TWI438570B - Photosensitive coloring composition and color filter - Google Patents

Description

Photosensitive coloring composition and color filter

The present invention relates to a photosensitive coloring composition, and more particularly to a filter segment and a black color, such as red, green, and blue, in a color filter used in a liquid crystal display device or a solid-state imaging device. A highly sensitive photosensitive coloring composition which is useful for forming a black matrix or the like. Further, the present invention relates to a color filter formed using the photosensitive coloring composition.

The color filter is configured by arranging two or more fine strip-shaped (striped) filter segments of different hue in parallel or in a cross on the surface of a transparent substrate such as glass, or by arranging fine filter segments in the vertical and horizontal directions. It is configured by arranging in a predetermined arrangement. The filter section has a fine size of several micrometers to several hundred micrometers, and each hue is neatly arranged in a prescribed arrangement.

Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for orienting the liquid crystal in a certain direction is further formed on the transparent electrode. In order to sufficiently obtain the properties of the transparent electrode and the alignment film, the formation of these transparent layers is generally required to be carried out at a high temperature of 200 ° C or higher, preferably 230 ° C or higher.

Therefore, as a method of producing a color filter, a method of using a pigment dispersion method in which a pigment excellent in light resistance and heat resistance is used as a coloring material has been mainstream.

When a pigment dispersion method is used, a photosensitive coloring composition (pigment resist) in which a pigment is dispersed in a photosensitive resin solution is applied onto a transparent substrate such as glass, and the solvent is removed by drying, and then a color filter is performed. The pattern of the color of the device is exposed, and then the unexposed portion is removed by the developing step to form a pattern of the first color, and after the processing such as heating as necessary, the same operation is sequentially repeated for all the color filters. A color filter can be manufactured.

In recent years, color liquid crystal display devices have formed a huge market as integrated notebook computers for color liquid crystal televisions, car navigation systems, and liquid crystal display devices, and as displays for desktop computers with energy saving and space saving features, and televisions. The machine has also begun to spread. The color liquid crystal display device has been attracting attention as a display device in place of the conventional CRT. However, the current state of the art is that the color reproduction characteristics of the liquid crystal display device are inferior to those of the CRT.

Therefore, in the color filter in which the color filter sections are arranged, the requirements for high color reproducibility are continuously improved.

Further, in order to improve the contrast, a black matrix is usually disposed between the filter nodes of the color filters, and the material for forming the black matrix has been used in recent years from the viewpoints of environmental problems, low reflection, and cost reduction. A resin-made black matrix in which a light-shielding pigment is dispersed in a resin is attracting attention instead of a black matrix made of metal chromium. However, in the black matrix made of resin, there is a problem that the light shielding property (optical density) is lower than that of the black matrix made of metal chromium.

In order to improve the color reproduction characteristics of the color filter and to improve the light shielding property of the black matrix, it is necessary to increase the pigment content or increase the film thickness in the photosensitive coloring composition. However, in the method of increasing the pigment content, there are problems such as a decrease in sensitivity, deterioration in developability and resolution. On the other hand, in the method of increasing the film thickness, there is a problem that the exposure light cannot reach the bottom of the film, and the shape of the pattern is poor.

In order to solve such problems, it is necessary to increase the sensitivity of the photosensitive coloring composition, and usually (1) impart a reactive double bond to the resin, (2) select a photopolymerization initiator, a sensitizer, or perform a photopolymerization initiator, The increment of the sensitizer, (3) the selection of the monomer or the increment of the monomer, etc., as examples, Patent Documents 1 and 2 can be cited.

Prior art literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2001-264530

Patent Document 2: Japanese Laid-Open Patent Publication No. 2003-156842

However, if only a resin double bond is imparted, and a photopolymerization initiator, a sensitizer, and a monomer are selected, the effect of improving sensitivity is limited. In particular, when the photopolymerization initiator is added, it is colored by the color peculiar to the photopolymerization initiator, and the heat resistance is lowered, the light transmittance is lowered, and the resolution is lowered. In addition, when the monomer is increased, problems such as stickiness are generated.

Therefore, an object of the present invention is to provide a photosensitive material which has high sensitivity, high residual film ratio, high linearity, pattern shape, resolution, development resistance, and chemical resistance even when the film content is high or the film thickness is thick. A coloring composition, and a color filter formed using the photosensitive coloring composition.

The photosensitive coloring composition of the present invention is characterized in that it has high sensitivity and excellent linearity, pattern shape, resolution, development resistance, and chemical resistance, and is characterized by using the following general formula (1) or (11). The photopolymerization initiator represented.

In other words, the photosensitive coloring composition of the present invention contains the photopolymerization initiator (A) represented by the following formula (1) or (11), and contains the resin (B), the photopolymerizable compound (C), and A photosensitive coloring composition of the pigment (D).

General formula (1)

(In the formula (1), R ₁ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. An aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, Substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinylene, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted Anthracenyl, substituted or unsubstituted anthraceneoxy, substituted or unsubstituted amino group, substituted or unsubstituted phosphinoyl, substituted or unsubstituted carbamoyl, or substituted or not Substituted sulfamoyl.

R ₂ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted Heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted An arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted amine group.

R ₃ to R ₅ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. Aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl sulphur A substituted, unsubstituted or unsubstituted thio group, or a substituted or unsubstituted amine group.

R ₆ to R ₉ each independently represent a hydrogen atom, a halogen atom, a cyano group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substitution. Or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted Arylthio, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinylene, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl A substituted or unsubstituted amino group or a substituent of the following formula (2).

General formula (2)

(In the formula (2), R _{1 '} and R _{2' are} synonymous with R ₁ and R ₂ .)

R ₁₀ to R ₁₄ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a halogenated alkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substitution or An unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted indenyl group, but R ₁₀ to R _{14 are} not all hydrogen atoms at the same time. Further, at least one of R ₁₀ to R ₁₄ is a nitro group or the following formula (3). )

General formula (3)

(In the formula (3), R ₁₅ to R ₁₉ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a halogenated alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substitution or Unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl sulphide a substituted or unsubstituted arylthio group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted amine group.))

General formula (11)

(In the formula (11), R ₅₁ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group. Oxyl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkyl group Sulfhydryl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted An oxiranyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted phosphino group, a substituted or unsubstituted aminomethyl fluorenyl group, or a substituted or unsubstituted amine sulfonyl group.

R ₅₂ represents an alkyl group having 1 to 20 carbon atoms which is substituted by a cycloalkyl group.

R ₅₃ to R ₅₅ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. Aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl sulphur A substituted, unsubstituted or unsubstituted thio group, or a substituted or unsubstituted amine group.

R ₅₆ to R ₅₈ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a halogenated alkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinylene group, a substitution or An unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted indenyl group.

R ₅₉ to R ₆₃ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a halogenated alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substitution. Or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted An arylthio group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted amine group.

R ₆₄ represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substitution or Unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted A mercapto group, or a substituted or unsubstituted amine group. )

Further, the present invention relates to the aforementioned photosensitive coloring composition characterized by further containing another photopolymerization initiator (Y).

Further, the present invention relates to the photosensitive coloring composition described above, characterized in that the other photopolymerization initiator (Y) contains at least one selected from the group consisting of an acetophenone-based compound, a phosphine-based compound, and an imidazole-based compound. compound of.

Further, the present invention relates to the aforementioned photosensitive coloring composition characterized by further containing a polyfunctional thiol (F).

Further, the present invention relates to a color filter characterized by having a filter section and/or a black matrix formed of the above-mentioned photosensitive coloring composition on a transparent substrate.

The photosensitive coloring composition of the present invention has a high sensitivity even when a pigment content is high or a film thickness of each color filter segment and black matrix is thick, by using a specific oximeester compound as a photopolymerization initiator. Moreover, it is possible to form respective color filter sections and black matrix patterns having excellent linearity, pattern shape, resolution, development resistance, and chemical resistance.

Therefore, a high-quality color filter can be obtained by using the photosensitive coloring composition of the present invention.

First, the photosensitive coloring composition of the present invention will be specifically described.

The photosensitive coloring composition of the present invention contains the photopolymerization initiator (A) represented by the above formula (1) or (11), and contains the resin (B), the photopolymerizable compound (C), and the pigment (D). .

The photopolymerization initiator (A) containing the compound represented by the above formulas (1) and (11) can provide a coating film having high sensitivity and particularly high residual film ratio, and thus excellent color filter production stability can be obtained. Photosensitive coloring composition. By using the photosensitive coloring composition containing the photopolymerization initiator, a filter segment and a black matrix having excellent linearity, pattern shape, resolution, development resistance, and chemical resistance can be formed.

Further, by using other initiators in combination, more excellent chemical resistance can be obtained.

<Photopolymerization initiator (A)>

The photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention is a compound represented by the formula (1) or (11).

First, the photopolymerization initiator (A) represented by the formula (1) will be described.

General formula (1)

In the formula (1), R ₁ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group. a substituted, unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkyl sulfinic acid Mercapto, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted An oxo group, a substituted or unsubstituted amino group, a substituted or unsubstituted phosphino group, a substituted or unsubstituted aminomethyl fluorenyl group, or a substituted or unsubstituted sulfonyl group.

Examples of the substituted or unsubstituted alkenyl group in R ₁ include a linear, branched, monocyclic or condensed polycyclic alkenyl group having 1 to 18 carbon atoms, and these structures may have Specific examples of the plurality of carbon-carbon double bonds include a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, and a 1-pentenyl group. 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, cyclopentyl The alkenyl group, the cyclohexenyl group, the 1,3-butadienyl group, the cyclohexadienyl group, the cyclopentadienyl group, and the like are not limited thereto.

The substituted or unsubstituted alkyl group in R ₁ may, for example, be a linear, branched, monocyclic or condensed polycyclic alkyl group having a carbon number of 1 to 18; or a carbon number of 2 to 18, and A linear, branched, monocyclic or condensed polycyclic alkyl group interrupted by one or more -O- depending on the case. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl and g. Base, octyl, decyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, second butyl, tert-butyl, second pentyl , third amyl, third octyl, neopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, borneol, 4-mercaptocyclohexyl, etc., but It is not limited to such groups. Further, specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and interrupted by one or more -O- depending on the case include -CH ₂ -O-CH ₃ and -CH _{2 .} -CH ₂ -O-CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ , -(CH ₂ -CH ₂ -O) _n -CH ₃ (here, n is 1 to 8), -(CH ₂ -CH ₂ -CH ₂ -O) _m -CH ₃ (here, m is 1 to 5), -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₃ -, -CH ₂ -CH-(OCH ₃ ) ₂ or the like, but is not limited to such groups.

Specific examples of the monocyclic or condensed polycyclic alkyl group having a carbon number of 2 to 18 and interrupted by one or more -O- as the case may be the following groups, but are not limited thereto. .

Examples of the substituted or unsubstituted alkoxy group in R ₁ include a linear, branched, monocyclic or condensed polycyclic alkoxy group having a carbon number of 1 to 18; or a carbon number of 2 to 18 And a linear, branched, monocyclic or condensed polycyclic alkoxy group interrupted by one or more -O-, as the case may be. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxy group having 1 to 18 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyl group. Oxy, hexyloxy, heptyloxy, octyloxy, decyloxy, decyloxy, dodecyloxy, octadecyloxy, isopropoxy, isobutoxy, isopentyloxy, a second butoxy group, a third butoxy group, a second pentyloxy group, a third pentyloxy group, a third octyloxy group, a neopentyloxy group, a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, Examples of the cyclohexyloxy group, the adamantyloxy group, the norbornyloxy group, the borneoloxy group, the 4-decylcyclohexyloxy group, and the like are not limited thereto. Further, specific examples of the linear or branched alkoxy group having a carbon number of 2 to 18 and interrupted by one or more -O- as the case may be -O-CH ₂ -O-CH ₃ , -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₃ , -O-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ , -O-(CH ₂ -CH ₂ -O) _n -CH ₃ (here, n is 1 to 8), -O-(CH ₂ -CH ₂ -CH ₂ -O) _m -CH ₃ (here, m is 1 to 5), -O-CH ₂ - CH(CH ₃ )-O-CH ₂ -CH ₃ -, -O-CH ₂ -CH-(OCH ₃ ) ₂ or the like, but is not limited thereto.

Specific examples of the monocyclic or condensed polycyclic alkoxy group having a carbon number of 2 to 18 and interrupted by one or more -O- as the case may be the following groups, but are not limited thereto. group.

Examples of the substituted or unsubstituted aryl group in R ₁ include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms, and specific examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. 1-fluorenyl, 9-fluorenyl, 2-phenanthryl, 3-phenanthryl, 9-phenanthryl, 1-pyrenyl, 5-cyphthene, 5-pyrene 1-indenyl, 2-azulenyl, 1-acenaphthyl, 2-indenyl, 9-indenyl, 3-indenyl, o-tolyl, m-tolyl, P-tolyl, 2,3-xylyl, 2,5-dimethylphenyl, 2,4,6-trimethyl (mesityl), p-cumenyl, p-dodecylbenzene Base, p-cyclohexylphenyl, 4-biphenylyl, o-fluorophenyl, m-chlorophenyl, p-bromophenyl, p-hydroxyphenyl, m-carboxyphenyl, o-nonylphenyl, p-cyanophenyl, The m-nitrophenyl group, the m-azidophenyl group and the like are not limited to these groups.

The substituted or unsubstituted aryloxy group in R ₁ may, for example, be a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples thereof include a phenoxy group, a 1-naphthyloxy group, and 2 -naphthyloxy, 9-decyloxy, 9-phenanthryloxy, 1-decyloxy, 5-fused tetraphenoxy, 1-decyloxy, 2-decyloxy, 1-decyloxy, 9 - an oxime or the like, but is not limited to such a group.

Examples of the substituted or unsubstituted heterocyclic group in R ₁ include an aromatic or aliphatic heterocyclic group having a carbon number of 4 to 24 containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, and examples thereof include 2- 2-thienyl, 2-benzothienyl, naphtho[2,3-b]thienyl, 3-thianthrenyl, 2-thianthrenyl, 2 -furanyl, 2-benzofuranyl, pyranyl, isobenzofuranyl, chromenyl, xanthenyl, brown Phenoxylinyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyridyl Pyrazinyl, pyrimidinyl, anthracene Pyridazinyl, indolizinyl, isoindolyl, 3H-mercapto, 2-mercapto, 3-mercapto, 1H-carbazolyl, purinyl 4H-quine (4H-quinolizinyl), isoquinolinyl, quinolinyl, anthracene (phthalazinyl), naphthyridinyl, quinine Quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, 4aH-carbazolyl, 2-oxazolyl, 3-oxazolyl, β-carboline Phenanthridinyl, 2-acridinyl, perimidinyl, phenanthrolinyl, brown Phenazinyl, arsenic Phenasazinyl, isothiazolyl, thiophene Phenothiazinyl, different Oxazolinyl, furazanyl, 3-morphine 3-phenoxazinyl, isochromanyl, chromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl , pyrazolinyl, piperidinyl, piperidine Piperazinyl, porphyrinyl, isoindolyl, quinuclidinyl, morpholinyl, thioxanthone, 4-quinolyl, 4-isoquinolinyl, 3 -morphine 2-morphine Thiyl, 3-coumarin, etc., but are not limited to these groups.

Examples of the substituted or unsubstituted heterocyclic oxy group in R ₁ include a monocyclic or condensed polycyclic heterocyclic oxy group having a carbon number of 4 to 18 and a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Specific examples thereof include 2-furanyloxy group, 2-thienyloxy group, 2-decyloxy group, 3-decyloxy group, 2-benzofuranyloxy group, 2-benzothiophenoxy group, and 2- The oxazolyloxy group, the 3-oxazolyloxy group, the 4-oxazolyloxy group, the 9-acridinyloxy group and the like are not limited to these groups.

The substituted or unsubstituted alkylthio group in R ₁ may, for example, be a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 8 carbon atoms, and as a specific example, Listed, but not limited to, methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, octylthio, decylthio, dodecylthio, octadecylthio, and the like Such groups.

The substituted or unsubstituted arylthio group in R ₁ may, for example, be a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group and a 1-naphthalene group. The thio group, the 2-naphthylthio group, the 9-fluorenylthio group, the 9-phenanthrylthio group and the like are not limited to these groups.

The substituted or unsubstituted alkylsulfinyl group in R ₁ is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. Specific examples thereof include methylsulfinyl group and ethyl group. Sulfonyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, hexylsulfinyl, cyclohexylsulfinyl, octylsulfinyl, 2-ethyl Hexylsulfinyl, fluorenylsulfinyl, dodecylsulfinyl, octadecylsulfinyl, cyanomethylsulfinyl, methoxymethylsulfinyl, etc. However, it is not limited to such groups.

The substituted or unsubstituted arylsulfinyl group in R ₁ is preferably an arylsulfinylene group having a carbon number of 6 to 30, and specific examples thereof include a phenylsulfinyl group and a 1-naphthalene group. Isosulfonyl, 2-naphthylsulfinyl, 2-chlorophenylsulfinyl, 2-methylphenylsulfinyl, 2-methoxyphenylsulfinyl, 2- Butoxyphenylsulfinyl, 3-chlorophenylsulfinyl, 3-trifluoromethylphenylsulfinyl, 3-cyanophenylsulfinyl, 3-nitrophenyl Sulfosyl, 4-fluorophenylsulfinyl, 4-cyanophenylsulfinyl, 4-methoxyphenylsulfinyl, 4-methylthiophenylsulfinyl And 4-phenylthiophenylsulfinyl group, 4-dimethylaminophenylsulfinyl group, etc., but it is not limited to such a group.

The substituted or unsubstituted alkylsulfonyl group in R ₁ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples thereof include a methylsulfonyl group and an ethylsulfonyl group. Propylsulfonyl, isopropylsulfonyl, butylsulfonyl, hexylsulfonyl, cyclohexylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, decylsulfonyl And a dodecylsulfonyl group, an octadecylsulfonyl group, a cyanomethylsulfonyl group, a methoxymethylsulfonyl group, etc., but it is not limited to such a group.

The substituted or unsubstituted arylsulfonyl group in R ₁ is preferably an arylsulfonyl group having a carbon number of 6 to 30, and specific examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonium group. , 2-naphthylsulfonyl, 2-chlorophenylsulfonyl, 2-methylphenylsulfonyl, 2-methoxyphenylsulfonyl, 2-butoxyphenylsulfonyl , 3-chlorophenylsulfonyl, 3-trifluoromethylphenylsulfonyl, 3-cyanophenylsulfonyl, 3-nitrophenylsulfonyl, 4-fluorophenylsulfonyl , 4-cyanophenylsulfonyl, 4-methoxyphenylsulfonyl, 4-methylthiophenylsulfonyl, 4-phenylthiophenylsulfonyl, 4-dimethyl The aminoaminophenylsulfonyl group or the like is not limited to these groups.

Examples of the substituted or unsubstituted fluorenyl group in R ₁ include a linear hydroxy group having a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic group having 1 to 18 carbon atoms. a carbonyl group substituted with an alkoxy group having 2 to 20 carbon atoms, a carbonyl group having a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms, a monocyclic or condensed carbon number of 6 to 18 a polycyclic aryloxy-substituted carbonyl group having a carbonyl group having a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms and containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom; as a specific example, Examples thereof include a mercapto group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a pivaloyl group, a lauryl group, a myristyl group, and a palmitoyl group. , stearyl sulfhydryl, cyclopentyl carbonyl, cyclohexylcarbonyl, acryl fluorenyl, methacryl fluorenyl, crotonyl, isocrotonyl, oleyl, cinnamylbenzhydryl, methoxycarbonyl , ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, hexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, octadecyloxycarbonyl , trifluoromethoxycarbonyl, benzamyl, toluoyl, 1-naphthoyl, 2-naphthylmethyl, 9-fluorenylcarbonyl, phenoxycarbonyl , 4-methylphenoxycarbonyl, 3-nitrophenoxycarbonyl, 4-dimethylaminophenoxycarbonyl, 2-methylthiophenoxycarbonyl, 1-naphthylmethoxycarbonyl , 2-naphthylmethoxycarbonyl, 9-decyloxycarbonyl, 3-furoyl, 2-thenoyl, nicotinoyl, isoniazid An alkali sulfhydryl group or the like is not limited to these groups.

Examples of the substituted or unsubstituted fluorenyloxy group in R ₁ include a decyloxy group having 2 to 20 carbon atoms, and specific examples thereof include an ethyl oxy group, a propyl oxy group, a butyl oxy group, and a pentylene group. An oxy group, a trifluoromethylcarbenyloxy group, a benzamidineoxy group, a 1-naphthalenecarbonyloxy group, a 2-naphthalenecarbonyloxy group, or the like.

Examples of the substituted or unsubstituted amino group in R ₁ include an amine group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, and a benzylamine. Base, dibenzylamine group, and the like.

Here, examples of the alkylamine group include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, and the like. Mercaptoamine, mercaptoamine, dodecylamino, octadecylamino, isopropylamino, isobutylamino, isoamylamino, second butylamino, Tributylamine, second amylamino, third amylamino, third octylamino, neopentylamino, cyclopropylamino, cyclobutylamino, cyclopentylamino a cyclohexylamino group, a cycloheptylamino group, a cyclooctylamino group, a cyclododecylamino group, a 1-adamantanyl group, a 2-adamantanyl group, or the like, but is not limited thereto. .

Examples of the dialkylamino group include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a dipentylamino group, a dihexylamino group, a diheptylamino group, Dioctylamino, dinonylamino, dimethylamino, di(dodecyl)amino, dioctadecylamino, diisopropylamino, diisobutylamine Base, diisoamylamino, methylethylamino, methylpropylamino, methylbutylamino, methyl isobutylamino, cyclopropylamino, pyrrolidinyl, piperidine Base Base or the like, but is not limited to such groups.

Examples of the arylamine group include an anilino group, a 1-naphthylamino group, a 2-naphthylamino group, an o-toluidino group, a m-toluidine group, a p-toluidine group, a 2-biphenylamino group, and 3 a benzidine group, a 4-biphenylamino group, a 1-nonylamino group, a 2-nonylamino group, a 2-thiazolylamino group, a p-triphenylamine group, or the like, but is not limited thereto.

Examples of the diarylamine group include a diphenylamino group, a xylylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group, but are not limited thereto. And other groups.

Examples of the alkylarylamine group include N-methylanilino, N-methyl-2-pyridyl, N-ethylanilino, N-propylanilino, N-butylanilino, N- Isopropyl, N-pentylanilino, N-ethylanilino, N-methyl-1-naphthylamine, etc., but are not limited to these groups.

The substituted or unsubstituted phosphino group in R ₁ may, for example, be a phosphino group having 2 to 50 carbon atoms, and specific examples thereof include a dimethylphosphino group, a diethylphosphino group, a dipropylphosphino group, and a second group. a phenylphosphino group, a dimethoxyphosphino group, a diethoxyphosphino group, a dibenzoylphosphino group, a bis(2,4,6-trimethylphenyl)phosphino group, etc., but is not limited thereto These groups.

Examples of the substituted or unsubstituted aminomethyl fluorenyl group in R ₁ include an aminomethyl fluorenyl group having 1 to 30 carbon atoms. Specific examples thereof include N-methylaminocarbamyl group and N-B. Aminomethylmercapto, N-propylaminocarbamimidyl, N-butylaminomethylguanidino, N-hexylaminomethylguanidinyl, N-cyclohexylaminomethylguanidinyl, N-octyl Aminomethyl fluorenyl, N-decylaminomethyl fluorenyl, N-octadecylaminomethyl fluorenyl, N-phenylaminomethyl fluorenyl, N-2-methylphenylaminoformamidine , N-2-chlorophenylaminocarboxamyl, N-2-isopropoxyphenylaminocarboxamyl, N-2-(2-ethylhexyl)phenylaminocarbamyl, N-3-chlorophenylaminocarbazinyl, N-3-nitrophenylaminocarbamimidyl, N-3-cyanophenylaminocarboxamyl, N-4-methoxyphenyl Aminomethyl sulfhydryl, N-4-cyanophenylaminocarbamimidyl, N-4-methylthiophenylaminocarbamimidyl, N-4-phenylthiophenylaminocarbamidine , N-methyl-N-phenylaminocarbamimidyl, N,N-dimethylaminocarbamimidyl, N,N-dibutylaminomethylguanidinyl, N,N-diphenyl An aminomethylmercapto group or the like is not limited to these groups.

Examples of the substituted or unsubstituted sulfonyl group in R ₁ include an amine sulfonyl group having a carbon number of from 0 to 30, and specific examples thereof include an amine sulfonyl group, an N-alkylamine sulfonyl group, and N. An arylamine sulfonyl group, an N,N-dialkylamine sulfonyl group, an N,N-diarylamine sulfonyl group, an N-alkyl-N-arylamine sulfonyl group, and the like. More specifically, it may, for example, be N-methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-butylaminesulfonyl, N-hexylaminesulfonyl , N-cyclohexylamine sulfonyl, N-octylamine sulfonyl, N-2-ethylhexylamine sulfonyl, N-decylamine sulfonyl, N-octadecylamine sulfonyl , N-phenylamine sulfonyl, N-2-methylphenylamine sulfonyl, N-2-chlorophenylamine sulfonyl, N-2-methoxyphenylamine sulfonyl, N -2-Isopropoxyphenylaminocarbamyl, N-3-chlorophenylamine sulfonyl, N-3-nitrophenylamine sulfonyl, N-3-cyanophenylamine sulfonate Sulfhydryl, N-4-methoxyphenylamine sulfonyl, N-4-cyanophenylamine sulfonyl, N-4-dimethylaminophenylamine sulfonyl, N-4- Methylthiophenylamine sulfonyl, N-4-phenylthiophenylamine sulfonyl, N-methyl-N-phenylamine sulfonyl, N,N-dimethylamine sulfonate The group is N,N-dibutylaminesulfonyl, N,N-diphenylaminesulfonyl or the like, but is not limited thereto.

R ₂ is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted Heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted An arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted amine group.

As a substituted or unsubstituted alkenyl group in R ₂ , a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or not Substituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkylsulfinyl group, substituted or Unsubstituted arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted amine, and the substituents R ₁ or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or Unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkylsulfinyl group, substituted Or unsubstituted arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted Sulfo acyl group, a substituted or unsubstituted acyl group, and a substituted or unsubstituted amine synonymous.

R ₃ to R ₅ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. Aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl sulphur A substituted, unsubstituted or unsubstituted thio group, or a substituted or unsubstituted amine group.

Examples of the halogen atom in R ₃ to R ₅ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group in R ₃ to R ₅ , a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted fluorenyl group, and a substituted or An unsubstituted amino group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group in the above R ₁ An aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted fluorenyl group And synonymous with substituted or unsubstituted amine groups.

R ₆ to R ₉ each independently represent a hydrogen atom, a halogen atom, a cyano group, a halogenated alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. Aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl sulfide Alkyl, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinylene, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, substituted or An unsubstituted amino group or a substituent of the following formula (2).

General formula (2)

(In the formula (2), R _{1 '} and R _{2' are} synonymous with R ₁ and R ₂ .)

The halogen atom in R ₆ to R ₉ has the same meaning as the halogen atom in R ₃ to R ₆ .

Examples of the halogenated alkyl group in R ₆ to R ₉ include an alkyl group having 1 to 15 carbon atoms in which all hydrogen atoms are substituted by the above halogen atom, and specific examples thereof include a trifluoromethyl group, a trichloromethyl group, and a trisium group. Bromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl, trifluorodibromoethyl, tribromodiiodoethyl, heptafluoropropyl, heptachlor Propyl, heptabromopropyl, nonafluorobutyl, nonachlorobutyl, nonabromobutyl, undecafluoropentyl, undecylpentyl, undecabromopentyl, decafluorohexyl, tridecylhexyl , pentafluoroheptyl, heptadecafluorooctyl, nonadecylfluorodecyl, hexadecafluoroindenyl, hexadecafluoroundecyl, twenty-fifylfluorododecyl, etc., but not limited thereto These groups.

The halogenated alkyl group is more preferably a trifluoromethyl group or a pentafluoroethyl group from the viewpoint of synthesis and properties of the coloring composition.

a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group in R ₆ to R ₉ , a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, and a substituted or unsubstituted amine group, and a substitution in the aforementioned R ₁ Or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heteroepoxy Alkenyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted aryl Sulfhydryl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, and substituted or unsubstituted On behalf of the amine synonymous.

R ₁₀ to R ₁₄ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a halogenated alkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substitution or An unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted indenyl group, but R ₁₀ to R _{14 are} not all hydrogen atoms at the same time.

a haloalkyl group in R ₁₀ to R ₁₄ which has the same meaning as the above haloalkyl group in R ₆ to R ₉ , a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or not a substituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, and a substituted or unsubstituted indenyl group, and a substituted or unsubstituted alkylsulfinyl group in the above R ₁ , substituted or unsubstituted An arylsulfinylene group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, and a substituted or unsubstituted fluorenyl group are synonymous.

The substituent in R ₁₀ to R ₁₄ is preferably a nitro group or a substituted or unsubstituted fluorenyl group, and more preferably a nitro group or a general formula, from the viewpoint of synthesis and characteristics as a coloring composition. (3) The situation.

General formula (3)

(In the formula (3), R ₁₅ to R ₁₉ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a halogenated alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substitution or Unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl sulphide a substituted or unsubstituted arylthio group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted amine group.)

a haloalkyl group in R ₁₅ to R ₁₉ which has the same meaning as the above haloalkyl group in R ₆ to R ₉ , a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or Unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl group a thiol group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted amino group, and a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group in R ₁ , substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylthio group, substituted or not A substituted arylthio group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted amine group are synonymous.

Here, the substitution position of the nitro group in R ₁₀ to R ₁₄ or the substituent represented by the formula (3) is more preferably a substitution at R ₁₂ from the viewpoint of synthesis and characteristics as a coloring composition.

The hydrogen atom of the substituent in the above R ₁ to R ₁₉ may be further substituted with another substituent.

Examples of the other substituent include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group; a phenoxy group; An aryloxy group such as a tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; an anthraceneoxy group such as an ethoxy group, a propenyloxy group or a benzhydryloxy group; a thiol group such as a benzyl group, a benzhydryl group, an isobutyl fluorenyl group, an acryl fluorenyl group, a methacryl fluorenyl group or a methoxalyl group; an alkylthio group such as a methylthio group or a t-butylthio group; An arylthio group such as a thiol group or a p-tolylthio group; an alkylamino group such as a methylamino group or a cyclohexylamino group; a dimethylamino group, a diethylamino group, a morpholino group, a dialkylamino group such as piperidinyl; an arylamine group such as a phenylamino group or a p-tolylamino group; an alkyl group such as a methyl group, an ethyl group, a t-butyl group or a dodecyl group; a phenyl group and a p-toluene group; An aryl group such as a dimethyl group, a dimethylphenyl group, a cumyl group, a naphthyl group, an anthranyl group or a phenanthryl group; a heterocyclic group such as a furyl group or a thienyl group; and, in addition, a hydroxyl group, a carboxyl group, a formazan group and an anthracene group. , sulfo, methanesulfonyl, p-toluenesulfonyl, amine, nitro, cyano, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphonic acid subunit (phosphinico), phosphonyl, trimethylammonium, dimethylindenyl, triphenylphenacylphosphoniumyl, and the like.

The photopolymerization initiator (A) represented by the formula (1) contained in the photosensitive coloring composition of the present invention is characterized in that an oxime ester photopolymerization initiator is a benzene group in the N-phenylcarbazole skeleton. Substituted with an electron withdrawing substituent. It is generally considered that the oxime ester photopolymerization initiator partially decomposes the oxime ester by absorbing ultraviolet rays to form an imino radical and an alkoxy radical, and further decomposes the active species radical to cause a reaction, but The photopolymerization initiator (A) contained in the photosensitive coloring composition of the invention has a structure represented by the formula (1), and the decomposition efficiency by ultraviolet irradiation is extremely high, and can be reduced to a small extent. The amount of exposure forms a pattern.

The photopolymerization initiator (A) represented by the formula (1) of the present invention has higher sensitivity than the conventional initiator, which may be due to the following three reasons, but the details thereof are not clear.

As a first reason, the photopolymerization initiator (A) represented by the formula (1) of the present invention has excellent ultraviolet absorption properties because of the structure represented by the formula (1), so that it can be absorbed extremely well. The energy of the energy line given. Further, it is considered that since the obtained energy is effectively used for the decomposition of the oxime ester site, it is rapidly decomposed by the irradiation of the energy ray, and a large amount of radicals can be generated instantaneously.

For the second reason, it is considered that the photopolymerization initiator (A) represented by the formula (1) of the present invention is derived from the decomposition of an imine radical generated by ultraviolet rays to an active species radical. The structure represented by the general formula (1) is very rapid. If the generated imino radical is quasi-stable, the decomposition becomes slow, the amount of active radicals is reduced, and the chemical structure of the ultraviolet absorbing portion has a large influence. In addition, the photopolymerization initiator (A) represented by the formula (1) of the present invention has a structure represented by the formula (1), and thus the imino radical generated by decomposition by light irradiation is considered. The decomposition is very rapid and results in a large amount of free radicals.

In addition, as described above, the photopolymerization initiator (A) represented by the formula (1) of the present invention suppresses recombination because the decomposition of the imino radical is extremely rapid. When there is a lot of recombination, the active species produced by the decomposition is reduced, and thus the function as a radical polymerization initiator is lowered.

The third cause is a synergistic effect between the effect of the carbazole substituted with an electron-withdrawing substituent which exhibits excellent ultraviolet absorption performance and the effect of the keto-type oxime ester.

Next, the photopolymerization initiator (A) represented by the formula (11) will be described.

General formula (11)

In the formula (11), R ₅₁ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group. a substituted, unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkyl sulfinic acid Mercapto, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted An oxo group, a substituted or unsubstituted amino group, a substituted or unsubstituted phosphino group, a substituted or unsubstituted aminomethyl fluorenyl group, or a substituted or unsubstituted sulfonyl group.

Among them, an alkyl group is particularly preferred from the viewpoint of synthesis and characteristics as a coloring composition.

R ₅₂ represents an alkyl group having 1 to 20 carbon atoms which is substituted by a cycloalkyl group.

The cycloalkyl group may, for example, be a cycloalkyl group having a carbon number of 3 to 20 such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a cyclooctadecyl group.

Among them, when R ₅₂ is an alkyl group substituted by a cyclopentyl group, it is advantageous from the viewpoint of synthesis of a photopolymerization initiator and stability.

R ₅₃ to R ₅₅ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. Aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl sulphur A substituted, unsubstituted or unsubstituted thio group, or a substituted or unsubstituted amine group.

Among them, a hydrogen atom is particularly preferred from the viewpoint of synthesis and characteristics as a coloring composition.

R ₅₆ to R ₅₈ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a halogenated alkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinylene group, a substitution or An unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted indenyl group.

Among them, a hydrogen atom is particularly preferred from the viewpoint of synthesis and characteristics as a coloring composition.

R ₅₉ to R ₆₃ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a halogenated alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substitution. Or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted An arylthio group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted amine group.

Among them, a hydrogen atom or an alkyl group is particularly preferred from the viewpoint of synthesis and characteristics as a coloring composition.

R ₆₄ represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substitution or Unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted A mercapto group, or a substituted or unsubstituted amine group.

Among them, an alkyl group is particularly preferred from the viewpoint of synthesis and characteristics as a coloring composition.

The hydrogen atom of the substituent in the aforementioned R ₅₁ to R ₆₄ may be further substituted with another substituent.

Examples of the other substituent include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group; a phenoxy group; An aryloxy group such as a tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; an anthraceneoxy group such as an ethoxy group, a propenyloxy group or a benzhydryloxy group; a mercapto group such as a benzyl group, a benzhydryl group, an isobutyl fluorenyl group, an acryl fluorenyl group, a methacryl fluorenyl group, or a methoxy sulfhydryl group; an alkylthio group such as a methylthio group or a t-butylthio group; An arylthio group such as a p-tolylthio group; an alkylamino group such as a methylamino group or a cyclohexylamino group; a dialkyl group such as a dimethylamino group, a diethylamino group, a morpholino group or a piperidinyl group; An arylamino group such as a phenylamino group or a p-tolylamino group; an alkyl group such as a methyl group, an ethyl group, a tert-butyl group or a dodecyl group; a phenyl group, a p-tolyl group, a xylyl group, An aryl group such as cumylphenyl group, naphthyl group, anthracenyl group or phenanthryl group; a heterocyclic group such as a furyl group or a thienyl group; and, in addition, a hydroxyl group, a carboxyl group, a formazan group, a fluorenyl group, a sulfo group or a methyl sulfonate.醯, p-toluenesulfonyl, amine, nitro, cyano, trifluoromethyl, trichloromethyl, trimethyldecyl, phosphonic acid subunit, phosphonium, trimethylammonium, dimethyl Mercapto, triphenyl benzamidine methyl fluorenyl and the like.

The structure of the photopolymerization initiator (A) represented by the formula (11) is preferably a compound represented by the following formula (12).

Formula (12)

The photopolymerization initiator (A) represented by the formula (11) contained in the photosensitive coloring composition of the present invention is an oxime ester photopolymerization initiator. It is generally considered that the oxime ester photopolymerization initiator partially decomposes the oxime ester by absorbing ultraviolet rays to form an imino radical and an alkoxy radical, and further decomposes the active species radical to cause a reaction, but The photopolymerization initiator (A) represented by the formula (11) contained in the photosensitive coloring composition of the invention has a structure represented by the formula (11), and the decomposition efficiency by ultraviolet irradiation is obtained. Very high, capable of forming patterns with less exposure.

The photopolymerization initiator (A) represented by the formula (11) of the present invention has higher sensitivity than the conventional initiator, and may be due to two reasons listed below, but the details thereof are not clear.

For the first reason, the photopolymerization initiator (A) represented by the formula (11) of the present invention has excellent ultraviolet absorption properties because of the structure represented by the formula (11), so that it can be absorbed extremely well. The energy of the energy line given. Further, it is considered that since the obtained energy is effectively used for the decomposition of the oxime ester site, it is rapidly decomposed by the irradiation of the energy ray, and a large amount of radicals can be generated instantaneously.

The second reason is that the photopolymerization initiator (A) represented by the general formula (11) of the present invention is derived from the decomposition of an imido radical generated by ultraviolet ray absorption to an active species radical. The structure represented by the formula (11) is very rapid. If the generated imino radical is quasi-stable, the decomposition becomes slow, the amount of active radicals is reduced, and the chemical structure of the ultraviolet absorbing portion has a large influence. It is considered that the photopolymerization initiator (A) of the present invention has a structure represented by the formula (11), and the decomposition of the imine radical generated by the light irradiation is very rapid, resulting in a large amount of production. Free radicals.

In addition, as described above, the photopolymerization initiator (A) represented by the formula (11) of the present invention has a very rapid decomposition of the imino radical, and thus recombination thereof is suppressed. When there is a lot of recombination, the active species produced by decomposition are reduced, and thus the function as a radical polymerization initiator is lowered.

The photopolymerization initiator (A) containing the compound represented by the above formula (1) or (11) can be compared with 100 parts by weight of the pigment (D) in the photosensitive coloring composition in consideration of sensitivity and patterning property. It is used in an amount of from 1 to 200 parts by weight, preferably from 1 to 150 parts by weight.

<Other photopolymerization initiators (Y)>

In the photosensitive coloring composition of the present invention, when another photopolymerization initiator (Y) is used in combination with the compound represented by the above formula (1) or (11), more excellent chemical resistance can be obtained. Preferably.

As other photopolymerization initiators (Y), 4-phenoxydichloroacetophenone, 4-tert-butyldichloroacetophenone, diethoxyacetophenone, p-dimethylamine can be used. Acetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane- 1-ketone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, etc. Acetophenone-based compounds; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzil dimethyl ketal ; benzophenone, benzamidine benzoic acid, methyl benzhydrazide, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-phenyl a benzophenone compound such as mercapto-4'-methyldiphenyl sulfide or 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2 - chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropyl Thioxanthone xanthone-based compound, 2,4-diethyl thioxanthone; 2,4,6-trichloro-three -s- 2-phenyl-4,6-di(trichloromethyl)-s-three , 2-(p-methoxyphenyl)-4,6-di(trichloromethyl)-s-three , 2-(p-tolyl)-4,6-di(trichloromethyl)-s-three , 2-piperidin-4,6-di(trichloromethyl)-s-three , 2,4-bis(trichloromethyl)-6-styryl-s-tris, 2-(naphthalen-1-yl)-4,6-di(trichloromethyl)-s-three , 2-(4-methoxy-naphthalen-1-yl)-4,6-di(trichloromethyl)-s-three 2,4-trichloromethyl-piperonyl-6-three 2,4-trichloromethyl (4'-methoxystyryl)-6-three Wait three Compound; 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(0-benzamide)], 0-(ethinyl)-N-(1- An oxime ester compound such as phenyl-2-oxo(oxo)-2-(4'-methoxy-naphthyl)ethylidene hydroxyamine; bis(2,4,6-trimethylbenzene) a phosphine compound such as phenylphosphine oxide or 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide; 2,2'-di(o-chlorophenyl)-4, 5,4',5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole , 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(p-methylphenyl)biimidazole and other imidazole compounds; 9,10-phenanthrenequinone, camphorquinone, B An anthracene-based compound; a borate-based compound, an oxazole-based compound, a titanocene-based compound, and the like.

In particular, it is more preferable to contain at least one or more photopolymerization initiators (Y) selected from the group consisting of acetophenone-based compounds, phosphine-based compounds, and imidazole-based compounds.

These photopolymerization initiators may be used alone or in combination of two or more kinds at any ratio as needed. The other photopolymerization initiator (Y) may be used in an amount of from 1 to 200 parts by weight, preferably from 1 to 150 parts by weight, per 100 parts by weight of the pigment (D) in the photosensitive coloring composition.

Further, it can be used in an amount of from 1 to 1000 parts by weight based on 100 parts by weight of the photopolymerization initiator (A). In order to obtain better chemical resistance, it is preferably an amount of 5 to 600 parts by weight based on 100 parts by weight of the photopolymerization initiator (A).

<sensitizer (E)>

Further, the photosensitive coloring composition of the present invention may further contain a sensitizer (E). The content of the sensitizer (E) can be used in an amount of from 1 to 100 parts by weight based on 100 parts by weight of the photopolymerization initiator (A) in the photosensitive coloring composition.

Examples of the sensitizer (E) include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, and benzophenone and camphorquinone. 2-dione derivative, benzoin derivative, anthracene derivative, naphthoquinone derivative, anthracene derivative, xanthene derivative, thioxanthene derivative, xanthone derivative, thioxanthene a polymethine such as a thioxanthone derivative, a coumarin derivative, a coumarin derivative, a cyanine derivative, a merocyanine derivative, or an oxonol derivative ( Polymethine) pigment, acridine derivative, hydrazine (azine) derivative, thio (thiazine) derivative, a derivative, a porphyrin derivative, an anthracene derivative, an azulenium derivative, a squarylium derivative, a porphyrin derivative, a tetraphenylporphyrin derivative, a triarylmethane derivative, Tetrabenzoporphyrin derivative, tetrapyridyl And a tetrapyrazinoporphyrazine derivative, a phthalocyanine derivative, a tetraazaporphyrazine derivative, tetraquinoline a porphyrin porphyrazine derivative, a naphthalocyanine derivative, a subphthalocyanine derivative, a pyrylium derivative, a thiopyranidine derivative, a tetraphylline derivative, Annulene derivative, spiropyran derivative, spiro (spiroxazine) derivatives, thiospirol derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives, and the like.

Further, as a specific example of the above, the "Pigment Handbook" (1986, Kodansha), Dahe Yuanxin, etc., "Chemistry of Functional Pigments" (1981, CMC), and Chisen-Sang Sanlang, etc. The sensitizer described in "Special Functional Materials" (1986, CMC) is not limited thereto. Further, in addition to this, a sensitizer that exhibits absorption of light from the ultraviolet ray to the near-infrared region may be contained.

In the above sensitizer (E), a sensitizer which is particularly suitable for sensitizing the compounds represented by the general formulae (1) and (11) may, for example, be a thioxanthone derivative or a derivative of Michelin. And carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthiophene can be used. Tons of ketone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-di(diethylamino)benzol Ketone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzylidene-N-ethylcarbazole, and 3,6-diphenyl Mercapto-N-ethylcarbazole and the like.

The sensitizer (E) may contain two or more kinds of sensitizers in an arbitrary ratio.

<Resin (B)>

The resin (B) contained in the photosensitive coloring composition of the present invention is preferably a resin having a transmittance of 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light region. The resin (B) includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and these may be used singly or in combination of two or more.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polyacetic acid. Vinyl ester, polyurethane resin, polyester resin, acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene, polybutylene Diene, polyimine resin, and the like.

Further, examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, a phenol resin, and the like.

As the photosensitive resin, a (meth)acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group, or a cinnamic acid and a linear substituent having a reactive substituent such as a hydroxyl group, a carboxyl group or an amine group can be used. A polymer obtained by introducing a photocrosslinkable group such as a (meth) acrylonitrile group or a styryl group into the linear polymer. Further, it is also possible to use an acid anhydride-containing compound such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer by using a (meth)acrylic compound having a hydroxyl group such as a hydroxyalkyl (meth)acrylate. A resin obtained by semi-esterifying a linear polymer.

The resin (B) can be used in an amount of 20 to 400 parts by weight, preferably 50 to 250 parts by weight, based on 100 parts by weight of the pigment (D) in the photosensitive coloring composition.

<Photopolymerizable Compound (C)>

The photopolymerizable compound (C) contained in the photosensitive coloring composition of the present invention is a photopolymerizable monomer or oligomer, and examples thereof include methyl (meth)acrylate and ethyl (meth)acrylate. 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(methyl) Acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tris(methyl) Acrylate, pentaerythritol tri(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl Alcohol diglycidyl ether di(meth) acrylate, dipentaerythritol hexa(meth) acrylate, tricyclodecyl (meth) acrylate, transester acrylate, methylolated melamine (meth) acrylate , various acrylates and methacrylates such as epoxy (meth) acrylate and amine acrylate, (meth) acrylic acid, styrene, vinyl acetate Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-methylol (meth) acrylamide, N-vinyl carbamide, Acrylonitrile and the like. These may be used alone or in combination of two or more.

The photopolymerizable compound (C) can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the pigment (D) in the photosensitive coloring composition.

In the photosensitive coloring composition, the ratio [I _a /M] of the weight [I _a ] of the photopolymerization initiator (A) to the weight [M] of the photopolymerizable compound (C) is preferably from 0.03 to 1.00. More preferably, it is 0.04 to 0.95.

Further, when the photosensitive coloring composition contains the sensitizer (E) and other photopolymerization initiators (Y), the photopolymerization initiator (A), the sensitizer (E), and other photopolymerization initiators (Y) The ratio [I _b /M] of the total weight (I _b ) to the weight [M] of the photopolymerizable compound (C) is preferably from 0.04 to 1.50, and more preferably from 0.05 to 1.45.

When [I _a /M] is 0.03 or more and [I _b /M] is 0.04 or more, the sensitivity is high and the effect is good. Further, when [I _a /M] is 1.00 or less and [I _b /M] is 1.50 or less, the linearity and resolution of the pattern shape are more excellent.

<Pigment (D)>

The pigment (D) contained in the photosensitive coloring composition of the present invention may be used singly or in combination of two or more kinds. Among the pigments, pigments having high color rendering properties and high heat resistance are preferred. Organic pigments can usually be used.

Hereinafter, specific examples of the organic pigment which can be used in the photosensitive coloring composition of the present invention are indicated by a pigment index number (C.I.).

In the red photosensitive coloring composition for forming a red filter section, for example, CI Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 81 can be used: 1, 81:2, 81:3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, Red pigments such as 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 272, 279. In the red photosensitive coloring composition, a yellow pigment or an orange pigment may also be used in combination.

As the yellow pigment which can be used in combination in the red photosensitive coloring composition, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18 can be used. 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, and the like.

Further, in the yellow photosensitive coloring composition for forming a yellow filter section, these yellow pigments may be used singly or in combination of two or more.

As the orange pigment which can be used in combination in the red photosensitive coloring composition, for example, an orange pigment such as C.I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73 can be used.

Further, in the orange photosensitive coloring composition for forming an orange filter section, these orange pigments may be used singly or in combination of two or more.

In the green photosensitive coloring composition for forming a green filter segment, for example, green pigments such as C.I. Pigment Green 7, 10, 36, 37, and 58 can be used. In the green photosensitive coloring composition, the above yellow pigment may also be used in combination.

In the blue photosensitive coloring composition for forming a blue filter section, for example, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, may be used. 22, 60, 64, 80 and other blue pigments. In the blue photosensitive coloring composition, a violet pigment such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 may be used in combination.

In the cyan photosensitive coloring composition for forming a cyan filter section, for example, CI Pigment Blue 15:1, 15:2, 15:3, 15:4, 15:6, 16, 80 can be used. Wait for blue pigments.

In the magenta photosensitive coloring composition for forming a magenta filter section, for example, violet pigments such as CI Pigment Violet 1, 19, and CI Pigment Red 81, 144, 146, 177, 169, etc. can be used. Red pigment. In the magenta photosensitive coloring composition, a yellow pigment may also be used in combination.

In the black photosensitive coloring composition for forming a black matrix, for example, carbon black, nigrosine, anthraquinone black pigment, an anthraquinone black pigment can be used, and specifically, a CI pigment black 1 can be used. 6, 6, 12, 20, 31, etc. A mixture of a red pigment, a blue pigment, and a green pigment may also be used in the black photosensitive coloring composition. The black pigment is preferably carbon black from the viewpoint of the price and the degree of light blocking property, and the carbon black may be surface-treated with a resin or the like. Further, in order to adjust the color tone, a blue pigment or a violet pigment may be used in combination in the black photosensitive coloring composition.

Further, examples of the inorganic pigment include barium sulfate, zinc white, lead sulfate, lead yellow, zinc yellow, iron oxide (iron oxide red (III)), cadmium red, ultramarine blue, Prussian blue, chrome oxide green, cobalt green, and brown. Metal oxide powder such as umber, titanium black, synthetic iron black, titanium oxide, iron oxide, metal sulfide powder, metal powder, and the like. In order to obtain a balance of chroma and brightness while ensuring good coatability, sensitivity, developability, and the like, an inorganic pigment and an organic pigment are used in combination.

In the photosensitive coloring composition of the present invention, in order to perform coloring, a dye may be contained in a range that does not lower heat resistance.

The concentration of the pigment (D) component is preferably 10% by weight or more, from the viewpoint of obtaining sufficient color reproducibility, based on the total nonvolatile content of the photosensitive coloring composition of the present invention (100% by weight). It is preferably 15% by weight or more, and most preferably 20% by weight or more. Further, from the viewpoint of improving the stability of the photosensitive coloring composition, the concentration of the pigment (D) component is preferably 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less.

<Multifunctional thiol (F)>

The photosensitive coloring composition of the present invention may contain a polyfunctional thiol (F). The polyfunctional thiol (F) is a compound having two or more thiol (SH) groups.

The polyfunctional thiol (F) is used together with the above photopolymerization initiator (A) to function as a chain transfer agent during radical polymerization after light irradiation to produce sulfur which is not easily inhibited by oxygen. Since the radical is thiylradical, the sensitivity of the obtained photosensitive coloring composition becomes high. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as a methylene group or an ethylene group is preferred.

For example, hexanedithiol, decanedithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithioglycolate, ethylene glycol dithioglycolic acid can be cited. Ester, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolethane tris(3-mercaptobutyrate ), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol IV (3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylnonylbenzene, 2 ,4,6-trisyl-s-three , 2-(N,N-dibutylamino)-4,6-dimercapto-s-three Wait. These polyfunctional thiols may be used alone or in combination of two or more.

The content of the polyfunctional thiol (F) is preferably from 0.05 to 100 parts by weight, and more preferably from 1.0 to 50.0 parts by weight, per 100 parts by weight of the pigment (D).

More excellent development resistance can be obtained by using 0.05 parts by weight or more of the polyfunctional thiol. When a monofunctional thiol having one thiol (SH) group is used, such improvement in developability cannot be obtained.

<UV absorber (G), polymerization inhibitor (H)>

The photosensitive coloring composition of the present invention may contain an ultraviolet absorber (G) or a polymerization inhibitor (H). The shape and resolution of the pattern can be controlled by containing an ultraviolet absorber (G) or a polymerization inhibitor (H). As the ultraviolet absorber, for example, 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]- 4,6-bis(2,4-dimethylphenyl)-1,3,5-three , 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-di(4-phenylphenyl)-1,3,5-tri Hydroxyphenyl 2-(5-Methyl-2-hydroxyphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-di(1-methyl-1-benzene Benzotriazole series such as phenylethyl)phenol, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole; 2,4-dihydroxydiphenyl Benzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, etc.; phenyl salicylate, third Salicylate such as butyl phenyl salicylate; cyanoacrylate such as ethyl-2-cyano-3,3'-diphenyl acrylate; 2,2,6,6-tetra Isopiperidin-1-oxyl (triacetone-amine-N-oxyl), bis(2,2,6,6-tetramethyl-4-piperidinyl)-sebacate, poly[[6 -[(1,1,3,3-tetrabutyl)amino]-1,3,5-three a hindered amine system or the like such as -2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imido], which may be used singly or in combination. Further, examples of the polymerization inhibitor include methylhydroquinone, tert-butylhydroquinone, 2,5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, and 4- Hydroquinone derivatives such as methoxy-1-naphthol and tert-butylcatechol and phenol compounds; (phenothiazine), bis(1-dimethylbenzyl) phenoxy 3,7-dioctylmorphothiophene An amine compound; copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. a manganese salt compound; a nitroso compound such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine, or an ammonium salt thereof or Aluminum salts and the like, which may be used singly or in combination.

The ultraviolet absorber and the polymerization inhibitor may be used in an amount of 0.01 to 20 parts by weight, and preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the pigment (D) in the coloring composition.

More excellent resolution can be obtained by using 0.01 part by weight or more of the ultraviolet absorber or the polymerization inhibitor.

<Storage Stabilizer (J)>

The storage coloring composition of the present invention may contain a storage stabilizer (J). By containing the storage stabilizer (J), the time-dependent viscosity of the composition can be stabilized. As the storage stabilizer, for example, 2,6-di(1,1-dimethylethyl)-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-) -hydroxyphenyl)propionate], 2,4-di(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino) 1,3,5-three Hindered phenolic; organophosphines such as tetraethylphosphine, triphenylphosphine, tetraphenylphosphine; zinc dimethyldithiophosphate, zinc dipropyldithiophosphate, molybdenum dibutyldithiophosphate a phosphite system; a sulfuric acid such as lauryl sulfide or benzothiophene; a quaternary ammonium chloride such as benzyltrimethyl chloride or diethylhydroxylamine; an organic acid such as lactic acid or oxalic acid and a methyl group thereof. Ether, etc., these may be used singly or in combination.

The storage stabilizer may be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the pigment (D) in the coloring composition.

By using 0.01 part by weight or more of the storage stabilizer, the temporal stability of the photosensitive coloring composition can be improved.

<solvent>

In order to sufficiently disperse the pigment (D) in a dye carrier such as a resin (B) or a photopolymerizable compound (C), and apply it to a transparent substrate such as a glass substrate to a dry film thickness of 0.2 to 10 μm, it is formed. The filter section and the black matrix may contain a solvent in the photosensitive coloring composition of the present invention. Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol diacetate, and 1,4- two Alkane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclo Hexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3 -methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N,N-dimethylformamide, n-butanol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chloro Toluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, t-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutanol, isophorone, Ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol single third Butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol single Methyl ether acetate, diisobutyl ketone, diethylene glycol diethyl , diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Acid ester, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol II Acetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, Dibasic acid esters and the like, these may be used singly or in combination.

The solvent may be used in an amount of from 100 to 10,000 parts by weight, and preferably from 500 to 5,000 parts by weight, based on 100 parts by weight of the pigment (D) in the coloring composition.

<Other ingredients>

In the photosensitive coloring composition of the present invention, in order to improve the adhesion to the transparent substrate, an adhesion improving agent such as a decane coupling agent may be contained.

Examples of the decane coupling agent include vinyl decanes such as vinyl tris(β-methoxyethoxy)decane, vinyl ethoxy decane, and vinyl trimethoxy decane; γ-methyl propylene oxime; (meth)acrylic decanes such as oxypropyltrimethoxydecane; β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, β-(3,4-epoxycyclohexyl Methyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltriethoxydecane, β-(3,4-epoxycyclohexyl)methyltriethoxydecane,环-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, etc.; N-β(aminoethyl)γ-aminopropyl Trimethoxydecane, N-β(aminoethyl)γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropylmethyldiethoxydecane, γ -Aminopropyltriethoxydecane, γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltri Amino decanes such as ethoxy decane; γ-mercaptopropyltrimethoxydecane, γ-mercaptopropyltriethoxydecane, etc. Sulfoxes and the like.

The decane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the pigment (D) in the coloring composition.

Further, the photosensitive coloring composition of the present invention may contain an amine compound having an action of reducing dissolved oxygen.

Examples of such an amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-di Isoamyl methylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, and the like.

<Method for Producing Photosensitive Coloring Composition>

The photosensitive coloring composition of the present invention can be produced by the following method. The pigment (D) is finely dispersed in the resin (B) using various dispersing devices such as a triple roll mill, a double roll mill, a sand mill, a kneader, an attritor or the like. A pigment dispersion is produced in a pigment carrier and/or a solvent, and then the photopolymerization initiator (A), the resin (B), the photopolymerizable compound (C), and other light added as the case may be mixed in the pigment dispersion. a polymerization initiator (Y), a sensitizer (E), a polyfunctional thiol (F), a UV absorber (G), a polymerization inhibitor (H), a storage stabilizer (J), a solvent, and other components, and The photosensitive coloring composition can be produced by stirring. Further, the photosensitive coloring composition containing two or more kinds of pigments may be mixed by separately dispersing each pigment in a pigment carrier and/or a solvent, and further mixing a photopolymerization initiator ( A) A photopolymerizable compound (C) or the like is produced by stirring.

When the pigment is dispersed in the resin (B) and/or the solvent, a dispersing aid such as a resin type pigment dispersant, a surfactant, or a pigment derivative may be appropriately contained. The dispersing aid makes the dispersion of the pigment excellent, and the effect of preventing the pigment after the dispersion from re-agglomerating is good, and therefore the photosensitivity formed by dispersing the pigment in the resin (B) and/or the solvent by using the dispersing aid is used. When the composition is colored, a color filter excellent in transparency can be obtained.

The dispersing aid may be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, per 100 parts by weight of the pigment (D).

The resin-type pigment dispersant is a substance containing a pigment affinity site having a property of adsorbing to a pigment and a site compatible with a pigment carrier, and exhibiting a function of adsorbing a pigment to stably disperse a pigment in a pigment carrier. . As the resin type pigment dispersant, specifically, a polycarboxylate such as a polyurethane or a polyacrylate, an unsaturated polyamine, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, a polycarboxylic acid ammonium salt, or a poly a carboxylic acid alkylamine salt, a polyoxyalkylene oxide, a long-chain polyamine guanamine phosphate, a hydroxyl group-containing polycarboxylate, a modification thereof, by poly(lower alkylene imine) and having An oily dispersant such as guanamine or a salt thereof formed by the reaction of a polyester having a free carboxyl group, a (meth)acrylic acid-styrene copolymer, a (meth)acrylic acid-(meth)acrylic acid ester copolymer, a styrene-matrix Water-soluble resin such as acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone or water-soluble polymer compound, polyester-based, modified polyacrylate-based, ethylene oxide/propylene oxide (propylene) Oxide) addition compound, phosphate ester, and the like. These may be used alone or in combination of two or more.

Examples of the commercially available resin-based dispersant include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, and 162 manufactured by BYK-Chemie Japan Co., Ltd. 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra -U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc., SOSOLERS-3000, 9000, 13000, 13240, 13650 manufactured by Japan Lubrizol , 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500 Etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, manufactured by Ciba Japan Co., Ltd. 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066 5070,7500,7554,1101,120,150,1501,1502,1503 other, Ajinomoto Fine Chemicals (Ajinomoto Fine-Techno) manufactured by Adisper PA111, PB711, PB821, PB822, PB824 and the like.

Examples of the surfactant include polyoxyethylene alkylether sulfate, sodium dodecylbenzenesulfonate, an alkali salt of a styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, and an alkyl group. Sodium phenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer Anionic surfactants such as polyoxyethylene alkyl ether phosphate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxygen Nonionic surfactants such as ethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl quaternary ammonium salts and cationic surfactants such as ethylene oxide adducts An amphoteric surfactant such as an alkylbetaine or an alkylimidazoline such as an alkyldimethylaminoacetic acid betaine, which may be used singly or in combination of two or more.

The pigment derivative is a compound obtained by introducing a substituent into an organic pigment, and the organic pigment also contains a pale yellow aromatic polycyclic compound such as a naphthalene or an anthracene which is not generally called a pigment. As a pigment derivative, JP-A-63-305173, JP-A-57-15620, JP-A-59-40172, JP-A-63-17102, and JP-A-5-9469 can be used. The materials described in the publications and the like may be used singly or in combination of two or more.

The photosensitive coloring composition of the present invention can be prepared in the form of a solvent developing type or an alkali developing type coloring resist material. The coloring resist material is a material obtained by dispersing the pigment (D) in a composition containing an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (A), and a solvent.

The photosensitive coloring composition is preferably a coarse particle having 5 μm or more, preferably a coarse particle of 1 μm or more, and more preferably a coarse particle of 0.5 μm or more, by using a centrifugal separation, a sintered filter, a membrane filter or the like. And the dust that comes in.

<color filter>

Next, the color filter of the present invention will be described.

The color filter of the present invention has a filter section and/or a black matrix formed of the photosensitive coloring composition of the present invention on a transparent substrate, and the general color filter has at least one red filter section and at least one green filter. And at least one blue filter section, or having at least one magenta filter section, at least one cyan filter section, and at least one yellow filter section.

As the transparent substrate, a glass plate such as soda lime glass, low alkali borosilicate glass or alkali-free aluminum boron borosilicate glass, or polycarbonate, polymethyl methacrylate or polyethylene terephthalate can be used. Resin board. Further, in order to drive the panelized liquid crystal, a transparent electrode made of indium oxide, tin oxide or the like may be formed on the surface of the glass plate or the resin plate.

The dry film thickness of the filter section and the black matrix is preferably 0.2 to 10 μm, and more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like can be used.

The color filter sections and the black matrix are formed by photolithography in the following manner. That is, the photosensitive coloring composition prepared as a solvent developing type or an alkali developing type coloring resist material is applied onto a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating, and dried. The film thickness is 0.2 to 10 μm. For the film dried as needed, ultraviolet exposure is performed by a mask having a predetermined pattern provided in a contact or non-contact state with the film.

Then, it may be immersed in a solvent or an alkali developing solution, or the developing solution may be sprayed by a sprayer or the like to remove the uncured portion to form a desired pattern, thereby forming a filter segment and a black matrix. Further, in order to promote polymerization of the filter segments and the black matrix formed by development, it is also possible to perform heating as needed. By photolithography, it is possible to form a filter section and a black matrix with higher precision than the printing method.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkali developing solution, and an organic base such as dimethylbenzylamine or triethanolamine may also be used. Further, an antifoaming agent or a surfactant may be added to the developer.

As the development treatment method, a shower development method, a spray development method, a dipping development method, a stirring (paddle) development method, or the like can be applied.

Further, in order to increase the ultraviolet exposure sensitivity, after applying and drying the photosensitive coloring composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied and dried to prevent generation of oxygen. The film that blocks the polymerization is then exposed to ultraviolet light.

Example

Hereinafter, the present invention will be specifically described based on the examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. In addition, in the examples and comparative examples, "parts" means "parts by weight".

In addition, the molecular weight of the resin in the acrylic resin solution is HLC-8220GPC (manufactured by Tosoh Corporation), and two TSK-GEL SUPER HZM-Ns are connected as a column, and THF is used. The polystyrene-equivalent weight average molecular weight measured by the solvent.

First, a photosensitive coloring composition containing the photopolymerization initiator (A) represented by the formula (1) was adjusted, and a color filter was produced using the same, and various characteristics were evaluated (Examples 1 to 24 and Comparative Examples 1 to 2) .

In the adjustment of the photosensitive coloring composition, the photopolymerization initiator (A) represented by the formula (1), the acrylic resin solution, and the pigment dispersion are separately synthesized and produced, and these are mixed.

In the synthesis of the photopolymerization initiator (A), an intermediate compound is first synthesized, followed by synthesis of a precursor compound from the intermediate compound, and then the photopolymerization initiator is synthesized from the precursor compound. The obtained compound was subjected to elemental analysis (C, H, N) (2400‧CHN manufactured by PerkinElmer Co., Ltd.) and mass spectrometry by EI-MS (Polaris Q manufactured by Thermo Co., Ltd.) to confirm the respective Structure.

<Method for Producing Photopolymerization Initiator (A) Represented by General Formula (1)> [Synthesis of Photopolymerization Initiator (A1)]

100.0 g of N-benzophenone carbazole was dissolved in 1000 ml of chloroform, and 85.0 g of aluminum chloride was further added thereto. After stirring at 0 ° C, 32.0 g of propylene chloride was dissolved in 500 ml of chloroform by dropwise addition over 2 hours. Solution. After the completion of the dropwise addition, the mixture was stirred at 25 ° C for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 2000 ml of chloroform. The organic layer was dried over magnesium sulfate, and the residue was filtered, and then the residue was recrystallized from chloroform/methanol to afford 113.0 g of the intermediate compound (a1). Next, 100.0 g of the compound (a1) was dissolved in a mixed solution of 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid, and while stirring at room temperature, 38.4 g of tributyl nitrite was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water, and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, and then filtered, and the solvent was evaporated, and the residue was washed with n-hexane to obtain 99.8 g of the precursor compound (b1). Next, 30.0 g of the compound (b1) was stirred in 300 ml of ethyl acetate, and 6.3 g of acetic anhydride and 10.6 g of sodium acetate were added, and the mixture was heated under reflux for 3 hours. Then, the reaction liquid was poured into 500 ml of ice water, and the composition was extracted with ethyl acetate, and the organic layer was washed with water (300 ml × 3 times), dried over magnesium sulfate, and then filtered, and the solvent was evaporated. The residue was recrystallized from the alkane to obtain 31.4 g of a photopolymerization initiator (A1).

Photopolymerization initiator (A1)

[Synthesis of Photopolymerization Initiator (A2)]

100.0 g of N-benzophenone carbazole was dissolved in 1000 ml of chloroform, and 84.0 g of aluminum chloride was further added. After stirring at 0 ° C, 36.8 g of butazone chloride was dissolved in 500 ml of chloroform by dropwise addition over 2 hours. Solution. After the completion of the dropwise addition, the mixture was stirred at 25 ° C for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 2000 ml of chloroform. The organic layer was dried over MgSO.sub.4, filtered, and then the residue was recrystallised from chloroform/methanol to give 109.3 g of intermediate compound (a2). Next, 100.0 g of the compound (a2) was dissolved in a mixed solution of 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid, and while stirring at room temperature, 43.1 g of tributyl nitrite was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water, and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, and then filtered, and the solvent was evaporated, and the residue was washed with n-hexane to obtain 89.3 g of the precursor compound (b2). Next, 30.0 g of the compound (b2) was stirred in 300 ml of ethyl acetate, and 6.1 g of acetic anhydride and 10.3 g of sodium acetate were added, and the mixture was heated under reflux for 3 hours. Then, the reaction liquid was poured into 500 ml of ice water, and the composition was extracted with ethyl acetate, and the organic layer was washed with water (300 ml × 3 times), dried over magnesium sulfate, and then filtered, and the solvent was evaporated to ethyl acetate. The residue was recrystallized from the alkane to obtain 30.0 g of a photopolymerization initiator (A2).

Photopolymerization initiator (A2)

[Synthesis of Photopolymerization Initiator (A3)]

100.0 g of N-(p-nitrophenyl)carbazole was dissolved in 1000 ml of chloroform, and then 101.8 g of aluminum chloride was added. After stirring at 0 ° C, 44.3 g of butazone chloride was dissolved in 500 ml over 2 hours. A solution of chloroform. After the completion of the dropwise addition, the mixture was stirred at 25 ° C for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 2000 ml of chloroform. The organic layer was dried over MgSO.sub.4, filtered, and then the residue was recrystallised from chloroform/methanol to afford 113.6 g of intermediate compound (a3). Next, 100.0 g of the compound (a3) was dissolved in a mixed solution of 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid, and while stirring at room temperature, 43.1 g of tributyl nitrite was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water, and extracted with 1500 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, and then filtered, and the solvent was evaporated, and the residue was washed with n-hexane to obtain 107.2 g of the precursor compound (b3). Next, 50.0 g of the compound (b3) was stirred in 500 ml of ethyl acetate, and 19.9 g of acetic anhydride and 11.7 g of sodium acetate were added, and the mixture was heated under reflux for 3 hours. Then, the reaction liquid was poured into 500 ml of ice water, and the composition was extracted with ethyl acetate, and the organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, and then filtered, and the solvent was evaporated to ethyl acetate-hexane The residue was recrystallized from the alkane to obtain 57.6 g of a photopolymerization initiator (A3).

Photopolymerization initiator (A3)

[Synthesis of Photopolymerization Initiator (A4)]

100.0 g of N-benzophenone-1,3-dimethyl-carbazole was dissolved in 1000 ml of chloroform, and then 78.6 g of aluminum chloride was added. After stirring at 0 ° C, 29.6 was added dropwise over 2 hours. A solution of g-propyl chloride in 500 ml of chloroform. After the completion of the dropwise addition, the mixture was stirred at 25 ° C for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 2000 ml of chloroform. The organic layer was dried over magnesium sulfate, and the residue was filtered, and then the residue was recrystallized from chloroform/methanol to afford 111.8 g of intermediate compound (a4). Next, 100.0 g of the compound (a4) was dissolved in a mixed solution of 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid, and while stirring at room temperature, 35.7 g of tributyl nitrite was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water, and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, and then filtered, and the solvent was evaporated, and the residue was washed with n-hexane to obtain 98.3 g of the precursor compound (b4). Next, 30.0 g of the compound (b4) was stirred in 300 ml of ethyl acetate, and 5.9 g of acetic anhydride and 10.0 g of sodium acetate were added, and the mixture was heated under reflux for 3 hours. Then, the reaction liquid was poured into 500 ml of ice water, and the composition was extracted with ethyl acetate, and the organic layer was washed with water (300 ml × 3 times), dried over magnesium sulfate, and then filtered, and the solvent was evaporated to ethyl acetate. The residue was recrystallized from the alkane to obtain 31.2 g of a photopolymerization initiator (A4).

Photopolymerization initiator (A4)

<Method for Producing Acrylic Resin Solution> [Modulation of Acrylic Resin Solution]

370 parts of cyclohexanone was added to the reaction vessel, and while heating to 80 ° C while injecting nitrogen into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, and 55.0 parts of A were added dropwise at this temperature for 1 hour. A polymerization reaction was carried out by mixing a mixture of n-butyl acrylate, 15.0 parts of 2-hydroxyethyl methacrylate, and 4.0 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further carried out at 80 ° C for 3 hours, and then a solution in which 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C for 1 hour to obtain an acrylic resin. Solution.

After cooling to room temperature, about 2 g of the acrylic resin solution was sampled, and it was dried by heating at 180 ° C for 20 minutes, and the nonvolatile matter was measured, and cyclohexanone was added to the above-mentioned synthetic acrylic resin solution to make it nonvolatile. The composition was 20% by weight. The obtained acrylic resin had a weight average molecular weight of 40,000.

<Method for Producing Pigment Dispersion> [Modulation of Red Pigment Dispersion]

After the mixture of the following composition was stirred and mixed uniformly, zirconia beads having a diameter of 1 mm were used, and dispersed by an EIGER mill ("M-250 MKII" manufactured by EIGER Japan Co., Ltd.) for 5 hours, and then a filter of 5 μm was used. Filtration was carried out to prepare a red pigment dispersion PR.

‧ Diketopyrrolopyrrole pigment (C.I. Pigment Red 254) 6.82 parts

("IMGAPHOR RED B-CF" by Ciba Japan)

‧蒽醌 pigment (C.I. Pigment Red 177) 1.08 parts

(CROMOPHTAL RED A2B by Ciba Japan)

‧ Nickel azo complex pigment (C.I. Pigment Yellow 150)

("E4GN" made by LANXESS) 0.88

‧Resin pigment dispersant

("SOLSPERSE 20000" made by Lubrizol Corporation of Japan) 1.74 copies

‧ Diketopyrrolopyrrole pigment derivative 2.05 parts

‧Acrylic resin solution 5.83 parts

‧cyclohexanone 81.60 parts

[Modulation of Green Pigment Dispersion]

A green pigment dispersion P-G was produced in the same manner as the red pigment dispersion using a mixture of the following composition.

‧ Halogenated copper phthalocyanine pigment (C.I. Pigment Green 36)

("LIONOL GREEN 6YK" by Toyo Ink Manufacturing Co., Ltd.) 8.93

‧Single azo pigments (C.I. Pigment Yellow 150)

("E4GN" made by LANXESS) 2.74 copies

‧Resin pigment dispersant

("SOLSPERSE 20000" made by Lubrizol Corporation of Japan) 2.80 copies

‧Acrylic resin solution 5.53 parts

‧cyclohexanone 80.00 parts

[Modulation of Blue Pigment Dispersion]

A blue pigment dispersion P-B was produced in the same manner as the red pigment dispersion using a mixture of the following composition.

‧ ε-type copper phthalocyanine pigment (C. I. Pigment Blue 15:6)

("Heliogen Blue L-6700F" by BASF) 12.88

‧Resin pigment dispersant

("SOLSPERSE 20000" made by Lubrizol Corporation of Japan) 5.62

‧Acrylic resin solution 1.50 parts

‧cyclohexanone 80.00 parts

[Modulation of Black Pigment Dispersion]

A black pigment dispersion P-BK was produced in the same manner as the red pigment dispersion using a mixture of the following composition.

‧carbon black ("MA77" by Mitsubishi Chemical Corporation) 11.67

‧Resin pigment dispersant

("SOLSPERSE 20000" made by Lubrizol Corporation of Japan) 2.80 copies

‧Acrylic resin solution 5.53 parts

‧cyclohexanone 80.00 parts

[Examples 1 to 24 and Comparative Examples 1 to 2] (Modulation of photosensitive coloring composition)

Each material was mixed and stirred at a formulation ratio shown in Tables 1 to 4, and filtered with a filter of 1 μm to obtain photosensitive coloring compositions of respective colors.

The abbreviations in Tables 1 to 4 are as follows.

Photopolymerization initiator Y1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one

("ICGACURE 907" made by Ciba Japan)

Photopolymerization initiator Y2: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butene ketone

("ICGACURE 379" made by Ciba Japan)

Photopolymerization initiator Y3: 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide

("Lucirin TPO" by BASF)

Photopolymerization initiator Y4: 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole

(Black Gold Chemical Co., Ltd. "Biimidazole")

Photopolymerization initiator Y5: p-dimethylaminoacetophenone

("DMA" by DAIKI Fine Chemical Co., Ltd.)

Photopolymerization initiator Y6: ethane-1-one, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl], 1-(O-B醯肟)

("ICGACURE OXE02" made by Ciba Japan)

Sensitizer E1: 2,4-diethylthioxanthone

(Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.)

Sensitizer E2: 4,4'-bis(diethylamino)benzophenone

("EAB-F" made by Hodogaya Chemical Industry Co., Ltd.)

Photopolymerizable compound C: dipentaerythritol hexaacrylate

("ARONIX M-402" by East Asia Synthetic Co., Ltd.)

Polyfunctional thiol F1: trimethylolethane tris(3-mercaptobutyrate)

("TEMB" made by Showa Denko)

Polyfunctional thiol F2: Trimethylolpropane tris(3-mercaptobutyrate)

(Showa Electric Co., Ltd. "TPMB")

Polyfunctional thiol F3: pentaerythritol tetrakis(3-mercaptopropionate)

("PEMP" manufactured by 堺Chemical Industries)

UV absorber G1: 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-di (2,4-dimethylphenyl)-1,3,5-three

("CONUBA400" made by Ciba Japan)

UV absorber G2: 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol

("COMUVIN900" made by Ciba Japan)

Inhibitor H1: N-nitrosophenylhydroxylamine Aluminium salt

("Q-1301" made by Wako Pure Chemical Industries Co., Ltd.)

Inhibitor H2: methylhydroquinone

(Seiko Chemical Co., Ltd. "MH")

Storage Stabilizer J1: 2,6-Di(1,1-dimethylethyl)-4-methylphenol

("BHT" made by Honshu Chemical Industry Co., Ltd.)

Storage Stabilizer J2: Triphenylphosphine

("TPP" made by Beixing Chemical Industry Co., Ltd.)

Organic solvent: cyclohexanone

The obtained photosensitive coloring composition was evaluated by the following method. The results are shown in Tables 5 and 6.

[Pattern section of filter section and black matrix]

The obtained photosensitive coloring composition was applied onto a 10 cm × 10 cm glass substrate by a spin coating method, and then the solvent was removed by heating at 70 ° C for 15 minutes in a clean oven to obtain a coating film of about 2 μm. Next, after the substrate was cooled to room temperature, an ultrahigh pressure mercury lamp was used, and ultraviolet exposure was performed through a mask having a stripe pattern of 100 μm width (200 μm pitch) and 25 μm width (50 μm pitch). Then, the substrate was spray-developed using a 23 ° C aqueous sodium carbonate solution, then washed with ion-exchanged water, air-dried, and heated at 230 ° C for 30 minutes in a clean oven. For the coating film of each photosensitive coloring composition, spray development was carried out in the shortest time period in which no development remained and the pattern could be formed, and this time was taken as an appropriate development time.

The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

[sensitivity evaluation]

The pattern thickness of the 100 μm mask portion in the filter segment or the black matrix formed by the above method was measured, and the minimum exposure amount of 90% or more was evaluated for the film thickness after coating. The smaller the minimum exposure amount, the better the photosensitive coloring composition having a higher sensitivity.

○: less than 50mJ/cm ²

△: 50 mJ/cm ² or more and less than 100 mJ/cm ²

×: 100 mJ/cm ² or more

[Linearity evaluation]

The pattern of the 100 μm mask portion in the filter section or the black matrix formed by the above method was observed and evaluated using an optical microscope. The evaluation level is as follows.

○: Good linearity

△: Partial linearity is poor

×: poor linearity

[Pattern shape evaluation]

The pattern section of the 100 μm mask portion in the filter section or the black matrix formed by the above method was observed and evaluated using an electron microscope. It is good that the pattern cross section is a forward taper. The evaluation level is as follows.

○: the section is a forward cone

×: the cross section is a reverse cone

[resolution evaluation]

The pattern of the 25 μm mask portion in the filter segment or the black matrix formed by the above method was observed and evaluated using an optical microscope. The evaluation level is as follows. Poor resolution means that adjacent stripe patterns are connected or defective. The evaluation level is as follows.

◎: good resolution and linearity

○: It is slightly inferior in linearity, but the resolution is good.

△: Poor partial resolution

×: poor resolution

[Development resistance evaluation]

At the time of spray development, the pattern thickness of the 100 μm mask portion formed in the filter section formed by development at twice the appropriate time or the black matrix was measured, and compared with the pattern thickness formed by development at an appropriate development time. The evaluation level is as follows.

◎: The film thickness difference is within 20%

○: The film thickness difference is more than 20%, and within 40%

△: film thickness difference is greater than 40%

×: Defect or peeling occurred when performing 2 times development

[Chemical resistance evaluation]

The filter segments or black matrix formed by the above method were immersed in N-methylpyrrolidone for 30 minutes, washed with ion-exchanged water, air-dried, and the pattern of the 100 μm mask portion was observed using an optical microscope. And evaluation. The evaluation level is as follows.

◎: The appearance and color did not change and were good.

○: Partial wrinkles, etc., but the color did not change and was good.

△: some fading

×: peeling or fading

[Evaluation of stability over time]

The obtained photosensitive coloring composition was measured for viscosity at the initial stage and after one month at room temperature, and the degree of increase in viscosity with respect to the initial viscosity was calculated and evaluated. The evaluation level is as follows.

◎: The ratio of viscosity increase is below 5% and is good.

○: The ratio of viscosity increase is more than 5% and is less than 10%

×: The ratio of viscosity increase is more than 10%

As shown in Tables 5 and 6, the filter segments and the black matrix formed using the photosensitive coloring compositions of Examples 1 to 24 have good sensitivity, linearity, and resolution, and further, photopolymerization of the present patent application Examples 2 to 7, 10 to 16, 18, 19, 21, 22, and 24 in which the initiator (A) and the other photopolymerization initiator (Y) were used together showed more excellent properties in terms of chemical resistance. Among them, the other photopolymerization initiator (Y) is 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)benzene Examples 3, 4, 10, 12, 14, 15, and 22 of keto-1-butanone were more excellent in developability.

Further, Examples 5, 14, 23, and 24 further containing a polyfunctional thiol (F) are excellent in developability.

Further, Examples 7, 8, 13, and 19 which further contained the ultraviolet absorber (G) or the polymerization inhibitor (H) were excellent in resolution.

Further, Examples 15 and 20 further containing a storage stabilizer (J) were excellent in stability over time.

When another oxime ester type photopolymerization initiator was used as in the case of Comparative Examples 1 and 2 or the case where the photopolymerizable compound (C) was not contained, the pattern characteristics were inferior, and it was not able to obtain the result that all the characteristics were favorable.

Then, the photosensitive coloring composition containing the photopolymerization initiator (A) represented by the formula (11) was adjusted, and a color filter was produced using the same, and various characteristics were evaluated (Examples 101 to 124 and Comparative Examples 101 to 102) .

The adjustment of the photosensitive coloring composition is carried out by separately producing an acrylic resin solution and a pigment dispersion, mixing with other components, and the like.

<Method for Producing Acrylic Resin Solution> [Modulation of Acrylic Resin Solution]

370 parts of cyclohexanone was added to the reaction vessel, and while heating to 80 ° C while injecting nitrogen into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, and 55.0 parts of A were added dropwise at this temperature for 1 hour. A polymerization reaction was carried out by mixing a mixture of n-butyl acrylate, 15.0 parts of 2-hydroxyethyl methacrylate, and 4.0 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further carried out at 80 ° C for 3 hours, and then a solution in which 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C for 1 hour to obtain an acrylic resin. Solution.

After cooling to room temperature, about 2 g of the acrylic resin solution was sampled, and it was dried by heating at 180 ° C for 20 minutes, and the nonvolatile matter was measured, and cyclohexanone was added to the above-mentioned synthetic acrylic resin solution to make it nonvolatile. The composition was 20% by weight. The obtained acrylic resin had a weight average molecular weight of 40,000.

<Method for Producing Pigment Dispersion> [Modulation of Red Pigment Dispersion]

After the mixture of the following composition was stirred and mixed uniformly, zirconia beads having a diameter of 1 mm were used, and dispersed by an EIGER mill ("M-250 MKII" manufactured by EIGER Japan Co., Ltd.) for 5 hours, and then a filter of 5 μm was used. Filtration was carried out to prepare a red pigment dispersion PR.

‧ Diketopyrrolopyrrole pigment (C.I. Pigment Red 254) 6.82 parts

("IMGAPHOR RED B-CF" by Ciba Japan)

‧ Lanthanide pigment (C. I. Pigment Red 177) 1.08 parts

(CROMOPHTAL RED A2B by Ciba Japan)

‧ Nickel azo complex pigment (C. I. Pigment Yellow 150)

("E4GN" made by LANXESS) 0.88

‧Resin type pigment dispersant 1.74 parts

("SOLSPERSE 20000" made by Lubrizol Corporation of Japan)

‧ Diketopyrrolopyrrole pigment derivative 2.05 parts

‧Acrylic resin solution 5.83 parts

‧cyclohexanone 81.60 parts

[Modulation of Green Pigment Dispersion]

A green pigment dispersion P-G was produced in the same manner as the red pigment dispersion using a mixture of the following composition.

‧ Copper halide phthalocyanine pigment (C. I. Pigment Green 36) 8.93

("LIONOL GREEN 6YK" by Toyo Ink Manufacturing Co., Ltd.)

‧ Single azo pigment (C. I. Pigment Yellow 150) 2.74

("E4GN" made by LANXESS)

‧Resin type pigment dispersant 2.80 parts

("SOLSPERSE 20000" made by Lubrizol Corporation of Japan)

‧Acrylic resin solution 5.53 parts

‧cyclohexanone 80.00 parts

[Modulation of Blue Pigment Dispersion]

A blue pigment dispersion P-B was produced in the same manner as the red pigment dispersion using a mixture of the following composition.

‧ ε-type copper phthalocyanine pigment (C. I. Pigment Blue 15:6)

("Heliogen Blue L-6700F" by BASF) 12.88

‧Resin type pigment dispersant 5.62 parts

("SOLSPERSE 20000" made by Lubrizol Corporation of Japan)

‧Acrylic resin solution 1.50 parts

‧cyclohexanone 80.00 parts

[Modulation of Black Pigment Dispersion]

A black pigment dispersion P-BK was produced in the same manner as the red pigment dispersion using a mixture of the following composition.

‧carbon black ("MA77" by Mitsubishi Chemical Corporation) 11.67

‧Resin type pigment dispersant 2.80 parts

("SOLSPERSE 20000" made by Lubrizol Corporation of Japan)

‧Acrylic resin solution 5.53 parts

‧cyclohexanone 80.00 parts

[Examples 101 to 124 and Comparative Examples 101 to 102] (Modulation of photosensitive coloring composition)

Each material was mixed and stirred at a formulation ratio shown in Tables 7 to 10, and filtered with a filter of 1 μm to obtain photosensitive coloring compositions of respective colors.

The abbreviations in Tables 7 to 10 are as follows.

Photopolymerization initiator A5: a compound of the formula (12): (12)

Photopolymerization initiator Y1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one

("ICGACURE 907" made by Ciba Japan)

Photopolymerization initiator Y2: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butene ketone

("ICGACURE 379" made by Ciba Japan)

Photopolymerization initiator Y3: 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide

("Lucirin TPO" by BASF)

Photopolymerization initiator Y4: 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole

(Black Gold Chemical Co., Ltd. "Biimidazole")

Photopolymerization initiator Y5: p-dimethylaminoacetophenone

("DMA" by DAIKI Fine Chemical Co., Ltd.)

Photopolymerization initiator Y6: ethane-1-one, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl], 1-(O-B醯肟)

("ICGACURE OXE02" made by Ciba Japan)

Sensitizer E1: 2,4-diethylthioxanthone

(Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.)

Sensitizer E2: 4,4'-bis(diethylamino)benzophenone

("EAB-F" made by Hodogaya Chemical Industry Co., Ltd.)

Photopolymerizable compound C: dipentaerythritol hexaacrylate

("ARONIX M-402" by East Asia Synthetic Co., Ltd.)

Polyfunctional thiol F1: trimethylolethane tris(3-mercaptobutyrate)

("TEMB" made by Showa Denko)

Polyfunctional thiol F2: Trimethylolpropane tris(3-mercaptobutyrate)

(Showa Electric Co., Ltd. "TPMB")

Polyfunctional thiol F3: pentaerythritol tetrakis(3-mercaptopropionate)

("PEMP" manufactured by 堺Chemical Industries)

UV absorber G1: 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-di (2,4-dimethylphenyl)-1,3,5-three

("CONUBA400" made by Ciba Japan)

UV absorber G2: 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol

("COMUVIN900" made by Ciba Japan)

Inhibitor H1: N-nitrosophenylhydroxylamine Aluminium salt

("Q-1301" made by Wako Pure Chemical Industries Co., Ltd.)

Inhibitor H2: methylhydroquinone

(Seiko Chemical Co., Ltd. "MR")

Storage Stabilizer J1: 2,6-Di(1,1-dimethylethyl)-4-methylphenol

("BHT" made by Honshu Chemical Industry Co., Ltd.)

Storage Stabilizer J2: Triphenylphosphine

("TPP" made by Beixing Chemical Industry Co., Ltd.)

Organic solvent: cyclohexanone

Using the obtained photosensitive coloring composition, the pattern of the filter segment and the black matrix was formed by the following method, and as described above, sensitivity, linearity evaluation, pattern shape evaluation, resolution evaluation, development resistance evaluation, and resistance were performed. Drug evaluation, stability evaluation over time. The results are shown in Tables 11 to 12.

[Pattern section of filter section and black matrix]

The obtained photosensitive coloring composition was applied onto a 10 cm × 10 cm glass substrate by a spin coating method, and then the solvent was removed by heating at 70 ° C for 15 minutes in a clean oven to obtain a coating film of about 2 μm. Next, after the substrate was cooled to room temperature, an ultrahigh pressure mercury lamp was used, and ultraviolet exposure was performed through a mask having a stripe pattern of 100 μm width (200 μm pitch) and 25 μm width (50 μm pitch). Then, the substrate was spray-developed using a 23 ° C aqueous sodium carbonate solution, then washed with ion-exchanged water, air-dried, and heated at 230 ° C for 30 minutes in a clean oven. For the coating film of each photosensitive coloring composition, spray development was carried out in the shortest time period in which no development remained and the pattern could be formed, and this time was taken as an appropriate development time.

The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

As shown in Tables 11 and 12, the filter segments and the black matrix formed using the photosensitive coloring compositions of Examples 101 to 124 have good sensitivity, linearity, and resolution, and further, the general formula of the present patent application (11) Examples 102 to 107, 110 to 116, 118, 119, 121, 122, and 124, which are used together with the photopolymerization initiator (A) and other photopolymerization initiators (Y), are shown to be resistant to drugs. More excellent characteristics in terms of sex. Among them, the other photopolymerization initiator (Y) is 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)benzene Examples 103, 104, 110, 112, 114, 115, and 122 of keto-1-butanone were also excellent in developability.

Further, Examples 105, 114, 123, and 124 further containing a polyfunctional thiol (F) were excellent in developability.

Further, Examples 107, 108, 113, and 119 further containing an ultraviolet absorber (G) or a polymerization inhibitor (H) were excellent in resolution.

Further, Examples 115 and 120 further containing a storage stabilizer (J) were excellent in stability over time. When another oxime ester photopolymerization initiator was used as in the case of Comparative Examples 101 to 102 or when the photopolymerizable compound (C) was not contained, the pattern characteristics were poor, and it was not possible to obtain good results with all the characteristics.

Next, even when the film thickness is thick or the pigment content is high, excellent characteristics can be obtained by the photosensitive coloring composition of the present invention, which are shown in Examples 201 and 202, respectively.

[Example 201] (in the case of a thick film)

The same photosensitive coloring composition as in Example 101 was used, and it was coated on a 10 cm × 10 cm glass substrate by a spin coating method, and then the solvent was removed by heating in a clean oven at 70 ° C for 15 minutes to obtain about 3 μm. Coating film. Next, after the substrate was cooled to room temperature, an ultrahigh pressure mercury lamp was used, and ultraviolet exposure was performed through a mask having a stripe pattern of 100 μm width (200 μm pitch) and 25 μm width (50 μm pitch). Then, the substrate was spray-developed using a 23 ° C aqueous sodium carbonate solution, then washed with ion-exchanged water, air-dried, and heated at 230 ° C for 30 minutes in a clean oven. For the coating film of each photosensitive coloring composition, spray development was carried out in the shortest time period in which no development remained and the pattern could be formed, and this time was taken as an appropriate development time.

The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

The results of the respective evaluations were as follows: sensitivity: ○, linearity evaluation: ○, pattern shape evaluation: ○, resolution evaluation: ○, development resistance evaluation: ○, chemical resistance evaluation: ○, stable over time Sex evaluation: ○.

[Example 202] (In the case of increasing the pigment content rate)

The same manner as in Example 101 except that the pigment dispersion of the photosensitive coloring composition of Example 101 was changed from 41.92 to 60.23, and the acrylic resin solution was changed from 24.85 to 6.54, it was applied to 10 cm by spin coating. The solvent was removed by heating on a glass substrate of ×10 cm in a clean oven at 70 ° C for 15 minutes to obtain a coating film of about 2 μm. Next, after the substrate was cooled to room temperature, an ultrahigh pressure mercury lamp was used, and ultraviolet exposure was performed through a mask having a stripe pattern of 100 μm width (200 μm pitch) and 25 μm width (50 μm pitch). Then, the substrate was spray-developed using a 23 ° C aqueous sodium carbonate solution, then washed with ion-exchanged water, air-dried, and heated at 230 ° C for 30 minutes in a clean oven. For the coating film of each photosensitive coloring composition, spray development was carried out in the shortest time period in which no development remained and the pattern could be formed, and this time was taken as an appropriate development time.

The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

The results of the respective evaluations were as follows: sensitivity: ○, linearity evaluation: ○, pattern shape evaluation: ○, resolution evaluation: ○, development resistance evaluation: ○, chemical resistance evaluation: ○, stable over time Sex evaluation: ○.

Next, a production example of the color filter will be described.

[Production of color filter]

The red photosensitive coloring composition of Example 101 was applied onto a 10 cm × 10 cm glass substrate by a spin coating method in the same manner as in Example 101, and then the solvent was removed by heating in a clean oven at 70 ° C for 15 minutes to obtain about 2 μm coating film. Next, after the substrate was cooled to room temperature, an ultrahigh pressure mercury lamp was used, and ultraviolet exposure was performed through a mask having a stripe pattern of 100 μm width (200 μm pitch) and 25 μm width (50 μm pitch). Then, the substrate was spray-developed using a 23 ° C aqueous sodium carbonate solution, then washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ° C for 30 minutes to obtain a red filter section. Next, using the green photosensitive coloring composition of Example 109, a green filter section was formed next to the red filter section by the same operation, and a color filter having a two-color filter section was produced.

As a result, a high-quality color filter which is excellent in light resistance and heat resistance and which has a large film thickness or a high pigment content and improved color reproduction characteristics can be obtained.

Claims (5)

A photosensitive coloring composition containing a photopolymerization initiator (A) represented by the following formula (1) or (11), a resin (B), a photopolymerizable compound (C), and a pigment (D) ), Here, in the formula (1), R ₁ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substitution or Unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl, substituted or unsubstituted arylsulfanyl , substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinylene, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, substituted or Unsubstituted indenyl, substituted or unsubstituted anthraceneoxy, substituted or unsubstituted amino group, substituted or unsubstituted phosphinoyl, substituted or unsubstituted carbamoyl, or substituted Or unsubstituted sulfamoyl, R ₂ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or Unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, taken Alken or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted alkane a sulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted decyloxy group, or a substituted or unsubstituted amino group, each of R ₃ to R ₅ independently represents a hydrogen atom, a halogen atom, a cyanogen Alkyl, nitro, substituted or unsubstituted alkenyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or not Substituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted fluorenyl group, or substituted or unsubstituted Amino, R ₆ to R ₉ each independently represent a hydrogen atom, a halogen atom, a cyano group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group. Alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted Epoxy, substituted or unsubstituted alkenyl, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted aromatic a sulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted amine group, or a substituent of the following formula (2), (2) In the formula (2), R _{1 '} and R _{2' are} synonymous with R ₁ and R ₂ , and R ₁₀ to R ₁₄ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a halogenated alkyl group, a substituted or unsubstituted group. An alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted fluorenyl group, However, R ₁₀ to R _{14 are} not all hydrogen atoms at the same time, and further, at least one of R ₁₀ to R ₁₄ is a nitro group or the following formula (3), In the formula (3), R ₁₅ to R ₁₉ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a halogenated alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or not Substituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylthio group a substituted or unsubstituted arylthio group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted amine group, the formula (11) In the formula (11), R ₅₁ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group. a substituted, unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkyl sulfinic acid Mercapto, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted a methoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted phosphino group, a substituted or unsubstituted aminomethyl fluorenyl group, or a substituted or unsubstituted amine sulfonyl group, and R ₅₂ represents a group selected from cyclopropyl a cycloalkyl group having a ring, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and a cyclooctadecyl group substituted with an alkyl group having 1 to 20 carbon atoms, and R ₅₃ to R ₅₅ each independently represent a hydrogen atom; a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted An arylthio group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted amino group, each of R ₅₆ to R ₅₈ independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a halogenated alkyl group, a substituted or unsubstituted group. Alkylsulfinyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, or substituted or unsubstituted fluorenyl R ₅₉ to R ₆₃ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a halogenated alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, Substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, a substituted or unsubstituted acyl, substituted or unsubstituted amino group, R ₆₄ a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group Aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted anthracene A group, or a substituted or unsubstituted amine group. The photosensitive coloring composition as described in claim 1, further comprising another photopolymerization initiator (Y). The photosensitive coloring composition according to claim 2, wherein the other photopolymerization initiator (Y) comprises a acetophenone-based compound At least one or more compounds selected from the group consisting of a compound, a phosphine compound, and an imidazole compound. The photosensitive coloring composition according to any one of the items 1 to 3, further comprising a polyfunctional thiol (F). A color filter comprising a photosensitive coloring composition according to any one of claims 1 to 4 on a transparent substrate, selected from a filter section ( At least one of a filter segment) and a black matrix.