ / cm ² from 30 mJ / cm ² is preferred.

  Next, the exposed film is developed into a desired shape by developing with a developer. The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. Examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

  Next, post-baking is performed at about 200 ° C. for patterning after development. Further, it is preferable to expose the entire surface of the formed pattern.

[Formation of other colored layers]
The photosensitive composition is coated, dried, exposed and developed on the glass substrate on which the black matrix formed by the above method is formed in the same manner as described above to form a colored layer of a predetermined color. A pattern (such as a stripe or a dot) is formed at the position (opening). For example, when manufacturing an RGB color filter, the above process is repeated using a photosensitive composition of each color of R, G, and B to form a color filter of three colors to form a color filter.

式中、Ｘは、一般式（８）で示される基である。

<Example 1>
[Synthesis of photopolymerizable compound]
First, a cardo resin represented by the following general formula (7) was synthesized.

In the formula, X is a group represented by the general formula (8).

  In a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tertbutyl-4-methylphenol and 72.0 g of acrylic acid were added at 25 ml / The solution was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of minutes.

  Next, the solution was slowly heated to 120 ° C. in a cloudy state and completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued for about 12 hours until the acid value became less than 1.0 mgKOH / g. And it cooled to room temperature and the colorless and transparent solid bisphenol fluorene type epoxy acrylate shown in following General formula (9) was obtained.

  Next, after adding 600 g of propylene glycol monomethyl ether acetate (PGMEA) to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained, 80.5 g of benzophenone tetracarboxylic dianhydride and bromide were added. 1 g of tetraethylammonium was mixed and reacted at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain a cardo resin represented by the above general formula (9). Got. The disappearance of the acid anhydride group was confirmed by IR spectrum. This cardo resin was referred to as Compound 1.

  Here, the compound 1 is a compound represented by the general formula (7), wherein X is a group represented by the general formula (8), and Y is an acid from 1,2,3,6-tetrahydrophthalic anhydride dianhydride. A residue excluding the anhydride group (—CO—O—CO—), Z is a residue obtained by removing the acid anhydride from 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, The Y / Z molar ratio is 50.0 / 50.0.

[Photopolymerization initiator]
The compound represented by the following general formula (6) was designated as photopolymerization initiator 1 according to the present invention (CGI 242 manufactured by Ciba Specialty Chemicals).

  As the compound 1 and the monomer, pentaerythritol tetraacrylate was used as a photopolymerizable compound, and the photosensitive composition according to the present invention was prepared as shown in Table 1. At this time, a carbon dispersion (CF black EX-1455 (containing 24% by mass of high-resistance carbon, manufactured by Mikuni Dye Co., Ltd.)) was used as the pigment, and 3-methoxybutyl acetate was used as the solvent. The mixture was mixed for a period of time and filtered through a 5 μm membrane filter to prepare a photosensitive composition.

<Example 2>
The photosensitive composition according to the present invention was prepared in the same procedure as in Example 1 except that the photopolymerization initiator was a compound having a structure represented by the following general formula (photopolymerization initiator 2) (Table). 1). This compound was produced according to the above synthesis scheme.

［式中Ｒ_２は、上述のスキーム中のＲ_２に対応し、本発明におけるＥを含むフェニル基に相当する。］

In the synthesis of this compound, a compound represented by the following general formula was produced according to the following scheme.

[Wherein R ₂ corresponds to R ₂ in the above-mentioned scheme and corresponds to a phenyl group containing E in the present invention. ]

  As the compound 1 and monomer, pentaerythritol tetraacrylate (PETTA) was used as a photopolymerizable compound, and the photosensitive composition according to the present invention was prepared according to the formulation shown in Table 1. At this time, a carbon dispersion (CF black EX-1455, containing 24% by mass of high-resistance carbon, manufactured by Mikuni Dye Co., Ltd.) was used as the pigment, and 3-methoxybutyl acetate was used as the solvent. All of these were mixed with a stirrer for 2 hours and filtered through a 5 μm membrane filter to prepare the photosensitive composition according to the present invention.

<Comparative Example 1>
A photosensitive composition was prepared in the same procedure as in Example 1 except that the photopolymerization initiator was a compound having the following structural formula (CGI124: photopolymerization initiator 3 manufactured by Ciba Specialty Chemicals) (see Table 1). ).

<Comparative example 2>
A photosensitive composition was prepared in the same procedure as in Example 1 except that the photopolymerization initiator was a compound having the following structural formula (photopolymerization initiator 4) (see Table 1). This photopolymerization initiator 4 was synthesized according to the following scheme.

<Evaluation>
The above photosensitive composition was applied on a glass substrate having a clean surface of 1 mm thickness using a spin coater (TR25000, manufactured by Tokyo Ohka Kogyo Co., Ltd.) so that the dry film thickness was 1.2 μm. The film was dried at 90 ° C. for 2 minutes to form a film (photosensitive layer) of the photosensitive composition. Subsequently, the film was selectively irradiated with ultraviolet rays through a negative mask. The exposure amount was set in four stages of 50, 80, 100, and 120 mJ.

  Then, a black matrix pattern including a line having a line width of 10 μm was formed by spray development with a 0.5 mass% sodium carbonate aqueous solution at 25 ° C. for 60 seconds. Thereafter, post-baking was performed in a circulation oven at 220 ° C. for 30 minutes. The film thickness of the prepared black matrix was 1.0 μm, and was measured with an OD measuring device (D-200II, manufactured by Gretag Macbeth). These results are shown in Table 2.

  The linearity of the pattern was determined by visual observation of whether or not the edge of the 10-micron line (line having a width of 10 μm) had rattling. Further, the pattern peeling was visually judged as to whether peeling or chipping occurred on a 5 micron line (a line having a width of 5 μm). The residue was visually determined whether or not the pigment residue remained on the glass. From this, the patterns obtained in Examples 1 and 2 were excellent in linearity, and peeling from the pigment residue and the substrate was not confirmed. On the other hand, Comparative Examples 1 and 2 showed that the pattern peeling was large and the linearity was not good at a low exposure amount.

Claims (11)

Containing a photopolymerizable compound, a photopolymerization initiator, and a colorant;
A photosensitive composition containing an acyloxime ester compound represented by the following general formula (1) as the photopolymerization initiator.

[Wherein, R ₁ represents a lower alkyl group having 1 to 5 carbon atoms, A represents a group selected from a hydrocarbon group, —CN, and —NO ₂ , and Ar represents carbazole or a substituent thereof. Or a benzoyl group which may have a substituent. ] 2. The photosensitive composition according to claim 1, wherein Ar is a group represented by the following general formula (2) or (3).

[In the formula, B represents the same or different hydrogen atom, halogen atom, alkyl group having 1 to 12 carbon atoms, phenyl group, C ₆ H ₅ S—, and k is a group selected from It is an integer from 0 to 5.
G may be the same or different, hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, -OR ₂ ,- It represents a group selected from NR ₃ R ₄ , and m is an integer of 0 to 5.
Here, R ₂ represents an alkyl group having 1 to 20 carbon atoms (a part of carbon atoms may be substituted with a heteroatom) or a cycloalkyl group having 3 to 20 carbon atoms (a part of carbon atoms). May be substituted with a heteroatom)
R ₃ and R ₄ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms or an alkoxycarbonyl group having 2 to 20 carbon atoms, or R ₃ and R ₄ together represent a carbon number. 3 to 20 rings may be formed, and in the case of forming a ring, some of the carbon atoms may be substituted with heteroatoms.
D represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms and optionally containing a hetero atom, which may be the same or different, and n is an integer of 0 to 3 It is.
E represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a phenyl group. ] The photosensitive composition according to claim 1, wherein R ₁ is a methyl group or an ethyl group. The photosensitive composition according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (4).

[Wherein, A represents a hydrocarbon group, a group selected from —CN, —NO ₂ , and G represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, which may be the same or different, This represents a group selected from an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, —OR ₂ , and —NR ₃ R ₄ , and m is an integer of 0 to 5.
Here, R ₂ represents an alkyl group having 1 to 20 carbon atoms (a part of carbon atoms may be substituted with a heteroatom) or a cycloalkyl group having 3 to 20 carbon atoms (a part of carbon atoms). May be substituted with a heteroatom)
R ₃ and R ₄ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms or an alkoxycarbonyl group having 2 to 20 carbon atoms, or R ₃ and R ₄ together represent a carbon number. 3 to 20 rings may be formed, and when the ring is formed, a part of carbon atoms may be substituted with a heteroatom. ] The photosensitive composition according to claim 1, wherein the photopolymerization initiator is a mixture of a compound represented by the general formula (1) and a compound represented by the following general formula (5). .

  The photosensitive composition according to claim 1, wherein the photopolymerization initiator further contains mercaptobenzimidazole.   The photosensitive composition according to claim 1, wherein the photopolymerizable compound is a compound having at least one ethylenic double bond in the molecule.   The photosensitive composition according to claim 1, wherein the photopolymerizable compound is an acrylic resin.   The photosensitive composition according to claim 1, wherein the photopolymerizable compound is a resin having a cardo structure in the molecule.   The photosensitive composition according to claim 1, wherein the colorant contains carbon black. The photosensitive composition in any one of Claim 1 to 10 used as a black resist which comprises the black matrix which comprises a liquid crystal display.