JP2007072034A - Photosensitive composition - Google Patents

Abstract

An object of the present invention is to provide a photosensitive composition that can form a black matrix pattern that has good linearity, is difficult to peel off, and has few residues.
As a photopolymerization initiator of a photosensitive composition, an oxime compound having a fluorene skeleton and benzoyl represented by the following general formula (1) was used. Moreover, in General formula (1), when the benzoyl part was made into the bulky group, it discovered that it became possible to suppress generation | occurrence | production of a sublimation in the heating after image development.
[Chemical 1]

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. The 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. . It is another object of the present invention to provide a photosensitive composition capable of forming a black matrix pattern with less generation of sublimation during heating after development.

  By using an oxime compound having a fluorene skeleton and benzoyl as the photopolymerization initiator of the photosensitive composition, the present inventors have formed a black matrix pattern that has good linearity, is difficult to peel off, and has few residues It has been found that a photosensitive composition can be provided. In addition, the present inventors have found that when the benzoyl portion is a bulky group, it is possible to suppress the generation of sublimates during heating after development.

  More specifically, the present invention provides the following.

［式中、
Ａは−Ｒ_１、−ＯＲ_１、−ＣＯＲ_１、−ＳＲ_１、又は−ＮＲ_１Ｒ_２を表し、
Ｂは−Ｒ_１、−ＯＲ_１、−ＣＯＲ_１、−ＳＲ_１、−ＣＯＮＲ_１Ｒ_２又は−ＣＮを表し、
Ｇは水素原子、−Ｒ_１、−ＯＲ_１、−ＣＯＲ_１、−ＳＲ_１、又は−ＮＲ_１Ｒ_２を表し、
上記Ｒ_１及びＲ_２は、それぞれ独立して、アルキル基、アリール基、アラルキル基又は複素環基を表し、これらはハロゲン原子及び／又は複素環基で置換されていてもよく、これらのうちアルキル基及びアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合により中断されていてもよく、また、Ｒ_１及びＲ_２は一緒になって環を形成していてもよく、
Ｄは、同一又は異なっていてもよい、ハロゲン原子、又は、炭素数１以上２０以下であってヘテロ原子を含んでいてもよい炭化水素系基を表し、
Ｅは、同一又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_３、−ＮＲ_４Ｒ_５を表し、
ここで、Ｒ_３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）、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_４、Ｒ_５は、同一又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、あるいはＲ_４とＲ_５とは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く、
さらに、Ｅの少なくとも１つは、分子量が３０以上の基を表し、
ｍは０から５の整数、ｎは０から３の整数であり、ｍ＋ｎ＞１を満たす。］ (1) contains a photopolymerizable compound, a photopolymerization initiator, and a colorant,
The photosensitive composition containing the compound shown by following General formula (1) as said photoinitiator.

[Where:
A is _{-R 1, -OR 1, -COR 1} , -SR 1, or represents _-NR 1 _{R 2,}
B is _{-R 1, -OR 1, -COR 1} , -SR 1, -CONR 1 R 2 or represents -CN,
G represents a hydrogen _{atom, -R 1, -OR 1, -COR} 1, -SR 1, or _-NR 1 _{R 2,}
R ₁ and R ₂ each independently represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, which may be substituted with a halogen atom and / or a heterocyclic group, The alkylene part of the group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond, and R ₁ and R ₂ may be combined to form a ring;
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;
E represents the same or different 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 ₃ , —NR ₄ R ₅ . ,
Here, R ₃ represents an alkyl group having 1 to 20 carbon atoms (a part of carbon atoms may be substituted with a heteroatom), a cycloalkyl group having 3 to 20 carbon atoms (a part of carbon atoms is heterogeneous). Which may be substituted with atoms)
R ₄ and R ₅ , which may be the same or different, are alkyl groups having 1 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, or R ₄ and R ₅ together are 20 rings may be formed, and when a ring is formed, some of the carbon atoms may be substituted with heteroatoms,
Further, at least one of E represents a group having a molecular weight of 30 or more,
m is an integer from 0 to 5, n is an integer from 0 to 3, and satisfies m + n> 1. ]

  According to the invention of (1), it is possible to improve the sensitivity to light by adopting the above-described structure as the photopolymerization initiator. Therefore, the photosensitive composition 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 having high linearity and free from peeling or residue. In addition, by using at least one of E as a group having a molecular weight of 30 or more, it is possible to suppress the generation of sublimates with less film slippage and without impairing sensitivity to light.

(2) E is the photosensitive group according to (1), wherein E is any one group of an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, —OR ₃ , or —NR ₄ R _5. Sex composition.

According to the invention of (2), E is a group such as an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, —OR ₃ , or —NR ₄ R _5, etc. It is possible to provide a photosensitive composition capable of forming a black matrix pattern with less generation of sublimates upon heating.

  (3) The photosensitive composition according to (1) or (2), wherein m is 1 or more and n is 0.

  According to the invention of (3), it is possible to further improve the sensitivity to light by setting the value of n to 0.

  (4) E is the photosensitive composition in any one of (1) to (3) which is a C7-C12 alkyl group.

  According to the invention of (4), when E is alkyl having 7 to 12 carbon atoms, E has a bulky structure. For this reason, it is possible to further suppress the generation of sublimates without impairing the sensitivity to light.

(5) 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 (2).

  According to the invention of (5), by adding a pyranyl group to the benzoyl part of the compound represented by the general formula (1), the benzoyl part can have a bulky structure without impairing sensitivity to light. Therefore, the photosensitive compound which can suppress generation | occurrence | production of a sublimation more can be provided.

(6) 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 (3).

According to the invention of (6), by adding a specific group to the benzoyl part of the compound represented by the general formula (1) as represented by the general formula (3), the light can be obtained similarly to the invention of (5). A benzoyl part can be made into a bulky structure, without impairing the sensitivity with respect to. Therefore, the photosensitive compound which can suppress generation | occurrence | production of a sublimation more can be provided. In addition, it is possible to suppress film slippage of the formed film.

(7) The said photoinitiator is a photosensitive composition in any one of (1) to (6) which further contains the compound shown by following General formula (4).

  According to the invention of (7), by containing the above 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 (6) and the compound represented by the general formula (4) further increases the sensitivity and development margin of the photosensitive composition, thereby increasing the black matrix. It becomes even easier to make the pattern a good shape with high linearity and no peeling or residue.

(8) The said photoinitiator is a photosensitive composition in any one of (1) to (6) which further contains the compound shown by following General formula (5).

  According to the invention of (8), the photopolymerization initiator according to the invention described in (1) to (6) and the compound represented by the general formula (5) are used in combination as in the invention described in (7). By doing so, it is possible to provide a black matrix pattern with higher linearity and no peeling or residue.

  (9) The photosensitive composition according to any one of (1) to (8), wherein the photopolymerization initiator further contains mercaptobenzimidazole.

  According to the invention of (9), similar to the inventions described in (7) and (8), by using in combination, a black matrix pattern having higher linearity and free from peeling and residue is provided. Can do. 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.

  (10) The photosensitive composition according to any one of (1) to (9), wherein the photopolymerizable compound is a compound having at least one ethylenic double bond in the molecule.

  According to the invention of (10), 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.

  (11) The photosensitive composition according to any one of (1) to (10), wherein the photopolymerizable compound is an acrylic resin.

  According to the invention of (11), 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.

  (12) The photosensitive composition according to any one of (1) to (11), wherein the photopolymerizable compound includes a resin having a cardo structure in a molecule and having at least one ethylenic double bond in the molecule. object.

  According to the invention of (12), the heat resistance and chemical resistance of the photosensitive composition can be improved by using the photopolymerizable compound as a resin having a cardo structure in the molecule.

  (13) The photosensitive composition according to any one of (1) to (12), wherein the colorant includes carbon black.

  According to the invention of (13), by using carbon black as the colorant, a black matrix pattern with a thin film and high light shielding properties can be provided.

  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. Furthermore, by using the polymerization initiator according to the present invention, it is possible to provide a photosensitive composition capable of forming a black matrix pattern with little generation of sublimation during heating after development.

  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、
Ａは−Ｒ_１、−ＯＲ_１、−ＣＯＲ_１、−ＳＲ_１、又は−ＮＲ_１Ｒ_２を表し、
Ｂは−Ｒ_１、−ＯＲ_１、−ＣＯＲ_１、−ＳＲ_１、−ＣＯＮＲ_１Ｒ_２又は−ＣＮを表し、
Ｇは水素原子、−Ｒ_１、−ＯＲ_１、−ＣＯＲ_１、−ＳＲ_１、又は−ＮＲ_１Ｒ_２を表し、
上記Ｒ_１及びＲ_２は、それぞれ独立して、アルキル基、アリール基、アラルキル基又は複素環基を表し、これらはハロゲン原子及び／又は複素環基で置換されていてもよく、これらのうちアルキル基及びアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合により中断されていてもよく、また、Ｒ_１及びＲ_２は一緒になって環を形成していてもよく、
Ｄは、同一又は異なっていてもよい、ハロゲン原子、又は、炭素数１以上２０以下であってヘテロ原子を含んでいてもよい炭化水素系基を表し、
Ｅは、同一又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_３、−ＮＲ_４Ｒ_５を表し、
ここで、Ｒ_３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る、あるいはエステル結合で置換されていてもよい）、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る、あるいはエステル結合で置換されていてもよい）を表し、
Ｒ_４、Ｒ_５は、同一又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、あるいはＲ_４とＲ_５とは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く、
さらに、Ｅの少なくとも１つは、分子量が３０以上の基を表し、
ｍは０から５の整数、ｎは０から３の整数であり、ｍ＋ｎ＞１を満たす。］ [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.

[Where:
A is _{-R 1, -OR 1, -COR 1} , -SR 1, or represents _-NR 1 _{R 2,}
B is _{-R 1, -OR 1, -COR 1} , -SR 1, -CONR 1 R 2 or represents -CN,
G represents a hydrogen _{atom, -R 1, -OR 1, -COR} 1, -SR 1, or _-NR 1 _{R 2,}
R ₁ and R ₂ each independently represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, which may be substituted with a halogen atom and / or a heterocyclic group, The alkylene part of the group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond, and R ₁ and R ₂ may be combined to form a ring;
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;
E represents the same or different 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 ₃ , —NR ₄ R ₅ . ,
Here, R ₃ represents 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 a cycloalkyl having 3 to 20 carbon atoms. A group (a part of carbon atoms may be substituted with a heteroatom, or may be substituted with an ester bond);
R ₄ and R ₅ , which may be the same or different, are alkyl groups having 1 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, or R ₄ and R ₅ together are 20 rings may be formed, and when a ring is formed, some of the carbon atoms may be substituted with heteroatoms,
Further, at least one of E represents a group having a molecular weight of 30 or more,
m is an integer from 0 to 5, n is an integer from 0 to 3, and satisfies m + n> 1. ]

Among _{A is, -R 1, -OR 1, -COR} 1, -SR 1, or shows a _-NR 1 _{R 2,} it is more preferable to use a -R _1. B represents -R ₁ , -OR ₁ , -COR ₁ , -SR ₁ , -CONR ₁ R ₂ or -CN, and it is more preferable to use -R ₁ as in the case of A. Further, G represents a hydrogen atom, —R ₁ , —OR ₁ , —COR ₁ , —SR ₁ , or —NR ₁ R ₂ , and it is more preferable to use —R ₁ in the same manner as A and B.

Among the A, B, and G, the alkyl group represented by R ₁ and R ₂ preferably has 1 to 20 carbon atoms, and more preferably has 1 to 5 carbon atoms. For example, 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, hexyl group, heptyl group, octyl And linear or branched saturated hydrocarbon groups such as a group, isooctyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, isononyl group, decyl group, and isodecyl group. Among these, it is preferable to use a methyl group having 1 carbon atom.

The aryl group represented by R ₁ and R ₂ preferably has 6 to 20 carbon atoms, and more preferably has 6 to 10 carbon atoms. Examples thereof include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

The aralkyl group represented by R ₁ and R ₂ preferably has 7 to 20 carbon atoms, and more preferably has 7 to 12 carbon atoms. Examples include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.

The heterocyclic group represented by R ₁ and R ₂ is a 5-membered ring or more, preferably 5 to 7 members, containing at least one atom of nitrogen atom (N), sulfur atom (S) and oxygen atom (O). A heterocyclic group of a ring. The heterocyclic group may contain a condensed ring, and examples thereof include a pyridyl group, a pyrimidyl group, a furyl group, and a thiophenyl group.

Further, these R ₁ and R ₂ may be substituted with a halogen atom. Examples thereof include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, a chlorophenyl group, and a chlorobenzyl group.

Furthermore, among these R ₁ and R ₂ , the alkyl group and the alkylene part of the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond. Specifically, it may have a linear or branched unsaturated hydrocarbon group such as vinyl group, allyl group, butenyl group, ethynyl group, propynyl group, or a substituent.

  As such, the group represented by A or B is a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group, a 2- (benzoxazol-2′-yl) ethenyl group, or the like. Can be mentioned.

As the ring which R ₁ and R ₂ may form together, and a heterocyclic. Examples of the heterocyclic ring include 5-membered or more, preferably 5- to 7-membered heterocyclic groups containing at least one atom of nitrogen atom (N), sulfur atom (S) and oxygen atom (O). The heterocyclic group may contain a condensed ring, and examples thereof include a piperidine ring, a piperazine ring, a morpholine ring, and a thiomorpholine ring.

  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, the unsaturated bond may be included and the ring may be formed.

  At least one of the groups of E is preferably a group having a molecular weight of 30 or more, and more preferably a molecular weight of 50 or more. Furthermore, the upper limit value of this group is preferably 250 or less, more preferably 150 or less in consideration of sensitivity, solubility in a solvent, and the like. Among these, it is more preferable to use a hydropyranyl group.

E may be the same or different and represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, —OR ₃ , —NR ₄ R ₅ . To express. Of these, -OR ₃ is preferably used. Examples of the alkyl group having 1 to 20 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.

  Further, 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.

R _{3 in} —OR ₃ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a heterocyclic group. 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. For example, a tetrahydrofuryl ring, a tetrahydropyranyl ring and the like can be mentioned. 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 used. Particularly preferred.

  Examples of the heterocyclic ring include 5-membered or more, preferably 5- to 7-membered heterocyclic groups containing at least one atom of nitrogen atom (N), sulfur atom (S) and oxygen atom (O). This heterocyclic group may contain a condensed ring.

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 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.

  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.

  In the general formula (1), it is preferable to use a compound in which m is 1 or more and n is 0.

The compound having such a structure is preferably a compound represented by the following general formula (2). By setting A and B as methyl groups, G as ethyl groups, and n as 0, the sensitivity with respect to light is improved. Further, by adding a bulky pyranyl group to E, it is possible to reduce the production of sublimates upon exposure.

  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 expected, and when it is 1 part by mass or more, the coating film forming ability can be improved and photocuring failure can be prevented. It is.

Further, R ₁ may be a group having a bulky skeleton other than the pyranyl group. For example, a compound represented by the following general formula (3) may be used.

  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 expected, and when it is 1 part by mass or more, the coating film forming ability can be improved and photocuring failure can be prevented. It is.

  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, 6-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-dimethyla Roh-1- (4-morpholinophenyl) - aminoketone compound butane -1 one, and the like.

Among such 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 (4). This is because the sensitivity to light can be further improved by using this compound in combination.

Moreover, even if it uses the compound shown by following General formula (5), the sensitivity with respect to light can be improved more.

  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 expected, and when it is 1 part by mass or less, the film forming ability can be improved and photocuring failure can be prevented. It is.

  Further, 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 formulas (4) and (5) and mercaptobenzimidazole) are used in combination, The ratio is preferably 10:90 to 90:10, particularly preferably 50:50 to 70:30. 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, R ₁ in the formula corresponds to B in the present invention, and R ₂ corresponds to a phenyl group containing E in the present invention. Further, R ₃ corresponds to A in the present invention, and R corresponds to G 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 obtained by reacting (meth) acrylic acid, polyol group Polyurethane (meth) acrylate obtained by reacting (meth) acrylic acid after reacting with a compound having two isocyanate groups; 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 resin An epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as (meth) acrylic acid and the like. Furthermore, a resin obtained by reacting the epoxy (meth) acrylate resin with a polybasic acid anhydride can be used.

  Among them, it is preferable to use an acrylic resin or 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 having the following structure.

ここで、一般式（６）で示される化合物のＸは、一般式（７）で示される基である。

Here, X of the compound represented by the general formula (6) is a group represented by the general formula (7).

  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 acid anhydrides from tetracarboxylic dianhydrides such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, etc. It is a residue excluding physical groups.

  The said photopolymerizable compound is contained in the range of 60 mass parts to 99.9 mass parts with respect to a total of 100 mass parts of the photosensitive composition. By making the content 99.9 parts by mass or less, sufficient heat resistance and chemical resistance can be expected, and by making the content 60 parts by mass or more, the coating film forming ability can be improved and photocuring failure can be prevented. This is because it can.

[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 preferable 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.

  This resin-coated carbon black has lower electrical conductivity than carbon black without resin coating, so there is less current leakage when used as a color filter (black matrix) for liquid crystal displays, etc., and high reliability and low power consumption Can be formed.

  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, a photopolymerizable compound, a photopolymerization initiator, and a colorant are combined in 100 parts by mass. 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. By setting the colorant to 10 parts by mass or more, the light shielding performance of the formed black pattern can be sufficiently obtained. Moreover, it is because sclerosis | hardenability can be improved when it irradiates the light of a predetermined wavelength by making a coloring agent 70 mass parts or less.

  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, a polymer binder may be further contained as a binder in addition to the above components. 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 a range of 0.1 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, as a solvent that can be added to the photosensitive composition, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, 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; aromas such as toluene and 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 and 3-methoxybutyl acetate are used, 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 coloring agent.

  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 placed on 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.

<Example 1>
[Synthesis of photopolymerizable compound]
As a photopolymerizable compound having an ethylenically unsaturated bond, a methacrylic acid / benzyl methacrylate / 1-hydroxyethyl methacrylate copolymer (hereinafter referred to as Compound 1) was synthesized. First, 400 g of propylene glycol monomethyl ether acetate (PGMEA), 75 g of methacrylic acid, 210 g of benzyl methacrylate, 15 g of 2-hydroxyethyl methacrylate, and 5 g of azobisisobutyronitrile are put into a 500 ml four-necked flask, and nitrogen is blown into this. While maintaining at 65 ° C. to 70 ° C., the mixture was stirred for 3 hours to react.

[Photopolymerization initiator]
The photopolymerization initiator was a compound having a structure represented by the following general formula (2). This compound was prepared according to the synthetic scheme described above.

［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, the compound of the following general formula (8) 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.

<Example 2>
A photosensitive composition was prepared in the same procedure as in Example 1 except that the photopolymerizable compound was a compound having the structure represented by the following general formula (Compound 2) (see Table 1).

式中、Ｘは、一般式（７）で示される構造を有する基である。

[Synthesis of photopolymerizable compound]
A cardo resin having a structure represented by the following general formula (6) was synthesized.

In the formula, X is a group having a structure represented by the general formula (7).

  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 (7). Got. The disappearance of the acid anhydride group was confirmed by IR spectrum. This cardo resin was designated as Compound 2.

  Here, the compound 2 is a compound represented by the general formula (6), wherein X is a group represented by the general formula (7), 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.

<Example 3>
In addition to the photopolymerization initiator of Example 2, compound 2- (Dimethylamino) -1- [4- (4-morpholinyl) phenyl] -2- (phenylmethyl) -1-butanone represented by the following general formula (4): (Photopolymerization initiator 2: trade name Irgacure 369, manufactured by Ciba-Geigy Co., Ltd.) was added, and the photosensitive composition according to the present invention was prepared in the same composition and procedure as in Example 2 (see Table 1). .

<Example 4>
A photosensitive composition according to the present invention was prepared in the same procedure as in Example 2 except that mercaptobenzimidazole (photopolymerization initiator 3) was further added to the photopolymerization initiator in Example 2 (see Table 1). ).

<Comparative Example 1>
A photosensitive composition was prepared in the same procedure as in Example 1 except that the photopolymerization initiator was a compound represented by the following general formula (5) (photopolymerization initiator 4: CGI242 manufactured by Ciba Specialty Chemicals) ( (See Table 1).

<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 40, 45, 50, and 60 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 the OD value was measured with an OD measuring device (D-200II, manufactured by Gretag Macbeth). These results are shown in Table 2.

  The straightness of the pattern was determined by visual observation of whether or not the edge of a 10-micron line (line having a width of 10 μm) was 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 2 to 4 were excellent in linearity, and the pigment residue and peeling from the substrate were not confirmed. On the other hand, in Comparative Example 1, it was shown that the pattern peeling was large and the straightness was not good at a low exposure amount.

Further, Table 3 shows the results of comparing the remaining film ratios of Example 2 and Comparative Example 1 when the post-baking temperatures are 200 ° C. and 220 ° C. The remaining film ratio refers to the ratio of the film thickness after post-baking to the film thickness before exposure and post-baking. From this, it was shown that the use of the photosensitive composition according to the present invention has a high residual film ratio of about 2%, which can suppress generation of sublimates after post-baking.

In addition, Example 2 and Comparative Example 1 were examined for the generation of sublimates during exposure. After exposure with 70 sheets 100 (mJ / cm ² ), the mask was washed with a predetermined amount of tetrahydrofuran (THF). Next, the amount of the mask deposit was determined using gel permeation chromatography (manufactured by Shimadzu Corporation). Comparison of the amount of generated sublimates was judged from the peak area around 16 minutes on the chart. The results are shown in Table 4. From this, it was shown that the direction which uses the photosensitive composition concerning this invention can suppress generation | occurrence | production of a sublimation.

Claims (13)

Containing a photopolymerizable compound, a photopolymerization initiator, and a colorant;
The photosensitive composition containing the compound shown by following General formula (1) as said photoinitiator.

[Where:
A is _{-R 1, -OR 1, -COR 1} , -SR 1, or represents _-NR 1 _{R 2,}
B is _{-R 1, -OR 1, -COR 1} , -SR 1, -CONR 1 R 2 or represents -CN,
G represents a hydrogen _{atom, -R 1, -OR 1, -COR} 1, -SR 1, or _-NR 1 _{R 2,}
R ₁ and R ₂ each independently represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, which may be substituted with a halogen atom and / or a heterocyclic group, The alkylene part of the group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond, and R ₁ and R ₂ may be combined to form a ring;
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;
E represents the same or different 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 ₃ , —NR ₄ R ₅ . ,
Here, R ₃ represents an alkyl group having 1 to 20 carbon atoms (a part of carbon atoms may be substituted with a heteroatom), a cycloalkyl group having 3 to 20 carbon atoms (a part of carbon atoms is heterogeneous). Which may be substituted with atoms)
R ₄ and R ₅ , which may be the same or different, are alkyl groups having 1 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, or R ₄ and R ₅ together are 20 rings may be formed, and when a ring is formed, some of the carbon atoms may be substituted with heteroatoms,
Further, at least one of E represents a group having a molecular weight of 30 or more,
m is an integer from 0 to 5, n is an integer from 0 to 3, and satisfies m + n> 1. ] 2. The photosensitive composition according to claim 1, wherein E is any one of an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, —OR ₃ , and —NR ₄ R ₅ . .   The photosensitive composition according to claim 1, wherein m is 1 or more and n is 0.   E is a C7-C12 alkyl group, The photosensitive composition in any one of Claim 1 to 3. 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 (2).

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 (3).

The said photoinitiator is a photosensitive composition in any one of Claim 1 to 6 which further contains the compound shown by following General formula (4).

The photosensitive composition according to any one of claims 1 to 7, wherein the photopolymerization initiator further comprises 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 includes a resin having a cardo structure in a molecule and having at least one ethylenic double bond in the molecule.   The photosensitive composition according to claim 1, wherein the colorant contains carbon black.