JP5627273B2 - Photosensitive coloring composition and color filter - Google Patents

Description

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

A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.
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 aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher.

For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.
In the case of the pigment dispersion method, a photosensitive coloring composition (pigment resist) in which a pigment is dispersed in a photosensitive transparent resin solution is applied to a transparent substrate such as glass, and the solvent is removed by drying. After exposure, the unexposed areas are removed in the development process to form a pattern for the first color, and after processing such as heating as necessary, the same operation is sequentially repeated for all filter colors. Can be manufactured.

In recent years, color liquid crystal display devices have formed a large market for liquid crystal color televisions, car navigation and liquid crystal display integrated laptops, and monitors and televisions for desktop computers that take advantage of energy and space saving features. As it has begun to spread. Although attention is paid to a display device that replaces a conventional CRT, the color reproduction characteristic of a liquid crystal display device is inferior to that of a CRT at present.
Therefore, there is an increasing demand for high color reproducibility in color filters in which filter segments for each color are arranged.

  In order to improve contrast, a black matrix is generally arranged between the filter segments of each color of the color filter. However, the material for forming this black matrix has recently become an environmental problem, low reflection, and low cost. In view of the above, attention is focused on a resin black matrix in which a light-shielding pigment is dispersed in a resin instead of a metal chromium black matrix. However, the resin black matrix has a problem that the light shielding property (optical density) is lower than that of the metal chromium black matrix.

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 content of the dye in the photosensitive coloring composition or to increase the film thickness. However, when the content of the dye is increased, problems such as a decrease in sensitivity and deterioration in developability and resolution occur. When the film thickness is increased, the exposure light does not reach the bottom of the film, resulting in problems such as a poor pattern shape.

On the other hand, with the recent increase in size of products using color filters, filter segments and photomasks for forming a black matrix are forced to increase in size, leading to an increase in manufacturing costs.
The commonly used proximity exposure method (ultraviolet light source exposure method) requires a large photomask that matches the substrate size in order to process a large substrate, but the laser exposure method reduces the size of the photomask. Alternatively, maskless is possible, and cost reduction can be expected.

  However, in the laser exposure method, when the photosensitive coloring composition is exposed with a laser, the surface of the colored coating film is easily cured as compared with the inside of the coating film. Depending on the difference, the coating film peels off (when the coating film is developed, only the cured coating film surface or the entire coating film peels off from the substrate), the coating film surface wrinkles (when baking after developing the coating film, heat The coating film contracts due to the above, but there are problems such as a phenomenon in which wavy wrinkles occur on the surface of the coating film due to the difference in the degree of curing, and deterioration of pattern linearity.

In particular, a blue coloring composition containing a blue pigment strongly absorbs light in a wavelength region of 310 to 380 nm and has a very high absorbance, so that the above problem appears remarkably.
For this reason, it is important to obtain a photosensitive coloring composition having high sensitivity with light in a wavelength region of 310 to 380 nm.

In addition, in the exposure process using a photomask, there are problems such as a phenomenon that diffraction fringes are generated on the pattern surface and surface roughness that is uneven on the pattern surface.
Laser light is highly diffractive, and the laser light is diffracted at the edge of the photomask and interferes with the light that has passed through the mask opening. It is estimated that decomposition will accelerate, but it is not certain.

In order to solve such a problem, Patent Document 1 proposes a color filter manufacturing method using a laser beam having a wavelength of 355 nm, but there is no specific photosensitive coloring composition.
Further, in Patent Documents 2 and 3, although a colored curable composition for ultraviolet laser exposure has been studied, it does not satisfy the required characteristics of a color filter by making both pattern formation and surface state compatible. It was.

JP 2003-287614 A JP 2010-15111 A JP 2010-15106 A

The present invention has been made under the circumstances as described above, and is a photosensitive coloring composition having good stability matched with a laser having a wavelength of 310 to 380 nm, and is free from peeling of the coating film surface and wrinkling of the coating film surface. Another object of the present invention is to provide a photosensitive coloring composition capable of forming a filter segment and a black matrix excellent in pattern shape and chemical resistance, and a color filter using the same.

  The photosensitive coloring composition of the present invention is expressed by the following formula (1) in order to obtain high sensitivity and an excellent pattern shape in the step of curing by laser irradiation with a wavelength of 310 to 380 nm. The photopolymerization initiator used is used.

  That is, the photosensitive coloring composition of the present invention comprises a photopolymerization initiator (A) represented by the following general formula (1), a resin (B), a photopolymerizable compound (C), and a pigment (D And a step of forming a colored coating film on the substrate using the photosensitive coloring composition, and a region for forming a filter segment or a black matrix of the colored coating film. And a method for producing a color filter comprising: a step of curing by laser irradiation with a wavelength of 310 to 380 nm; and a step of forming a filter segment or a black matrix by removing an uncured portion of the colored coating film. Is a photosensitive coloring composition.

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 alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl, Oxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted Or an unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted amino group, It represents a substituted or unsubstituted sulfamoyl group.
R ₂ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group Represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted amino group.
R _{3 to} R ₅ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or Unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl Represents a group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.
R _{6 to} R ₉ are each independently a hydrogen atom, halogen atom, cyano group, haloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or Unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl Represents a group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted amino group, or a substituent represented by the following general formula (2).
General formula (2)
(In formula (2), R _{1 ′} and R _{2 ′} have the same meanings as R ₁ and R _2. )
R _{10 to} R ₁₄ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkyl A sulfonyl group, a substituted or unsubstituted arylsulfonyl group, and a substituted or unsubstituted acyl group are represented, but all of R _{10 to} R ₁₄ are not hydrogen atoms at the same time. Further, at least one of R _{10 to} R ₁₄ is a nitro group or the following general formula (3).
General formula (3)
(In formula (3), R _{15 to} R ₁₉ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl Represents a sulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.))

  Moreover, this invention relates to the said photosensitive coloring composition characterized by resin (B) containing a thermosetting resin.

  The present invention also relates to the photosensitive coloring composition, wherein the thermosetting resin is a melamine resin.

Moreover, this invention relates to the said photosensitive coloring composition characterized by the melamine resin being a mixture of the thermosetting melamine compound represented by following General formula (4), and / or its partial condensate.
General formula (4):
(In General Formula (4), D _{1 to} D ₆ are independent substituents, and are CH ₂ OCH ₃ or CH ₂ OC ₄ H _9. )

  The present invention also relates to a color filter comprising a filter segment or a black matrix formed from the photosensitive coloring composition on a transparent substrate.

  The present invention also includes a step of forming a colored coating film by applying the photosensitive coloring composition on a substrate, and a laser having a wavelength of 310 to 380 nm in a region where the filter segment or black matrix of the colored coating film is to be formed. And a step of forming a filter segment or a black matrix by removing an uncured portion of the colored coating film, and a method for producing a color filter.

The photosensitive coloring composition of the present invention has a high pigment content or a large film thickness of each color filter segment and black matrix by using a specific oxime ester compound as a photopolymerization initiator in a laser exposure method. In both cases, there is provided a photosensitive coloring composition capable of forming a filter segment excellent in pattern shape without peeling of the coating film surface, generation of coating film surface wrinkles and diffraction fringes.
In addition, according to the present invention, the photosensitive coloring composition can be cured in a very short time by irradiating with a laser having a specific wavelength for a short time. Thus, a method for producing a color filter capable of forming a filter segment having an excellent shape at low cost is provided.
Therefore, a high-quality and inexpensive color filter can be obtained by using the photosensitive coloring composition of the present invention.

First, the photosensitive coloring composition in this invention is demonstrated.
The photosensitive coloring composition of the present invention comprises a photopolymerization initiator (A) represented by the general formula (1), a resin (B), a photopolymerizable compound (C), and a pigment (D). A photosensitive coloring composition containing the step of coating the photosensitive coloring composition on a substrate to form a coating film, and forming a filter segment or a black matrix formation region of the colored coating film with a wavelength of 310 It is used for the manufacturing method of the color filter which comprises the process hardened | cured by laser irradiation of -380nm, and the process of removing the uncured part of the said colored coating film, and forming a filter segment or a black matrix.

  The photopolymerization initiator (A) represented by the general formula (1) has a high sensitivity, and a coating film having a particularly high residual film ratio is obtained. Therefore, a photosensitive coloring composition having excellent production stability of a color filter. Thus, it is possible to form an excellent pattern-shaped filter segment and a black matrix without generation of diffraction fringes and surface roughness due to laser exposure.

<Photopolymerization initiator (A)>
The photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention is a compound represented by the general formula (1). In the general formula (1), R ¹ is substituted or unsubstituted. Alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted Heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group Substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted Acyloxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted phosphinoyl group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group,.

General formula (1)

Examples of the substituted or unsubstituted alkenyl group for R ¹ include straight-chain, branched-chain, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms. Specific examples include a vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2- Pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3- Examples thereof include butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like, but are not limited thereto.

The substituted or unsubstituted alkyl group in R ¹ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and optionally one or more Examples thereof include a linear, branched, monocyclic or condensed polycyclic alkyl group interrupted by -O-. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —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 (where n is 1) To 8), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH ₂ —. Examples thereof include, but are not limited to, CH ₃ —, —CH ₂ —CH— (OCH ₃ ) _{2 and the} like.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include the following, but are not limited thereto. Is not to be done.

The substituted or unsubstituted alkyloxy group in R ¹ is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and optionally 1 Examples include a linear, branched, monocyclic or condensed polycyclic alkyloxy group interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group, hexyloxy Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boroni Group, 4-decyl cyclohexyl although group and the like, but is not limited thereto. Specific examples of the linear or branched alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —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 (wherein n is 1 to _{8), - O- (CH 2} -CH 2 -CH 2 -O) m -CH 3 ( here m is 5 1), - O-CH _{2 -CH (CH 3) -O-} CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include the following. It is not limited.

Examples of the substituted or unsubstituted aryl group in R ¹ include monocyclic or condensed polycyclic aryl groups having 6 to 24 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, 1 -Anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 2 -Fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p-cumenyl group P-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromopheny Group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group, and the like, but are not limited thereto. It is not a thing.

Examples of the substituted or unsubstituted aryloxy group in R ¹ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9- Although a fluorenyloxy group etc. can be mentioned, it is not limited to these.

Examples of the substituted or unsubstituted heterocyclic group for R ¹ include aromatic or aliphatic heterocyclic groups having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl group, chromenyl Group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, 2- Indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquino Group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, Imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group, - quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl of the group and the like, but is not limited thereto.

Examples of the substituted or unsubstituted heterocyclic oxy group in R ¹ include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Examples include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group , 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group and the like, but are not limited thereto.

Examples of the substituted or unsubstituted alkylsulfanyl group in R ¹ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms. Specific examples include a methylthio group and an ethylthio group. Propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like, but are not limited thereto.

Examples of the substituted or unsubstituted arylsulfanyl group in R ¹ include a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms, and specific examples include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, Examples thereof include, but are not limited to, a 9-anthrylthio group and a 9-phenanthrylthio group.

The substituted or unsubstituted alkylsulfinyl group in R ¹ is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, and a butylsulfinyl group. Group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group, etc. However, it is not limited to these.

  As the substituted or unsubstituted arylsulfinyl group, an arylsulfinyl group having 6 to 30 carbon atoms is preferable, and specific examples include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, a 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2-butyloxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group Group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfinyl group § sulfonyl phenylsulfinyl group, 4-dimethylaminophenyl sulfinyl but Le group and the like, but is not limited thereto.

The substituted or unsubstituted alkylsulfonyl group for R ¹ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, and a butylsulfonyl group. Hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group and the like. It is not limited to these.

The substituted or unsubstituted arylsulfonyl group for R ¹ is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specific examples include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, and 2-chlorophenyl. Sulfonyl group, 2-methylphenylsulfonyl group, 2-methyloxyphenylsulfonyl group, 2-butyloxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3- Nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methyloxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfo Group, 4-but-dimethylaminophenyl sulfonyl group and the like, but is not limited thereto.

Examples of the substituted or unsubstituted acyl group for R ¹ include a hydrogen atom or a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or 2 to 20 carbon atoms. A carbonyl group substituted with an alkyloxy group, a carbonyl group bonded with a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms, or a carbonyl group substituted with a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms A carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a group, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom is bonded. Specific examples include a formyl group, an acetyl group Group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl , Stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxy Carbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthryl Carbonyl group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminophenyl Oxycarbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrylyloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, Although an isonicotinoyl group etc. can be mentioned, it is not limited to these.

Examples of the substituted or unsubstituted acyloxy group in R ¹ include an acyloxy group having 2 to 20 carbon atoms, and specific examples include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, A fluoromethylcarbonyloxy group, a benzoyloxy group, a 1-naphthylcarbonyloxy group, a 2-naphthylcarbonyloxy group, and the like can be given.

Examples of the substituted or unsubstituted amino group in R ¹ include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, and a dibenzylamino group.

  Here, as the alkylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group , Octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentyl Amino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantami Group, and the like, but not limited thereto.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, Examples include, but are not limited to, piperazino groups.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- A biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, and the like are exemplified, but the invention is not limited thereto.

  Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like are exemplified, but not limited thereto.

Examples of the substituted or unsubstituted phosphinoyl group in R ¹ include phosphinoyl groups having 2 to 50 carbon atoms. Specific examples thereof include dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenyl. Examples include, but are not limited to, phosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group. is not.

Examples of the substituted or unsubstituted carbamoyl group in R ¹ include a carbamoyl group having 1 to 30 carbon atoms, and specific examples thereof include N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N- Butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N 2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3 -Cyanoff Nylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl Group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group, and the like, but are not limited thereto.

Examples of the substituted or unsubstituted sulfamoyl group in R ¹ include a sulfamoyl group having 0 to 30 carbon atoms, and specific examples include a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, an N N-dialkylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like. It is not limited to.

R ² represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl 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, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted amino group.

R ² is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, Examples of the substituted or unsubstituted alkylsulfonyl group, the substituted or unsubstituted arylsulfonyl group, the substituted or unsubstituted acyloxy group, and the substituted or unsubstituted amino group include the substituted or unsubstituted alkenyl group in R ¹ described above. Substituted or unsubstituted Alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or Unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl It is synonymous with a group, a substituted or unsubstituted acyloxy group, and a substituted or unsubstituted amino group.

R ^{3 to} R ⁵ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or Unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl A group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.

As a halogen atom in R < ³ > -R < ⁵ >, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

A substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted in R ^{3 to} R ⁵ Unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted acyl group, and substituted or unsubstituted The amino group is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group in R ¹ described above. Substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic group It is synonymous with a Si group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, and a substituted or unsubstituted amino group.

R ^{6 to} R ⁹ are each independently a hydrogen atom, halogen atom, cyano group, haloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or Unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl Group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted amino group, or It is a substituent represented by Formula (2).

General formula (2)

(In formula (2), R ¹ ′ and R ² ′ have the same meanings as R ¹ and R ^2. )

The halogen atom in R < ⁶ > -R < ⁹ > is synonymous with the halogen atom in R < ³ > -R < ⁵ >.

Examples of the haloalkyl group in R ^{6 to} R ⁹ include an alkyl group having 1 to 15 carbon atoms in which all the hydrogen atoms are substituted with the halogen atoms described above, and specific examples include a trifluoromethyl group and a trichloromethyl group. , Tribromomethyl group, triiodomethyl group, pentafluoroethyl group, pentachloroethyl group, pentabromoethyl group, pentaiodoethyl group, trifluorodibromoethyl group, tribromodiiodoethyl group, heptafluoropropyl group, hepta Chloropropyl group, heptabromopropyl group, nonafluorobutyl group, nonachlorobutyl group, nonabromobutyl group, undecafluoropentyl group, undecachloropentyl group, undecabromopentyl group, tridecafluorohexyl group, tridecachlorohexyl Group, pentadecafluoro Examples thereof include, but are not limited to, a ptyl group, a heptadecafluorooctyl group, a nonadecafluorononyl group, a henicosafluorodecyl group, a tricosafluoroundecyl group, and a pentacosafluorododecyl group. .

  The haloalkyl group is more preferably a trifluoromethyl group or a pentafluoroethyl group from the viewpoint of the synthesis surface and the characteristics as a colored composition.

A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, or a substituted group in R ^{6 to} R ⁹ Or an unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted aryl The sulfinyl group, the substituted or unsubstituted alkylsulfonyl group, the substituted or unsubstituted arylsulfonyl group, and the substituted or unsubstituted amino group are the substituted or unsubstituted alkyl group, substituted or unsubstituted in R ¹ described above. Alkyloxy group, substituted or unsubstituted A reel group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkylsulfanyl group, substituted or Unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, and substituted or unsubstituted Synonymous with amino group.

Examples of the substituent position of the substituent in R ⁶ to R ^9, from the characteristic surface of the synthetic surface and coloration composition, if substituted at the R ⁷ is preferred.

R ^{10 to} R ¹⁴ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkyl Although they are a sulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group, all of R ^{10 to} R ¹⁴ do not become hydrogen atoms at the same time.

The haloalkyl group in R ^{10 to} R ¹⁴ has the same meaning as the haloalkyl group in R ^{6 to} R ⁹ described above, and is 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 acyl group, a substituted or unsubstituted alkylsulfinyl group for R ¹ described above, a substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted It is synonymous with an alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, and a substituted or unsubstituted acyl group.

The haloalkyl group in R ^{10 to} R ¹⁴ is preferably a nitro group or a substituted or unsubstituted acyl group from the viewpoints of synthesis and coloring composition, and is a nitro group or the following general formula (3) Is more preferable.

General formula (3)

(In formula (3), R ^{15 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl A sulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.)

The haloalkyl group in R ^{15 to} R ¹⁹ has the same meaning as the haloalkyl group in R ^{6 to} R ⁹ described above, and is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, Substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted An arylsulfanyl group, a substituted or unsubstituted acyl group, and a substituted or unsubstituted amino group are a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group in R ¹ , Substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group Substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted acyl group, and substituted or unsubstituted It is synonymous with the amino group.

Here, the substitution position of the substituent in R ^{10 to} R ¹⁴ is more preferably substituted with R ¹² from the viewpoint of the synthesis surface and the characteristics as the coloring composition.

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

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryl groups such as phenoxy group and p-tolyloxy group. Oxy group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, Acyl group such as methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexyla Alkyl groups such as alkyl groups, dimethylamino groups, diethylamino groups, morpholino groups, piperidino groups and other dialkylamino groups, phenylamino groups, p-tolylamino groups and other arylamino groups, methyl groups, ethyl groups, tert-butyl groups In addition to alkyl groups such as dodecyl groups, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, and other heterocyclic groups such as furyl groups and thienyl groups, hydroxy groups Group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, Trimethylammonium, dimethylsulfonium, trif Cycloalkenyl phenacyl phosphonium Niu mill group, and the like.

The photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention has an electron-withdrawing substituent substituted on the phenyl group of the N-phenylcarbazole skeleton, among oxime ester photopolymerization initiators. It is a feature. Oxime ester-based photopolymerization initiators are believed to decompose the oxime ester moiety by absorbing ultraviolet rays to produce iminyl radicals and alkyloxy radicals, and the radicals of the active species produced by further decomposition cause the reaction. However, the photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention has a structure represented by the general formula (1), so that the decomposition efficiency by ultraviolet irradiation is very high, A pattern can be formed with a small exposure amount.
The reason why the photopolymerization initiator (A) of the present invention can function with higher sensitivity than the conventional initiator is considered as the following three reasons, but details are not clear.

  The first reason is that the photopolymerization initiator (A) of the present invention has extremely good ultraviolet absorption performance due to the structure represented by the general formula (1). It can absorb well. Furthermore, it is conceivable that the obtained energy is efficiently used for the decomposition of the oxime ester moiety, so that the decomposition by the energy beam irradiation is fast and a large amount of radicals can be generated instantaneously.

The second reason is that the photopolymerization initiator (A) of the present invention has a structure represented by the general formula (1), in which decomposition of an iminyl radical generated by absorbing ultraviolet rays into an active species radical occurs. It can be considered that it is very fast. If the iminyl radical to be produced is metastable, the decomposition is slowed down and the amount of active radicals produced is reduced, but this is greatly affected by the chemical structure of the UV-absorbing moiety. The photopolymerization initiator (A) of the present invention has a structure represented by the general formula (1), so that iminyl radicals generated by decomposition by light irradiation are decomposed very quickly, and a large amount of radicals are generated. It is thought that it has brought.
Moreover, since the photoinitiator (A) of this invention is decomposition | disassembly of an iminyl radical is very quick as mentioned above, it is thought that recombination is suppressed. When the number of recombination is large, the active species generated by the decomposition is reduced, so that the function as a radical polymerization initiator is lowered.

  The third reason is the synergistic effect of the effect of the carbazole substituted with the above-described electron-withdrawing substituent that can function as a good ultraviolet absorption performance and the effect of the keto oxime ester.

  The photopolymerization initiator (A) containing the compound represented by the general formula (1) is 1 to 200 parts by weight, preferably 1 to 100 parts by weight with respect to 100 parts by weight of the pigment (D) in the photosensitive coloring composition. It can be used in an amount of 150 parts by weight.

<Other photopolymerization initiator (Y)>
In the photosensitive coloring composition of the present invention, in addition to the compound represented by the above formula (1), in combination with another photopolymerization initiator (Y), a more favorable pattern shape can be obtained. The resolution is preferable.
Other photopolymerization initiators (Y) include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 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) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Acetophenone compounds such as butanone, benzoin, benzoin methyl ether, benzoin ethyl ether Benzoin compounds such as benzoin isopropyl ether and benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3, Benzophenone compounds such as 3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4- Thioxanthone compounds such as diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazi 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine compounds such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O -Benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine and the like, bis (2,4,4) 6-trimethylbenzoyl) phenylphosphine oxide, phosphine compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,2′-bis (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) Imidazole compounds such as -4,4 ', 5,5'-tetra (p-methylphenyl) biimidazole, 9,10-phenanthrenequinone, potassium Use may be made of quinone-based compounds such as nephroquinone and ethylanthraquinone, borate-based compounds, carbazole-based compounds, titanocene-based compounds and the like.

Among these, it is more preferable to include at least one photopolymerization initiator (Y) selected from the group consisting of acetophenone compounds, phosphine compounds, and imidazole compounds.
These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. The other photopolymerization initiator (Y) can be used in an amount of 1 to 200 parts by weight, preferably 1 to 150 parts by weight, based on 100 parts by weight of the pigment (D) in the photosensitive coloring composition.
Moreover, it can use in the quantity of 1-1000 weight part with respect to 100 weight part of photoinitiators (A). In order to obtain better chemical resistance, an amount of 5 to 600 parts by weight is preferable with respect to 100 parts by weight of the photopolymerization initiator (A).

<Sensitizer (E)>
Furthermore, the sensitizer (E) can be contained in the photosensitive coloring composition of the present invention. The content of the sensitizer (E) is 100 parts by weight of the photopolymerization initiator (A) in the photosensitive coloring composition.
It can be used in an amount of 1 to 100 parts by weight.
As the sensitizer (E), unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives Body, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran derivative, Examples include spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler ketone derivatives, and the like.

Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.
Among the sensitizers (E), examples of the sensitizer capable of particularly suitably sensitizing the compound represented by the general formula (1) include thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.
The sensitizer (E) may contain two or more sensitizers in any ratio.

<Resin (B)>
The resin (B) contained in the photosensitive coloring composition of the present invention is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region 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 can be used alone or in admixture of two or more.

  The resin (B) can be used in an amount of 10 to 400 parts by weight, preferably 30 to 350 parts by weight, with respect to 100 parts by weight of the pigment (D) in the photosensitive coloring composition. Use in an amount of 10% by weight or more improves film forming properties and various resistances, and use in an amount of 500% by weight or less is preferable because the colorant concentration is high and good color characteristics can be expressed.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

In the laser exposure method, when the photosensitive coloring composition is exposed, since the surface of the colored coating film is easily cured as compared with the inside of the coating film, the difference in the degree of curing between the coating film surface and the coating film tends to be large. The surface condition of the coating film is likely to deteriorate due to thermal shrinkage during firing, which is a color filter manufacturing process.
In this invention, since the surface state is excellent by hardening the inside of a coating film at the time of baking with a thermosetting resin, it is preferable to contain a thermosetting resin.

  Among thermosetting resins, epoxy resins and melamine resins are preferred because of their good coating state, and color filters and black matrices having excellent chemical resistance can be obtained by using melamine resins. It is preferably used for the coloring composition. Further, it is also preferable from the viewpoint of thermosetting reactivity and stability over time.

  The epoxy resin used in the present invention refers to a compound having an epoxy group, and is a resin in which an epoxy group undergoes a thermosetting reaction during curing, which is a color filter manufacturing process, and the coating film surface / inside is cured by crosslinking. The epoxy resin may be a low molecular compound or a high molecular compound, and representative examples include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, and novolac epoxy. Resins, cycloaliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, epoxy resins such as epoxidized oil; brominated derivatives of the above epoxy resins, tris (glycidylphenyl) methane, Triglycidyl isocyanurate etc. are mentioned. Among them, bisphenyl A type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac type epoxy resin, cycloaliphatic type epoxy resin, glycidyl ester type resin, glycidylamine type resin, tris (glycidylphenyl) methane This is preferable in that the cured density is high and the adverse effect on the developability of the colored composition is small.

  Examples of preferred commercially available epoxy compounds that can be used in the present invention include Nagase Chemtex EX111, EX201, EX411, EX901, Nippon Kayaku EPPN501H, Japan Epoxy Resin JER152, and the like.

The melamine resin used in the present invention is a synthetic resin produced by polycondensation of melamine and formaldehyde, which is a thermosetting resin belonging to an amino resin, and is a compound that acts as a thermal crosslinking agent by thermal condensation in the same manner as an epoxy resin. is there.
Representative examples include alkylated melamine resins (methylated melamine resins, butylated melamine resins, etc.), mixed etherified melamine resins, and the like, such as a high condensation type and a low condensation type. Any of these may be used alone or in admixture of two or more. Moreover, an epoxy resin can also be mixed and used as needed.

  As a more preferred melamine resin, a thermosetting melamine compound represented by the following general formula (4), a mixture of partial condensates thereof, or a mixture of thermosetting melamine compounds and partial condensates thereof (hereinafter referred to as heat) It is abbreviated as a curable melamine mixture.), Is low in viscosity and stable at room temperature, has high curability, and can be expected to improve resistance.

General formula (4):
(In General Formula (4), D _{1 to} D ₆ are independent substituents, and are CH ₂ OCH ₃ or CH ₂ OC ₄ H _9. )

Examples of the thermosetting melamine mixture include the following commercially available products.
As products in which D _{1 to} D ₆ are CH ₂ OCH ₃ , Nicarak MW-30M, Nicarac MW-30, Nicarac MW-22, and Nicarac MW-21 (manufactured by Nippon Carbide Industries Co., Ltd.), Cymel 300, Cymel 301 , Cymel 303, Cymel 350 (manufactured by Nippon Cytec Industries, Inc.), etc., D _{1 to} D ₆ are CH ₂ OCH ₃ and CH ₂ OC ₄ H ₉ products, such as Nicarax MX-45, Nicarax MX-500, Nicarax MX -520, and Nikalac MX-43 (manufactured by Nippon carbide Industries Co.), as well as, Cymel 232, Cymel 235, Cymel 236, and Cymel 238 (all manufactured by Nippon Cytec Industries Inc.), D ₁ to D ₆ is CH ₂ OC as a product of ₄ H _9, CYMEL 506 (Nippon Cytec Industries Inc.) full alkyl ether compound of hexamethylol melamine and the like, and / or The mixture of partial condensate (the average polymerization degree of 1-2) can be mentioned.

Inner one D ₁ to D one or more of _6, Iminotaipu and is H, CH ₂ OH methylol type and is, D ₁ one or more H and D ₁ to D ₆ of the to D ₆ The imino-methylol type in which the above is CH ₂ OH is not preferable because the reactivity is high and the photosensitive coloring composition thickens with time.

  The average polymerization degree of the thermosetting melamine mixture is a value obtained by dividing the weight average molecular weight of the thermosetting melamine mixture by the weight average molecular weight of the thermosetting melamine compound represented by the general formula (4). The average degree of polymerization is more than 1.05 and less than 2.00, more preferably 1.2 to 1.6. If it is 1.05 or less, the purity of the single substance is too high to form crystals, and the compatibility with the photopolymerizable compound (C) contained in the photosensitive coloring composition is unfavorably deteriorated. When it is larger than 2.00, the viscosity becomes high, which is not preferable from the viewpoint of the coating property of the photosensitive coloring composition.

  The content of the thermosetting resin is preferably 10 to 400 parts by weight, more preferably 30 to 350 parts by weight with respect to 100 parts by weight of the pigment (D) in the photosensitive coloring composition. When the addition amount is less than 10 parts by weight, the cured density of the film is low and the effect of thermal crosslinking is not exhibited. When the addition amount exceeds 300 parts by weight, the addition amount of a photopolymerizable monomer, a photopolymerization initiator, etc. In addition to being limited and unable to ensure sufficient developability, stability over time is a problem

  Moreover, it is preferable that content of the thermosetting resin in the photosensitive coloring composition contains 10 weight% or more on the basis (100 weight%) of the whole quantity of resin (B). More preferably, it is 20 to 100% by weight. When the content is less than 10% by weight, the thermosetting does not proceed sufficiently and the effect of the surface state is not exhibited.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

<Photopolymerizable compound (C)>
The photopolymerizable compound (C) contained in the photosensitive coloring composition of the present invention is a photopolymerizable monomer or oligomer, such as methyl (meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglyme Sidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester Acrylate and methylolated melamine (meth) acrylic ester, epoxy (meth) acrylate, urethane acrylate and other acrylic and methacrylic esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol di Vinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformer De, acrylonitrile, and the like. These can be used alone or in admixture 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, with respect to 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 0.03 to 0.001. 80, more preferably 0.04 to 0.60.
Furthermore, when a photosensitive coloring composition contains a sensitizer (E) and other photoinitiators (Y), a photoinitiator (A), a sensitizer (E), and other photopolymerization The ratio [I _b / M] of the total weight (I _b ) of the initiator (Y) and the weight [M] of the photopolymerizable compound (C) is preferably 0.04 to 1.20, 0 More preferably, it is 10 to 0.80.
When [I _a / M] is 0.03 or more and [I _b / M] is 0.04 or more, the sensitivity is high and good. Further, when [I _a / M] is 0.80 or more and [I _b / M] is 1.20 or more, the occurrence of surface roughness, pattern linearity and resolution are deteriorated.

<Pigment (D)>
As the pigment (D) contained in the photosensitive coloring composition of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance are preferable, and organic pigments are usually used.
Below, the specific example of the organic pigment which can be used for the photosensitive coloring composition of this invention is shown with a color index number.
Examples of the red photosensitive coloring composition for forming the red filter segment include CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 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, 217, 220 Red pigments such as 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 272, and 279 can be used. A yellow pigment and an orange pigment can be used in combination with the red photosensitive coloring composition.

Examples of yellow pigments that can be used in combination with the red photosensitive coloring composition include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 1 Or the like can be used 0,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214.
Moreover, these yellow pigments can be used for the yellow photosensitive coloring composition for forming a yellow filter segment individually or in combination of 2 or more types.

As an orange pigment that can be used in combination with the red photosensitive coloring composition, for example, orange pigments such as CI Pigment orange 36, 43, 51, 55, 59, 61, 71, 73 can be used.
Moreover, these orange pigments can be used for the orange photosensitive coloring composition for forming an orange filter segment individually or in combination of 2 or more types.

Green pigments such as CI Pigment Green 7, 10, 36, 37 and 58 can be used for the green photosensitive coloring composition for forming the green filter segment. The above-mentioned yellow pigment can be used in combination with the green photosensitive coloring composition.
Blue photosensitive coloring compositions for forming blue filter segments include, for example, CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64. , 80 and the like can be used. Purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 can be used in combination with the blue photosensitive coloring composition.

For example, CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 80 or the like is used as a cyan photosensitive coloring composition for forming a cyan filter segment. Can be used.
As the magenta color photosensitive coloring composition for forming the magenta color filter segment, purple pigments and red pigments such as CI Pigment Violet 1, 19, CI Pigment Red 81, 144, 146, 177, 169 can be used. . A yellow pigment can be used in combination with the magenta photosensitive coloring composition.

  Examples of the black photosensitive coloring composition for forming the black matrix include carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically CI pigment black 1, 6, 7, 12, 20, 31 or the like can be used. For the black photosensitive coloring composition, a mixture of a red pigment, a blue pigment, and a green pigment can also be used. As the black pigment, carbon black is preferable from the viewpoint of price and light shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together in a black photosensitive coloring composition.

Also, inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black. Examples thereof include metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
The photosensitive coloring composition of the present invention may contain a dye within a range that does not reduce heat resistance for color matching.

  In all the non-volatile components of the photosensitive coloring composition of the present invention, a preferable concentration of the pigment (D) component is 10% by weight or more from the viewpoint of obtaining sufficient color reproducibility, more preferably 15% by weight or more, Most preferably, it is 20 weight% or more. Further, since the stability of the photosensitive coloring composition is improved, the preferable concentration of the pigment (D) component is 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less. is there.

<Multifunctional thiol (F)>
The photosensitive coloring composition of the present invention can contain a polyfunctional thiol (F). The polyfunctional thiol (F) is a compound having two or more thiol (SH) groups.
When the polyfunctional thiol (F) is used together with the above-described photopolymerization initiator (A), in the radical polymerization process after light irradiation, a thiyl radical is generated that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen. The resulting photosensitive coloring composition has high sensitivity. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.
For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tris Thioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), Pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaeryth Tallhexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- ( N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.

The content of the polyfunctional thiol (F) is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the pigment (D).
By using 0.05 part by weight or more of polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

<Ultraviolet absorber (G), polymerization inhibitor (H)>
The photosensitive coloring composition of the present invention can contain an ultraviolet absorber (G) or a polymerization inhibitor (H). By containing the ultraviolet absorber (G) or the polymerization inhibitor (H), the shape and resolution of the pattern can be controlled. Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, etc. Hydroxyphenyltriazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Benzotriazoles such as 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4- Benzophenone series such as hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, salicylate series such as phenyl salicylate, p-tert-butylphenyl salicylate, Cyanoacrylates such as ethyl-2-cyano-3,3′-diphenylacrylate, 2,2,6,6, -tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis (2, 2,6,6-tetramethyl-4-piperidyl) -sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl] And hindered amines such as [(2,2,6,6-tetramethyl-4-piperidinyl) imino] and the like. Or in a mixture used. Examples of the polymerization inhibitor include methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol. Hydroquinone derivatives and phenol compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. Copper and manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxyl Min such nitroso compounds and their ammonium salts or aluminum salts and the like, and used alone or in combination.

The ultraviolet absorber and the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, with respect to 100 parts by weight of the pigment (D) in the coloring composition.
By using 0.01 part by weight or more of the ultraviolet absorber or the polymerization inhibitor, better resolution can be obtained.

<Storage stabilizer (J)>
The photosensitive coloring composition of the present invention can contain a storage stabilizer (J). By containing a storage stabilizer (J), the viscosity with time of the composition can be stabilized. Examples of the storage stabilizer include 2,6-bis (1,1-dimethylethyl) -4-methylphenol, pentaerystyryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl). Propionate], hindered phenols such as 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, tetraethylphosphine, tri Organic phosphines such as phenylphosphine and tetraphenylphosphine, phosphites such as zinc dimethyldithiophosphate, zinc dipropyldithiophosphate and molybdenum dibutyldithiophosphate, sulfurs such as dodecyl sulfide and benzothiophene, benzyltrimethyl chloride, Quaternary ammonium chloride such as diethylhydroxyamine , Lactic acid, and organic acids and their methyl ethers such as oxalic acid. Used alone or in combination.

The storage stabilizer can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the pigment (D) in the coloring composition.
By using 0.01 parts by weight or more of the storage stabilizer, the temporal stability of the photosensitive coloring composition is improved.

<Solvent>
In the photosensitive coloring composition of the present invention, the pigment (D) is sufficiently dispersed in a dye carrier such as the resin (B) or the photopolymerizable compound (C), and a dry film thickness is formed on a transparent substrate such as a glass substrate. In order to make it easy to form a filter segment and a black matrix by coating so as to be 0.2 to 10 μm, a solvent can be contained. Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 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-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o- Xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene Glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol mono Hexyl ether, ethylene glycol monomethyl ether Ter, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, 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, dip Pyrene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, 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, propyl acetate, include dibasic acid esters such as, used alone or in combination.
The solvent can be used in an amount of 100 to 10,000 parts by weight, preferably 500 to 5000 parts by weight, with respect to 100 parts by weight of the pigment (D) in the coloring composition.

<Other ingredients>
The photosensitive coloring composition of the present invention can contain an adhesion improving agent such as a silane coupling agent in order to improve the adhesion to the transparent substrate.
Examples of the silane coupling agent include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy (Cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-amino Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Examples include aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

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

Moreover, the photosensitive coloring composition of the present invention can contain an amine compound having a function of reducing dissolved oxygen.
Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like.

<Production method of photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the pigment (D) is dispersed in a dye carrier such as the resin (B) and / or a solvent using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. The pigment dispersion is finely dispersed to produce a pigment dispersion. The photopolymerization initiator (A), the resin (B), the photopolymerizable compound (C), and in some cases other photopolymerization initiators (Y ), Sensitizer (E), polyfunctional thiol (F), ultraviolet absorber (G), polymerization inhibitor (H), storage stabilizer (J), solvent, and other components can be mixed and stirred. it can. Further, the photosensitive coloring composition containing two or more kinds of pigments is prepared by mixing each pigment dispersion separately finely in a dye carrier and / or a solvent, and further mixing a photopolymerization initiator (A) or light. The polymerizable compound (C) and the like can be produced by mixing and stirring.

When the pigment is dispersed in the resin (B) and / or the solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, the photosensitivity obtained by dispersing the pigment in the resin (B) and / or solvent using the dispersion aid. When the coloring composition is used, a color filter having excellent transparency can be obtained.
The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment (D).

  The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the dye carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the dye carrier. It works. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 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 SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 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, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more.

  The pigment derivative is a compound in which a substituent is introduced into an organic pigment, and the organic pigment also includes light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called pigments. Examples of the pigment derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone 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 alkali developing type colored resist material. The colored resist material is 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. is there.

  The photosensitive coloring composition is obtained by means of centrifugal separation, sintering filter, membrane filter or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust. Is preferably removed.

<Color filter manufacturing method>
Next, a method for manufacturing the color filter of the present invention will be described.
The method for producing a color filter of the present invention comprises a step of forming a colored coating film by applying the photosensitive coloring composition on a substrate, and a region where a filter segment or a black matrix of the colored coating film is to be formed. A step of curing by laser irradiation of ˜380 nm, and a step of forming a filter segment or a black matrix by removing an uncured portion of the colored coating film.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention is a photosensitive material containing a photopolymerization initiator (A) represented by the general formula (1), a resin (B), a photopolymerizable compound (C), and a pigment (D). A step of forming a colored coating film using a colored composition (colored coating film forming step), and a step of curing a region to be formed of a filter segment or a black matrix of the colored coating film by laser irradiation with a wavelength of 310 to 380 nm ( A filter segment or a black matrix formed by an exposure / curing step) and a step of removing a non-cured portion of the colored coating film to form a filter segment or a black matrix (uncured portion removing step). .
A typical color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, and at least One yellow filter segment is provided.

  As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, 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 in order to drive the liquid crystal after forming the panel.

Hereinafter, each step will be described.
(Colored coating film forming process)
In the colored coating film forming step, the above-described photosensitive coloring composition of the present invention is applied by spin coating or die coating, and the excess coating is removed as necessary to form a colored coating on the substrate. To do.

(Exposure and curing process)
In the exposure / curing process, the filter segment formation planned region of the colored coating film is cured by laser irradiation with a wavelength of 310 to 380 nm. Specifically, a coating film formed on a large-sized substrate is irradiated with a laser through a photomask that is smaller than the substrate to cure the filter segment of the coating film.

A laser wavelength of 343 nm and 355 nm is particularly used for a solid (YAG) laser, 351 nm (XeF) is particularly used for an excimer laser, and 375 nm is particularly used for a semiconductor laser. Among these, 355 nm is more preferable from the viewpoints of stability and cost. The pulse energy range of the laser used in the present invention is 0.01 to 150 mJ / cm ² , and the laser can be applied to the coating film once or multiple times. The coating is preferably cured by applying weak energy that does not decompose the film.

(Uncured part removal process)
In the uncured portion removing step, the uncured portion of the exposed and cured coating film is removed to form a filter segment or a black matrix. When removing the uncured portion, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide or the like is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, 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 may be used.

  EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples and comparative examples, “parts” means “parts by weight”.

First, prior to the examples, a method for producing the photopolymerization initiator (A) represented by the general formula (1), the acrylic resin solution, and the pigment dispersion used in the examples and comparative examples will be described.
In the synthesis of the photopolymerization initiator (A), an intermediate compound was first synthesized, then a precursor compound was synthesized from the intermediate compound, and the photopolymerization initiator was synthesized from the precursor compound. The obtained compounds were subjected to elemental analysis (C, H, N) (Perkin Elmer 2400 · CHN) and EI-MS (Thermo PolarisQ) to perform mass spectrometry, and the respective structures were confirmed.
In addition, the molecular weight of the resin was measured in terms of polystyrene measured using HLC-8220GPC (manufactured by Tosoh Corporation) as a device, TSK-GEL SUPER HZM-N connected in series as a column, and THF as a solvent. Weight average molecular weight.

<Method for producing photopolymerization initiator (A)>
[Synthesis of Photopolymerization Initiator (A1)]
Dissolve 100.0 g of N-benzophenoylcarbazole in 1000 ml of chloroform, add 85.0 g of aluminum chloride, and stir at 0 ° C., and then add a solution of 32.0 g of propionyl chloride in 500 ml of chloroform over 2 hours. It was dripped. After completion of dropping, 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, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 113.0 g of the intermediate compound (a1). Next, 38.4 g of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature when dissolved in a mixed solution of 100.0 g of compound (a1), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid. After completion of dropping, 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, the desiccant was filtered to remove the solvent, and the residue was washed with n-hexane to give precursor compound (b1) 99. .8 g was obtained. Next, 6.3 g of acetic anhydride and 10.6 g of sodium acetate were added to 30.0 g of compound (b1) in 300 ml of ethyl acetate, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 500 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 31.4 g of a photopolymerization initiator (A1).

Photopolymerization initiator (A1)

[Synthesis of Photopolymerization Initiator (A2)]
Dissolve 100.0 g of N-benzophenoylcarbazole in 1000 ml of chloroform, add 84.0 g of aluminum chloride and stir at 0 ° C., and then add a solution of 36.8 g of butanoyl chloride in 500 ml of chloroform over 2 hours. And dripped. After completion of dropping, 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, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 109.3 g of the intermediate compound (a2). Next, 40.0 g of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature when dissolved in a mixed solution of 100.0 g of compound (a2), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid. After completion of dropping, 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, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to give precursor compound (b2) 89 .3 g was obtained. Next, when 30.0 g of compound (b2) was stirred in 300 ml of ethyl acetate, 6.1 g of acetic anhydride and 10.3 g of sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 500 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 30.0 g of a photopolymerization initiator (A2).

Photopolymerization initiator (A2)

[Synthesis of Photopolymerization Initiator (A3)]
A solution in which 100.0 g of N- (p-nitrophenyl) carbazole was dissolved in 1000 ml of chloroform, 101.8 g of aluminum chloride was further added, and 44.3 g of butanoyl chloride was dissolved in 500 ml of chloroform was stirred at 0 ° C. It was dripped over 2 hours. After completion of dropping, 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, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 113.6 g of an intermediate compound (a3). Next, 40.0 g of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature when dissolved in a mixed solution of 100.0 g of compound (a3), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid. After completion of dropping, 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, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to give precursor compound (b3) 107. 0.2 g was obtained. Next, when 50.0 g of compound (b3) was stirred in 500 ml of ethyl acetate, 19.9 g of acetic anhydride and 11.7 g of sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 500 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 57.6 g of a photopolymerization initiator (A3).

Photopolymerization initiator (A3)

[Synthesis of Photopolymerization Initiator (A4)]
Dissolve 100.0 g of N-benzophenoyl-1,3-dimethyl-carbazole in 1000 ml of chloroform, add 78.6 g of aluminum chloride and dissolve 29.6 g of propionyl chloride in 500 ml of chloroform with stirring at 0 ° C. The solution was added dropwise over 2 hours. After completion of dropping, 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, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 111.8 g of intermediate compound (a4). Next, 35.7 g of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature when dissolved in a mixed solution of 100.0 g of compound (a4), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid. After completion of dropping, 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, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to give precursor compound (b4) 98. .3 g was obtained. Next, when 30.0 g of compound (b4) was stirred in 300 ml of ethyl acetate, 5.9 g of acetic anhydride and 10.0 g of sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution was poured into 500 ml of ice water, the composition organism was extracted with ethyl acetate, the organic layer was washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 31.2 g of a photopolymerization initiator (A4).

Photopolymerization initiator (A4)

<Method for producing acrylic resin solution>
[Preparation of acrylic resin solution (resin (B1))]
370 parts of cyclohexanone was put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate at the same temperature, A mixture of 15.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.
After cooling to room temperature, about 2 g of acrylic resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized acrylic resin solution so that the nonvolatile content was 20% by weight. Addition gave Resin (B1). The weight average molecular weight of the obtained resin (B1) was 40000.

<Method for producing pigment dispersion>
[Preparation of red pigment dispersion]
After the mixture having the following composition is stirred and mixed uniformly, the mixture is dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A red pigment dispersion PR was prepared.
Diketopyrrolopyrrole pigment (CIPigment Red 254) 6.82 parts ("Irga Four Red B-CF" manufactured by Ciba Japan)
1.08 parts of anthraquinone pigment (CI Pigment Red 177) (Chromotal Red A2B manufactured by Ciba Japan)
Nickel azo complex pigment (CI Pigment Yellow 150) 0.88 parts ("E4GN" manufactured by LANXESS)
Resin-type pigment dispersant ("Solsperse 20000" manufactured by Nippon Lubrizol) 1.74 parts Diketopyrrolopyrrole pigment derivative 2.05 parts
Acrylic resin solution 5.83 parts Cyclohexanone 81.60 parts

[Preparation of green pigment dispersion]
A green pigment dispersion PG was prepared in the same manner as the red pigment dispersion using a mixture having the following composition.
Halogenated copper phthalocyanine pigment (CI Pigment Green 36) 8.93 parts ("Rionol Green 6YK" manufactured by Toyo Ink Co., Ltd.)
Monoazo pigment (CI Pigment Yellow 150) 2.74 parts ("E4GN" manufactured by LANXESS)
Resin-type pigment dispersant (“Solsperse 20000” manufactured by Nippon Lubrizol Corporation) 2.80 parts Acrylic resin solution 5.53 parts Cyclohexanone 80.00 parts

[Preparation of blue pigment dispersion]
A blue pigment dispersion P-B was prepared in the same manner as the red pigment dispersion using a mixture having the following composition.
ε-type copper phthalocyanine pigment (CIPigment Blue15: 6) 12.88 parts (“Heliogen Blue L-6700F” manufactured by BASF)
Resin-type pigment dispersant (“Solsperse 20000” manufactured by Nippon Lubrizol Corporation) 5.62 parts Acrylic resin solution 1.50 parts Cyclohexanone 80.00 parts

[Preparation of black pigment dispersion]
A black pigment dispersion P-BK was prepared in the same manner as the red pigment dispersion using a mixture having the following composition.
Carbon black (“MA77” manufactured by Mitsubishi Chemical Corporation) 11.67 parts Resin-type pigment dispersant (“Solsperse 20000” manufactured by Nippon Lubrizol Corporation) 2.80 parts Acrylic resin solution 5.53 parts Cyclohexanone 80.00 parts

[Examples 1 to 20 and Comparative Examples 1 to 6]
(Preparation of photosensitive coloring composition)
Each material was mixed and stirred at a prescription ratio shown in Tables 1 to 3, and filtered through a 1 μm filter to obtain a photosensitive coloring composition of each color.

Abbreviations in Tables 1 to 3 are shown below.
・ Resin (B)
Resin B1: previously prepared acrylic resin solution Resin B2: Epoxy resin ("EX111" manufactured by Nagase Chemtech)
Resin B3: Epoxy resin (“EX201” manufactured by Nagase Chemtech)
Resin B4: Melamine resin represented by the general formula (4), wherein D _{1 to} D ₆ are CH ₂ OCH ₃
("Nikarak MW-30" manufactured by Nippon Carbide Industries Co., Ltd.)
Resin B5: Melamine resin represented by the general formula (4),
D _{1 to} D ₆ are CH ₂ OCH ₃ and CH ₂ OC ₄ H ₉
("Nikarak MX-45" manufactured by Nippon Carbide Industries Co., Ltd.
Resin B6: Melamine resin represented by the general formula (4), and D _{1 to} D ₆ are
CH ₂ OCH ₃ and CH ₂ OH.
("Nicarac MS-11" manufactured by Nippon Carbide Industries Co., Ltd.
(Solid content 60% n-butanol / xylene diluted solution))

・ Other photoinitiators (Y)
Photoinitiator Y1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one
("Irgacure 907" manufactured by Ciba Japan)
Photopolymerization initiator Y2: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone
("Irgacure 379" manufactured by Ciba Japan)
Photopolymerization initiator Y3: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
("Lucirin TPO" manufactured by BASF)
Photopolymerization initiator Y4: 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole
("Biimidazole" manufactured by Kurokin Kasei)
Photoinitiator Y5: p-dimethylaminoacetophenone
("DMA" manufactured by Daiki Fine)
Photopolymerization initiator Y6: ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime)
("Irgacure OXE02" manufactured by Ciba Japan)
・ Sensitizer (E)
Sensitizer E1: 2,4-Diethylthioxanthone
(“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Sensitizer E2: 4,4'-bis (diethylamino) benzophenone
("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
・ Photopolymerizable compound (C)
Photopolymerizable compound C: dipentaerythritol hexaacrylate
("Aronix M-402" manufactured by Toagosei Co., Ltd.)
・ Multifunctional thiol (F)
Multifunctional thiol F1: trimethylolethane tris (3-mercaptobutyrate)
("TEMB" manufactured by Showa Denko KK)
Multifunctional thiol F2: trimethylolpropane tri (3-mercaptobutyrate)
("TPMB" manufactured by Showa Denko KK)
Multifunctional thiol F3:
Pentaerythritol tetrakis (3-mercaptopropionate)
(“PEMP” manufactured by Sakai Chemical Industry Co., Ltd.)
・ Ultraviolet absorber (G)
UV absorber G1: 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine
("TINUVIN400" manufactured by Ciba Japan)
UV absorber G2: 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol
("TINUVIN900" manufactured by Ciba Japan
・ Polymerization inhibitor (H)
Polymerization inhibitor H1: N-nitrosophenylhydroxylamine aluminum salt
("Q-1301" manufactured by Wako Pure Chemical Industries, Ltd.)
Polymerization inhibitor H2: Methylhydroquinone
(“MH” manufactured by Seiko Chemical Co., Ltd.)
・ Storage stabilizer (J)
Storage stabilizer J1: 2,6-bis (1,1-dimethylethyl) -4-methylphenol
("BHT" manufactured by Honshu Chemical Industry Co., Ltd.)
Storage stabilizer J2: Triphenylphosphine
("TPP" manufactured by Hokuko Chemical Co., Ltd.)
・ Solvent Organic solvent: cyclohexanone

(Evaluation of photosensitive coloring composition)
[Stability over time]
About the obtained photosensitive coloring composition, the viscosity of the initial stage and 1 month after room temperature was measured, and the viscosity increase degree with respect to an initial stage viscosity was calculated and evaluated. The rank of evaluation is as follows.
A: Viscosity increase rate is 3% or less and good B: Viscosity increase rate is greater than 3% and 10% or less X: Results of viscosity increase rate greater than 10% are shown in Tables 5-7.

(Formation of filter segment and black matrix)
The obtained photosensitive coloring composition 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 form a colored coating film of about 2 μm. Obtained. Next, after cooling the substrate to room temperature, the light source shown in Table 4 below was exposed through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) from the colored coating film at intervals of 150 μm. Irradiation was performed so that the amount was 20 mJ / cm ² . The exposure dose was measured using “PE10B-V2” manufactured by OPHIR.
Further, the unexposed portion was removed by spray development with a developer comprising a 0.2% by weight aqueous sodium carbonate solution, and then washed with ion-exchanged water. A matrix was formed.

  About the photosensitive coloring composition obtained by the Example and the comparative example, the following method evaluated the coating film peeling, the coating-film surface state, the presence or absence of a diffraction fringe, and the resolution. The results are shown in Tables 5-7.

The filter segments or black matrix obtained in the examples and comparative examples were observed using an optical microscope and evaluated according to the following criteria.
[Coating peeling]
○: No peeling △: Partial peeling ×: There is peeling on the entire coating surface [Surface condition]
◎: No surface wrinkles or surface roughness (coating surface is smooth)
○: There are minute surface wrinkles and surface roughness (a level that causes no practical problems).
X: There are surface wrinkles and surface roughness (a state in which wrinkles and irregularities are generated on the coating film surface)
[Diffraction fringes]
With the above evaluation method, regular fringes of the coating film due to diffracted light were observed for the pattern in the 100 μm photomask portion to evaluate diffraction fringes.
○: No diffraction fringes ×: Diffraction fringes (regular stripes are generated on the coating surface)

[resolution]
With the above evaluation method, the pattern in the 25 μm photomask portion was evaluated.
The rank of evaluation is as follows. The poor resolution means that adjacent stripe patterns are connected or chipped. The rank of evaluation is as follows.
◎: Good resolution and linearity ○: Slightly inferior in linearity but good resolution ×: Poor resolution

[Evaluation of chemical resistance]
The filter segment or black matrix formed by the above method is immersed in an N-methylpyrrolidone solution for 30 minutes, then washed with ion-exchanged water, air-dried, and the pattern on the 100 μm photomask portion is observed and evaluated using an optical microscope. went. The rank of evaluation is as follows.
◎: Appearance and color are good without change ○: Some wrinkles are generated, but color is good without change

  As shown in Tables 5 to 7, in Examples 1 to 23, the photosensitive coloring composition of the present invention is excellent in stability over time, and a filter segment formed using the photosensitive coloring composition and Although there are some differences in the black matrix depending on the formulation, all of the laser exposure methods peel off the coating film, no diffraction fringes occur, the coating film surface condition and resolution are good, and practically comparable filter segments are obtained. It was.

  In addition, when comparing Example 13 and Examples 21 to 23 using only the same photosensitive coloring composition (RB-13) and differing only in the type of the laser light source when forming the filter segment, in any laser light source, There was no peeling of the coating film, no generation of diffraction fringes, a coating film surface state and a good resolution, and a practically inferior filter segment was obtained.

Especially, in Examples 3, 5, 8, 10, 12, 13, 16, 17, 21, 22, and 23 containing a thermosetting resin as the resin (B), the surface of the coating film becomes smooth, and the surface The condition was excellent.
Furthermore, in Examples 8, 10, 12, 13, 16, 21, 22, and 23 in which the thermosetting resin is a melamine resin, the thermosetting property was improved and the chemical resistance was also excellent.
Further, in Examples 10, 13, 16, 21, 22, and 23 represented by the general formula (4) and containing a melamine resin having a specific structure, the photosensitive coloring composition is particularly excellent in stability over time. Indicated.

On the other hand, in Comparative Examples 1 and 2, the coating film was peeled off and defects in pattern characteristics occurred, and in Comparative Examples 3 to 6, there were cases where the surface condition was poor and diffraction fringes were also generated. In Comparative Examples 1-6, the thing from which all became favorable was not obtained.

Claims (5)

A photosensitive coloring composition containing a photopolymerization initiator (A) represented by the following general formula (1), a resin (B), a photopolymerizable compound (C), and a pigment (D). The resin (B) contains a thermosetting resin, and a colored coating film is formed on the substrate using the photosensitive coloring composition, and a filter segment or a black matrix of the colored coating film is to be formed. It is used in a method for producing a color filter comprising a step of curing a region by laser irradiation with a wavelength of 310 to 380 nm and a step of removing a non-cured portion of the colored coating film to form a filter segment or a black matrix. The photosensitive coloring composition characterized by these.
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 alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl, Oxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted Or an unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted amino group, It represents a substituted or unsubstituted sulfamoyl group.
R ₂ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group Represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted amino group.
R _{3 to} R ₅ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or Unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl Represents a group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.
R _{6 to} R ₉ are each independently a hydrogen atom, halogen atom, cyano group, haloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or Unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl Represents a group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted amino group, or a substituent represented by the following general formula (2).
General formula (2)

(In formula (2), R _{1 ′} and R _{2 ′} have the same meanings as R ₁ and R _2. )
R _{10 to} R ₁₄ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkyl A sulfonyl group, a substituted or unsubstituted arylsulfonyl group, and a substituted or unsubstituted acyl group are represented, but all of R _{10 to} R ₁₄ are not hydrogen atoms at the same time. Further, at least one of R _{10 to} R ₁₄ is a nitro group or the following general formula (3).
General formula (3)

(In formula (3), R _{15 to} R ₁₉ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl Represents a sulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.)) The photosensitive coloring composition according to claim 1 , wherein the thermosetting resin is a melamine resin. The photosensitive coloring composition according to claim 2 , wherein the melamine resin is a mixture of a thermosetting melamine compound represented by the following general formula (4) and / or a partial condensate thereof.
General formula (4):

(In General Formula (4), D _{1 to} D ₆ are independent substituents, and are CH ₂ OCH ₃ or CH ₂ OC ₄ H _9. ) A color filter comprising a filter segment or a black matrix formed from the photosensitive coloring composition according to any one of claims 1 to 3 on a transparent substrate. Applying the photosensitive coloring composition according to any one of claims 1 to 3 on a substrate to form a colored coating film, and forming a filter segment or a black matrix in the colored coating film, A method for producing a color filter, comprising: a step of irradiating and curing a laser having a wavelength of 310 to 380 nm; and a step of forming a filter segment or a black matrix by removing an uncured portion of the colored coating film. .