JP2011022384A - Black colored composition, method for producing black matrix and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a black colored composition which is applied to an exposure system using laser light of 330-430 nm wavelength as an exposure light source, and which has a high pigment content or a large film thickness, is excellent in development resistance/resolution, and shows high sensitivity and a high residual film ratio, a method for producing a color filter with a black matrix using the black colored composition, and a color filter produced by the method. <P>SOLUTION: The black colored composition comprises: a black pigment; a resin: a monomer having an ethylenically unsaturated double bond; and a specific oxime ester-based photopolymerization initiator, and can be cured upon irradiation with laser light. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a black coloring composition used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like. The present invention relates to a method for producing a color filter using the black coloring composition, and a color filter produced by this method.

  The color filters that make up a liquid crystal display (LCD) are made by arranging two or more kinds of fine band (striped) filter segments of different hues in parallel or intersecting on the surface of a transparent substrate such as glass or the like. The filter segments are arranged in a constant arrangement. The filter segments are as fine as several μm to several 100 μm, and are arranged regularly in a predetermined arrangement for each hue such as red, green, and blue.

  In order to improve contrast, a black matrix is generally disposed between the filter segments of each color of the color filter. In recent years, from the viewpoint of environmental issues, low reflection, and low cost, the black matrix has been focused on resin black matrix in which a light-shielding black pigment, such as carbon black, is dispersed in the resin instead of a metal chromium black matrix. Has been.

  The color filter is one of the important members that influence the visibility of the color liquid crystal display device. In order to improve the visibility, that is, to obtain a clear image, it is necessary to achieve the light shielding improvement in the black matrix. The black matrix is arranged in a lattice pattern between a plurality of colors, and plays a role of improving contrast at the time of display.

  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, in the method of increasing the content of the dye, problems such as a decrease in sensitivity, developability and resolution are generated. In the method of increasing the film thickness, there is a problem that the exposure light does not reach the bottom of the film and the pattern shape becomes defective.

  In order to solve such problems, the photosensitive coloring composition generally includes (1) provision of a reactive double bond of a resin, (2) increase of a photopolymerization initiator and a sensitizer, and (3) a monomer. Is selected or increased. For example, in Patent Document 1, as a radiation-sensitive composition exhibiting excellent developability even when a pigment is contained at a high concentration, a colorant, an alkali-soluble resin, a polyfunctional monomer, and a compound having a specific structure are used. Disclosed are compositions containing selected photoradical generators. Moreover, in patent document 2, as a photopolymerization initiator as a colored photosensitive resin composition capable of giving a colored pattern with a low exposure amount even when the colorant concentration is increased, at least one acetophenone compound and at least one kind are used. A composition containing a triazine compound and containing at least one amine compound as a photopolymerization initiator is disclosed.

On the other hand, with the recent increase in the size of products using color filters, the photomask for forming the black matrix is forced to increase in size, leading to an increase in manufacturing cost. In the commonly used proximity exposure method (ultraviolet light source proximity exposure method), a large photomask that matches the size of the substrate is required to process a large substrate, but in the laser exposure method, a small photomask is required. Or maskless, and cost reduction can be expected. For example, Patent Document 3 discloses a highly sensitive curable composition containing an ethylenically unsaturated group-containing compound having 5 or more carbon atoms in a curable composition using a semiconductor laser having a wavelength of 405 nm as an exposure light source. ing. Patent Document 4 uses an initiator that uses a laser device having a light source wavelength of less than 430 nm as an exposure light source and does not have a spectral sensitivity of 430 nm or more. The mass ratio between the initiator and the polysynthetic compound is as follows. A curable composition suitable for high-sensitivity exposure in a specific numerical range is disclosed. Patent Document 5 discloses an oxime ester compound for an initiator species, and Patent Document 6 discloses an oxime ester compound and a photopolymerization initiator containing the compound for an initiator species.

JP 2001-264530 A JP 2003-156842 A Japanese Patent No. 3912405 JP 2007-114602 A JP 2008-179611 A Japanese Patent No. 4223071

  The present invention is a black coloring composition that is applied to a method of exposing using a laser having a wavelength of 330 to 430 nm as an exposure light source, and is excellent in development resistance and resolution even when the pigment content is high or the film thickness is large. An object of the present invention is to provide a black colored composition having a high sensitivity and a high residual film ratio, a method for producing a color filter having a black matrix using the black colored composition, and a color filter produced by the method. Yes.

〔式（１）において、Ｒ^１は、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又はＣＮを表し、アルキル基、アリール基及びアリールアルキル基の水素原子は、更にＯＲ^２１、ＣＯＲ^２１、ＳＲ^２１、ＮＲ^２２Ｒ^２３、−ＮＣＯＲ^２２−ＯＣＯＲ^２３、ＣＮ、ハロゲン原子、−ＣＲ^２１＝ＣＲ^２２Ｒ^２３又は−ＣＯ−ＣＲ^２１＝ＣＲ^２２Ｒ^２３で置換されていてもよく、Ｒ^２１、Ｒ^２２及びＲ^２３は、それぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、Ｒ^２は、Ｒ^１１又はＯＲ^１１を表し、Ｒ^１１は、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基又は炭素原子数７〜３０のアリールアルキル基又を表し、アルキル基、アリール基及びアリールアルキル基の水素原子は、更にハロゲン原子で置換されていてもよく、Ｒ^３は、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基又は炭素原子数７〜３０のアリールアルキル基を表し、上記Ｒ^１、Ｒ^３、Ｒ^２１、Ｒ^２２及びＲ^２３で表される置換基のアルキレン部分のメチレン基は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合、チオエステル結合、アミド結合又はウレタン結合により１〜５回中断されていてもよく、上記置換基
のアルキル部分は分岐側鎖があってもよく、環状アルキルであってもよく、上記置換基のアルキル末端は不飽和結合であってもよく、Ｒ^３は、隣接するベンゼン環と一緒になって環を形成していてもよい。Ｒ^４及びＲ^５は、それぞれ独立に、Ｒ^１１、ＯＲ^１１、ＣＮ又はハロゲン原子を表し、ａ及びｂは、それぞれ独立に、０〜３である。） The present invention is for solving the above problems, and the invention according to claim 1 of the present invention is represented by a black pigment, a resin, a monomer having an ethylenically unsaturated double bond, and the following formula (1). The black coloring composition is characterized by containing an oxime ester photopolymerization initiator and curable by irradiation with a laser beam.

[In the formula (1), R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or CN; Group and arylalkyl group are further OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , —NCOR ²² —OCOR ²³ , CN, halogen atom, —CR ²¹ = CR ²² R ²³ or —CO—CR ²¹ = CR ²² R ²³ may be substituted, and R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms. represents an aryl group or a heterocyclic group having 2 to 20 carbon atoms carbon atoms 7 to 30, ^{R 2 represents R 11} or ^{oR 11, R 11} is C 1 -C 20 alkyl groups, aryl groups having 6 to 30 carbon atoms or arylalkyl groups having 7 to 30 carbon atoms, wherein the hydrogen atoms of the alkyl group, aryl group and arylalkyl group are further substituted with halogen atoms. R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and the above R ¹ , R ³ , R ²¹ The methylene group of the alkylene part of the substituent represented by R ²² and R ²³ is interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. The alkyl part of the substituent may have a branched side chain or may be a cyclic alkyl, and the alkyl terminal of the substituent is an unsaturated bond. There may be a, R ³ may form a ring together with the adjacent benzene ring. R ⁴ and R ⁵ each independently represent R ¹¹ , OR ¹¹ , CN or a halogen atom, and a and b are each independently 0 to 3. )

  Next, the invention according to claim 2 of the present invention includes a step of forming a colored coating film on the substrate using the black coloring composition according to claim 1, and a region where the black matrix of the colored coating film is to be formed. And a step of irradiating and curing a laser having a light source wavelength of 330 to 430 nm, and a step of forming a black matrix by removing an uncured portion of the colored coating film. It is.

  According to a third aspect of the present invention, there is provided a color filter comprising a black matrix produced by the method according to the second aspect.

  The black coloring composition of the present invention contains a black pigment, a resin, a monomer having an ethylenically unsaturated double bond, and a specific oxime ester photopolymerization initiator. Thus, a black matrix excellent in sensitivity, pattern linearity, and cross-sectional shape can be formed.

  In addition, since the oxime ester compound according to the present invention generates highly active radicals, it can form a pattern with a small amount of exposure, and further has an absorption wavelength at 330 to 430 nm. Is expensive. Therefore, according to the method for producing a color filter of the present invention, by irradiating a laser of a specific wavelength for a short time, the black coloring composition can be cured in a very short time, so a small photomask is used, Alternatively, a filter segment having an excellent shape can be formed at a low cost without using a mask. Furthermore, according to the present invention, a high-quality and inexpensive color filter is provided.

  First, the black coloring composition of this invention is demonstrated. The black coloring composition of the present invention is a black coloring composition containing a pigment, a monomer having an ethylenically unsaturated double bond, and a photopolymerization initiator, and curable by laser irradiation at 330 to 430 nm.

式（１）で表される化合物を含む光重合開始剤を含有することによって、現像耐性に優れ、カラーフィルタの生産安定性に優れた黒色着色組成物が得られる。この光重合開始剤を含有する感光性着色組成物を用いることにより、高濃度で薄膜な、高品質なブラックマトリックスを形成することができる。 [Photopolymerization initiator]
The photopolymerization initiator according to the present invention contains a compound of the formula (1).

By containing the photoinitiator containing the compound represented by Formula (1), a black colored composition having excellent development resistance and excellent color filter production stability can be obtained. By using the photosensitive coloring composition containing this photopolymerization initiator, a high-quality black matrix having a high concentration and a thin film can be formed.

The compound represented by Formula (1) is an oxime ester compound. When this oxime ester compound absorbs ultraviolet rays, the oxime N—O bond is cleaved to generate an iminyl radical and an alkyloxy radical. Since these radicals are further decomposed to generate radicals with high activity, a pattern can be formed with a small exposure amount. Furthermore, since it has an absorption wavelength at 330 nm to 430 nm by adding a nitrocarbazole group, the reaction efficiency with various ultraviolet and visible light sources is high. Further, R ¹ site in the formula (1) is considered to enhance the development resistance.

In the black colored composition of the present invention, other photopolymerization initiators can be used in combination with the compound represented by the formula (1). Other photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 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)- Acetophenone compounds such as butan-1-one, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzoate Benzophenone compounds such as zophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2- Thioxanthone compounds such as chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6- Bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2-pi Peronyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine , 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine and other triazine compounds, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, Phosphine compounds such as su (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, quinones such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone Compounds, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds and the like are used. These other photopolymerization initiators can be used alone or as a mixture of two or more at any ratio as required. These other photopolymerization initiators are used in an amount of 5 to 25 parts by mass, preferably 10 to 20 parts by mass with respect to 100 parts by mass of the compound represented by the formula (1) in the black colored composition. it can.

[Black pigment]
When forming a black matrix using the black coloring composition of the present invention, black pigments such as carbon black, aniline black, anthraquinone black pigment, and perylene black pigment can be used. Specifically, C.I. I. Pigment Black 1, 6, 7, 12, 20, 31, etc. can be used. A mixture of a red pigment, a blue pigment, and a green pigment can also be used for the black coloring composition. 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 coloring composition.

Carbon black having a specific surface area of 50 to 200 m ² / g by the BET method (Brunauer-Emmett-Teller Method) is preferable from the viewpoint of the shape of the black matrix. If the specific surface area carbon black is used less than 50 m 2 / ^g causes deterioration of the black matrix shape, in the case of using 200 meters 2 / ^g larger than carbon black, dispersing aids carbon black is excessively adsorbed This is because in order to express various physical properties, it is necessary to add a large amount of a dispersion aid.

As the carbon black, in terms of sensitivity, the oil absorption of dibutyl phthalate thereof is preferably 120 cm ^3/100 g or less, preferably from about one fewer. Furthermore, it is preferable that the average primary particle diameter of carbon black is 20-50 nm. Carbon black having an average primary particle diameter of less than 20 nm is difficult to disperse at a high concentration, and it is difficult to obtain a photosensitive black composition having good stability over time. This is because the matrix shape may be deteriorated.

[Monomer having an ethylenically unsaturated double bond]
A monomer having an ethylenically unsaturated double bond is a component that is cured by laser irradiation of 330 to 430 nm. Examples of monomers having an ethylenically unsaturated double bond include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tris. Various acrylic esters such as (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, epoxy (meth) acrylate and the like Examples include methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, acrylonitrile and the like.

  Further, a polyfunctional (meth) acrylate containing a carboxy group may be used as the monomer having an ethylenically unsaturated double bond. The polyfunctional (meth) acrylate containing a carboxy group is more preferable because the linearity and cross-sectional shape of the filter segment are further improved as compared with the polyfunctional acrylate not containing a carboxy group. Examples of the polyfunctional (meth) acrylate containing a carboxy group include esterified products of a trihydric or higher polyhydric alcohol, (meth) acrylate, and polyvalent carboxylic acid. The polyfunctional (meth) acrylate containing a carboxy group may have a urethane bond in the structure. As a commercial item of the polyfunctional (meth) acrylate containing a carboxy group, for example, trade name: TO-1382 containing a dibasic acid anhydride adduct of dipentaerythritol penta (meth) acrylate manufactured by Toagosei Co., Ltd. Is mentioned.

[resin]
The resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and these can be used alone or in combination of two or more. Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, 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, phenol resins, and polyimide resins.

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 carboxy group, and 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.

[solvent]
In the black coloring composition of the present invention, the pigment is sufficiently dispersed in a dye carrier such as a resin or a photopolymerization initiator so that the dry film thickness is 0.2 to 10 μm on a transparent substrate such as a glass substrate. A solvent can be included to facilitate application to form filter segments and black matrix. 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 monohexyl ether, ethylene glycol monomethyl ether, 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, dipropylene 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 Methylcyclohexanol acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, include dibasic acid esters such as, used these alone or in mixtures.

  Next, the method for producing the black matrix of the present invention will be described. The method for producing a black matrix of the present invention comprises a step of forming a black coating film on a substrate using a photosensitive coloring composition, and a laser having a wavelength of 330 to 430 nm on the portion of the colored coating film that becomes the black matrix. A black matrix is formed by sequentially performing a step of irradiating and curing, a step of removing an uncured portion of the black coating film, and a step of firing.

[Black film formation process]
In the black coating film forming step, a black coloring composition is applied by a spin coating method or a die coating method, and a black coating film is formed on the substrate by removing excess solvent as necessary. As the black matrix substrate, a known transparent substrate material such as a glass substrate, a quartz substrate, or a plastic substrate can be used. In particular, a glass substrate is preferable because of its excellent transparency, strength, heat resistance, and weather resistance. Moreover, in order to remove the solvent component of the coated black coloring composition, a vacuum drying process and a prebaking process can be performed as needed.

[Exposure and curing process]
In the exposure / curing step, the black matrix of the black coating film is irradiated with a laser of 330 to 430 nm from the coating film side to be cured. Examples of the exposure light source include a HeNe laser, an argon ion laser, a YAG laser, a HeCd laser, a semiconductor laser, and a ruby laser.

  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 405 nm is particularly used for a semiconductor laser. Among these, 405 nm is particularly preferable from the viewpoint of output and stability. In the present invention, a 405 nm semiconductor laser is used, and drawing is performed by a DMD (Digital Micromirror Device) drawing method. The output of the laser is 3 to 20 mW and the bandwidth is 1 to 20 mm. More preferably, the output is 6 to 9 mW and the bandwidth is 8 to 12 mm.

[Step of removing the uncured portion of the black coating]
In the uncured portion removing step, the uncured portion of the black coating film is removed to form a black matrix. When removing the uncured portion, an aqueous solution such as sodium carbonate or sodium hydroxide 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.

[Curing process]
In the curing step, the formed black matrix is completely cured by heat treatment at 200 ° C. to 250 ° C., and sufficient resistance can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this form.

  In the following examples and comparative examples, alkali-free glass “# 1737” (manufactured by Corning) was used as the transparent substrate.

In the following examples and comparative examples, exposure was performed by a DMD drawing method using a 405 nm semiconductor laser as an exposure light source. The laser output was 6 mW, the bandwidth was 9 mm, and the average illuminance was 5500 mW / cm ² (FieldMAX II PM30 “manufactured by CHIIRENT”). Further, 10 μm line width data was projected and irradiated through an exposure engine, and the exposure amount was controlled to 10 to 200 mJ / cm ² by changing the scanning speed.

  Next, the manufacturing method of the compound of Formula (11)-(1-19) which is a photoinitiator of above-described Formula (1) based on this invention used for the Example is shown below.

<Step 1 Production of Acyl Form>
In a nitrogen atmosphere, 10.4 g (78 mmol) of aluminum chloride and 33.0 g of ethane dichloride were charged, and 36 mmol of acid chloride was gradually added dropwise under ice cooling, followed by 30 mmol of a nitrocarbazole compound and 33.0 g of ethane dichloride. And stirred at 5 ° C. for 30 minutes. The reaction solution was poured into ice water and oil-water separation was performed. Solvent was removed to obtain the desired acyl form.

<Step 2 Preparation of Compounds (1-1) to (1-19) of Formula (1)>
Under a nitrogen stream, 20 mmol of the acyl compound obtained in Step 1 above, 2.1 g (30 mmol) of hydroxylamine hydrochloride and 16.9 g of dimethylformamide were charged and stirred at 80 ° C. for 1 hour. Oil-water separation was performed after cooling to room temperature. The solvent was distilled off, 25.4 g of butyl acetate was added to the residue, followed by 2.45 g (24 mmol) of acetic anhydride, and the mixture was stirred at 90 ° C. for 1 hour and cooled to room temperature. It is neutralized with a 5% aqueous sodium hydroxide solution, subjected to oil / water separation, desolvation, and recrystallization from ethyl acetate, and is represented by formulas (1-1) to (1-19) which are the target photopolymerization initiators. Respectively obtained. The structural formulas of these obtained compounds are shown below.

<Example 1>
(Preparation of black coloring composition)
The following materials were mixed and stirred to obtain a black photosensitive resin composition.
(A) Photopolymerization initiator “oxime ester compound of formula (1-1)”: 5.3 parts by mass (B) acrylic resin: 10.7 parts by mass (C) Monomer having an ethylenically unsaturated double bond: 4.4 parts by mass (D) Black pigment dispersion: 23.4 parts by mass (E) Solvent “propylene glycol monomethyl ether acetate”: 56.2 parts by mass

(Formation of black matrix)
The black colored composition was coated on a 10 cm × 10 cm glass substrate with a spin coater to a thickness of about 1.4 μm and dried naturally. This coating film was dried under reduced pressure and heated at 90 ° C. for 1 minute to remove excess solvent and dry. Then, it exposed and developed. The development time was 1.3 times as long as the coating film in the unexposed portion was completely dissolved. Thereafter, the black matrix pattern was cured in an oven at 230 ° C. for 1 hour.

<Example 2 to Example 19>
As shown in Table 1, a black colored composition was produced in the same manner as in Example 1 except that the compounds represented by formulas (1-2) to (1-19) were used as the photopolymerization initiator (A). Example 2 to Example 19 were carried out.

<Comparative Example 1>
A black colored composition was prepared and a black matrix was formed in the same manner as in Example 1 except that the following oxime ester compound was used as a photopolymerization initiator.
(A) Photopolymerization initiator “IRGACURE OXE 02” “Ciba Japan Co., Ltd.”

<Comparative Example 2>
A black photosensitive resin composition was prepared and a black matrix was formed in the same manner as in Example 1 except that the following oxime ester compound was used as a photopolymerization initiator.
(A) Photopolymerization initiator “IRGACURE OXE 01” “Ciba Japan Co., Ltd.”

[Resist sensitivity evaluation]
The resist sensitivity was determined by the exposure amount at which the black matrix pattern was finished according to the drawing dimensions of the light source. In the evaluation, when exposure was performed using a mask having an opening of 30 μm, the minimum exposure amount at which the finished line width was 30 μm or more was determined as the appropriate exposure amount. The rank of evaluation is as follows. The results are shown in Table 2.
◎: Less than 20 mJ / cm ² ○: 20 mJ / cm ² or more, less than 50 mJ / cm ² Δ: 50 mJ / cm ² or more, less than 100 mJ / cm ² ×: 100 mJ / cm ² or more

<Comparison result>
As shown in Table 2, in the case of the black coloring composition using the photopolymerization initiator of the formulas (1-1 to 1-19) according to the present invention of Examples 1 to 19, the appropriate exposure amount is very low. It was found to show high sensitivity. In addition, as shown in Table 2, Examples 1 to 19, Comparative Example 1 and Comparative Example 2 all use an oxime ester compound as a photopolymerization initiator, but Examples 1 to 19, that is, according to the present invention, The black coloring composition using the photoinitiator represented by Formula (1-1 to 1-19) which is Formula (1) showed a remarkably excellent effect.

Claims (3)

It contains a black pigment, a resin, a monomer having an ethylenically unsaturated double bond, and an oxime ester photopolymerization initiator represented by the following formula (1), and can be cured by irradiation with laser light. A black coloring composition characterized by the above.

[In the formula (1), R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or CN; Group and arylalkyl group are further OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , —NCOR ²² —OCOR ²³ , CN, halogen atom, —CR ²¹ = CR ²² R ²³ or —CO—CR ²¹ = CR ²² R ²³ may be substituted, and R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms. represents an aryl group or a heterocyclic group having 2 to 20 carbon atoms carbon atoms 7 to 30, ^{R 2 represents R 11} or ^{oR 11, R 11} is C 1 -C 20 alkyl groups, aryl groups having 6 to 30 carbon atoms or arylalkyl groups having 7 to 30 carbon atoms, wherein the hydrogen atoms of the alkyl group, aryl group and arylalkyl group are further substituted with halogen atoms. R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and the above R ¹ , R ³ , R ²¹ The methylene group of the alkylene part of the substituent represented by R ²² and R ²³ is interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. The alkyl part of the substituent may have a branched side chain or may be a cyclic alkyl, and the alkyl terminal of the substituent is an unsaturated bond. There may be a, R ³ may form a ring together with the adjacent benzene ring. R ⁴ and R ⁵ each independently represent R ¹¹ , OR ¹¹ , CN or a halogen atom, and a and b are each independently 0 to 3. )   A step of forming a colored coating film using the black coloring composition according to claim 1 on the substrate, and a region where the black matrix of the colored coating film is to be formed is irradiated with a laser having a light source wavelength of 330 to 430 nm to be cured. And a step of removing a non-cured portion of the colored coating film to form a black matrix.   A color filter comprising a black matrix produced by the method according to claim 2.