JP4821206B2 - Photosensitive coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a photosensitive coloring composition, and more particularly to a photosensitive coloring composition useful for forming a colored layer, a black matrix, and the like in a color filter used in a liquid crystal display device or a solid-state imaging device. The present invention also relates to a color filter formed using the photosensitive coloring composition.

  In order to colorize a liquid crystal display, a color filter is used in which pixels of three colors R (red), G (green), and B (blue) are arranged in a line shape or a mosaic shape on a transparent substrate. For example, a TFT (thin film transistor) color liquid crystal display that is widely used at present is called a backlight in which a liquid crystal is sealed between a transparent glass substrate on which a color filter is formed and a transparent glass substrate on which a TFT is formed. The light source is made up of. When light emitted from the backlight passes through the liquid crystal panel, an image is displayed by controlling the transmittance by the voltage applied to the liquid crystal. In the past, a chromium-based material has been used to form the light shielding portion, but a resin black matrix is often used in consideration of environmental considerations.

  Conventionally, many methods for producing a color filter using an acrylic photosensitive coloring composition have been proposed. Among them, a negative type (exposed portion curing) including a pigment, an acrylic resin, a reactive monomer, and a photopolymerization initiator. Type) photosensitive coloring compositions are widely known. Curing of such a photosensitive composition is initiated by decomposing or activating the photopolymerization initiator by ultraviolet irradiation to generate free radicals, which activate the ethylenically unsaturated compounds present in the vicinity. It progresses when it is converted to radical polymerization. When forming a color filter using such a negative photosensitive composition, usually after applying a negative photosensitive composition containing a pigment on a substrate and irradiating ultraviolet rays through a photomask, The pixel pattern is formed by developing and dissolving the ultraviolet non-irradiated portion with a developer.

  However, when trying to form a color filter from such a negative photosensitive composition, when developing with an alkali developer, the pixel portion cured by irradiation with radiation expands with the alkali developer, resulting in a pixel. In some cases, the resolution of the pattern is lowered or the pixel pattern is deformed. In addition, the adhesion strength of the pixel pattern is reduced by development, and there is a disadvantage that the pixel pattern is peeled off from the substrate after the pixel array is formed. Furthermore, even if an attempt is made to form a pattern according to the mask size design, the irradiation light tends to be a rough pattern due to the diffraction of the mask, making it difficult to manufacture a highly accurate pixel array. Therefore, even when forming a fine pixel array, development of a negative photosensitive coloring composition that is highly accurate and has excellent adhesion strength to the substrate and can form a pixel array even under mild exposure conditions. Was desired.

  As a photosensitive coloring composition for producing a conventional color filter, a thiophosphite compound is added to a photosensitive coloring composition mainly composed of an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, and a coloring agent. A method of improving sensitivity by containing 0.01 to 20% by mass has been proposed (for example, see Patent Document 1). In addition, a method for improving sensitivity and shortening the exposure time by including an oxime-based photopolymerization initiator in a photosensitive coloring composition mainly composed of a transparent resin, a pigment and the like has been proposed (for example, , See Patent Document 2).

However, patterning using the photosensitive coloring composition as described above causes a problem that the pixels become thicker than the mask size, and it is difficult to obtain a high-definition pixel array as designed regardless of the exposure conditions. It was. Further, when the development conditions are strengthened, problems such as pixel chipping and peeling occur, and the development of a photosensitive coloring composition having a wide development margin has been desired.
Examples of countermeasures against variations in pattern shape with respect to changes in exposure dose include examples in which hindered phenolic antioxidants are used in photosensitive coloring compositions (see, for example, Patent Document 3), and phosphoric acid antioxidants. An example in use (see, for example, Patent Document 4) has been proposed. However, when these compositions are used, the pattern thickness that occurs when the exposure amount or exposure illuminance is raised above a certain level can be improved, but the effect on the pixel thickness that occurs when the exposure gap is widened is insufficient. there were. Further, when these antioxidants are used, the sensitivity is likely to be lowered, and there is a possibility that the pixel is chipped or peeled off.

  It is known that a polymerization inhibitor can be used for improving storage stability such as prevention of gelation and suppressing a polymerization reaction during the production of a polymer, as having a function similar to that of an antioxidant. For example, a coloring composition containing a hydroquinone-based polymerization inhibitor has been proposed (see, for example, Patent Document 5), and is said to be effective in preventing gelation of a thermosetting type composition. Examples of polymers used in polymer production include phenol-based and phosphite-based polymerization for suppressing radical-polymerizable groups when reacting amide bonds by reacting radical-polymerizable group-containing isocyanate compounds with acidic functional groups in the main chain. Inhibitors are used (see, for example, Patent Document 6).

However, the addition of these polymerization inhibitors to the photosensitive coloring composition has not been studied in detail so far.
On the other hand, it has been proposed to use an acidic group-containing monomer as a method for achieving high definition of pixels (see, for example, Patent Document 7). However, it is difficult to obtain satisfactory exposure and development margins using only these materials, and development of photosensitive coloring compositions that can form high-definition pixel arrays as designed while maintaining high sensitivity. Was anxious.
JP-A-5-255419 JP 2005-99488 A JP 2002-22925 A JP 2003-25524 A Japanese Patent Laid-Open No. 7-228811 JP 2001-106765 A JP 2004-287232 A

  The present invention was devised in view of the shortcomings of the prior art, and the object of the present invention is that a high-definition pattern can be formed as designed even when the exposure conditions vary with high sensitivity and practical use. It is an object of the present invention to provide a coloring composition for an advantageous color filter.

（式中、ｎは１〜４の整数を表し、−Ｒ ^１ は−Ｈもしくは−ＣＨ _３ を表し、−Ｘ−は−Ｏ−、−Ｏ（ＣＨ _２ ＣＨ _２ ） _ｍ Ｏ−、または−Ｏ（ＣＨ _２ ＣＨ _２ ＣＨ _２ ） _ｍ Ｏ−を表し、−Ｙ−は炭素数１〜８のアルキレン基、ならびにそれぞれ置換されていても良いフェニレン基、シクロヘキシレン基、およびシクロヘキシレン基の一部が不飽和結合である基、からなる群から選ばれる基を表す。但し、ｍは１〜８の整数を表す。）

（式中、Ａｒは置換されていても良いアリール基を表し、Ｒ ^２ は炭素数１〜６のアルキル基を表す）
（２）前記反応性モノマー全体の酸価が５〜５０ｍｇＫＯＨ／ｇであるものを含有することを特徴とする（１）に記載のカラーフィルター用感光性着色組成物。
（３）前記重合禁止剤が顔料を除く固形分量に対して、０．１〜３質量％含まれることを特徴とする（１）または（２）に記載のカラーフィルター用感光性着色組成物。
（４）前記重合禁止剤として、下記構造式（３）または（４）で表される化合物を含有することを特徴とする（１）〜（３）のいずれかに記載のカラーフィルター用感光性着色組成物。

（式中、Ｒ ^３ 、Ｒ ^４ 、Ｒ ^５ 、はそれぞれ独立に水素原子もしくは炭素数１〜１０のアルキル基、脂環式基を表す）
（５）任意の色数で各色別に所望のパターン状に設けられた着色層からなる画素を有するカラーフィルターにおいて、該着色層が（１）〜（４）のいずれかに記載のカラーフィルター用感光性着色組成物により形成される着色膜を含有することを特徴とするカラーフィルター。 In order to solve the above problems, the present invention has the following configuration. That is,
(1) In a photosensitive color composition for a color filter containing at least a pigment, an acrylic resin, a reactive monomer, a photopolymerization initiator, a polymerization inhibitor, and an organic solvent, the polymerization inhibitor is a hydroquinone-based or catechol-based polymerization. It is an inhibitor, and the reactive monomer contains one represented by the following structural formula (1), and further contains a compound represented by the following structural formula (2) as a photopolymerization initiator. A photosensitive coloring composition for a color filter.

(Wherein, n represents an integer of 1 to 4, -R ¹ represents -H or -CH _3, -X- is _{-O -, - O (CH 2} CH 2) m O-, or -O (CH ₂ CH ₂ CH ₂ ) _m O—, wherein —Y— is an alkylene group having 1 to 8 carbon atoms, and a phenylene group, a cyclohexylene group, and a part of the cyclohexylene group, each of which may be substituted. Represents a group selected from the group consisting of a group that is an unsaturated bond, provided that m represents an integer of 1 to 8.)

(In the formula, Ar represents an optionally substituted aryl group, and R ² represents an alkyl group having 1 to 6 carbon atoms)
(2) The photosensitive coloring composition for color filters as described in (1), wherein the total reactive monomer has an acid value of 5 to 50 mgKOH / g.
(3) The photosensitive coloring composition for color filters according to (1) or (2), wherein the polymerization inhibitor is contained in an amount of 0.1 to 3% by mass based on the solid content excluding the pigment.
(4) The photosensitizer for a color filter according to any one of (1) to (3), wherein the polymerization inhibitor contains a compound represented by the following structural formula (3) or (4): Coloring composition.

(In the formula, R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alicyclic group)
(5) A color filter having a pixel composed of a colored layer provided in a desired pattern for each color with an arbitrary number of colors, wherein the colored layer is a photosensitive material for a color filter according to any one of (1) to (4). A color filter comprising a colored film formed from a conductive coloring composition.

  By using the photosensitive coloring composition of the present invention, a high-definition pattern can be formed as designed even when there is variation in exposure conditions with high sensitivity. Obtainable.

  As the pigment used in the photosensitive coloring composition of the present invention, an organic pigment, an inorganic pigment, or the like can be used, but an organic pigment is preferable from the viewpoint of heat resistance and transparency. Among them, those having high transparency and excellent light resistance, heat resistance, and chemical resistance are preferable. When specific examples of typical organic pigments are represented by color index (CI) numbers, the following are preferably used, but they are not limited to these.

  Examples of yellow pigments include pigment yellow (hereinafter abbreviated as PY) 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 168, 185, etc. are used.

  Examples of orange pigments include pigment orange (hereinafter abbreviated as PO) 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, and the like.

  Examples of red pigments include pigment red (hereinafter abbreviated as PR) 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217. 220, 223, 224, 226, 227, 228, 240, 254, etc. are used.

  Examples of purple pigments include pigment violet (hereinafter abbreviated as PV) 19, 23, 29, 30, 32, 37, 40, 50, and the like.

  Examples of blue pigments include pigment blue (hereinafter abbreviated as PB) 15, 15: 3, 15: 4, 15: 6, 22, 60, 64, and the like.

  Examples of green pigments include pigment green (hereinafter abbreviated as PG) 7, 10, 36, and the like.

  These pigments may be subjected to surface treatment such as rosin treatment, acidic group treatment, basic treatment and the like, if necessary, and can contain a dye to such an extent that the light resistance and solvent resistance are not impaired.

The pigment is, for example, a color filter R (red), G (green), or B (blue) three-color pixel, chromaticity characteristics of a CRT (cathode ray tube) phosphor, liquid crystal used in a backlight or a liquid crystal display. To match the characteristics, it is possible to mix and use several colors.
Taking the case of R (red) as an example, a combination of PR-254 and PR-177, a combination of PR-254 and PY-138, a combination of PR-254 and PY-139, a combination of PR-209 and PO-38 The chromaticity is adjusted by combination or the like.

  In the case of G (green), PG-7, PG-36 and the above yellow pigment, for example, PY-17, PY-83, PY-138, PY-139, PY-150, etc. To adjust the chromaticity.

  In the case of B (blue), the color is adjusted by a combination of PB15: 3 or PB: 15: 6 and a purple pigment such as PV-19 or PV-23.

The pigment used in the resin black matrix is not particularly limited as long as it is insoluble in the organic solvent and water used and plays a role as a light shielding agent. In addition to pigment black 7 as an organic pigment, carbon black, graphite, iron oxide, manganese oxide, titanium black and the like are used as a light shielding agent, and surface treatment can be preferably performed. If necessary, these light-shielding agents can be mixed and used, and pigments of other colors can be added. Among these light-shielding agents, titanium black is preferably included because high light-shielding properties can be obtained with a small amount of use.
The photosensitive coloring composition of the present invention preferably uses a pigment and is uniformly dispersed in a solution using a disperser. The method for dispersing the pigment is not particularly limited, and known methods such as a ball mill, a sand grinder, a three-roll mill, a high speed impact mill, and a bead mill can be used. A bead mill using media is preferably used because it can disperse fine pigments, and is suitable for forming a high-definition pattern.

  As a step of dispersing the pigment using a disperser, the pigment, an acrylic polymer, a reactive monomer, a photopolymerization initiator, an organic solvent, and a polymerization inhibitor are directly added to the disperser, and a photosensitive coloring composition is prepared. Although it can be obtained, it is preferable to prepare in advance as a pigment dispersion containing a pigment, an organic solvent, preferably an acrylic polymer, and preferably a dispersant, from the viewpoint of productivity and ease of equipment.

  The organic solvent is not particularly limited, for example, methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, (Poly) alkylene glycol ether solvents such as diethylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl ethyl ether, or propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl acetoacetate, methyl-3-methoxypropio , Ethyl-3-ethoxypropionate, methoxybut Aliphatic esters such as rubacetate and 3-methyl-3-methoxybutyl acetate, or aliphatic alcohols such as ethanol, butanol, isopropanol and 3-methyl-3-methoxybutanol, and ketones such as cyclopentanone and cyclohexanone These can be used, and these alone or two or more kinds of mixed solvents can also be preferably used. Mixing with other solvents is also preferably used.

  The acrylic resin that can be used is not particularly limited, but a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound can be preferably used. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides.

  These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, and methacrylic acid. Isopropyl, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, N-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, and other unsaturated carboxylic acid alkyl esters, styrene, p-methyls Rene, aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene and α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene and isoprene, acryloyl groups at the terminals, Alternatively, macromonomers such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysilicone having a methacryloyl group And the like, but is not limited to these.

Further, when an acrylic resin having an ethylenically unsaturated group added to the side chain is used, it can be preferably used because the sensitivity during processing is improved. Examples of ethylenically unsaturated groups include vinyl groups, allyl groups, acrylic groups, and methacrylic groups. As a method for adding such a side chain to an acrylic (co) polymer, when it has a carboxyl group or a hydroxyl group of an acrylic (co) polymer, an ethylenically unsaturated compound having an epoxy group therein In general, an addition reaction of acrylic acid or methacrylic acid chloride is used. In addition, a compound having an ethylenically unsaturated group can be added using isocyanate.
Examples of the epoxy compound having an unsaturated group that can be added to the main chain include an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group.

  Although not particularly limited, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-l Examples thereof include glycidyl) benzylacrylamide, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and epoxy compounds described in JP-A No. 2002-12607. In particular, those obtained by adding glycidyl methacrylate to a 3-4 quaternary copolymer selected from methacrylic acid and / or acrylic acid and methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, and styrene have good sensitivity and developability. Therefore, it is preferably used.

  The addition amount of the epoxy compound having an unsaturated group is preferably in the range of 0.05 to 0.8 equivalent, more preferably 0.1 to 0.6 equivalent, relative to the carboxyl group of the acrylic copolymer. . When the addition amount of the epoxy compound is less than 0.05 equivalent, the allowable development width is narrow and the pattern edge is likely to be cut off. When the addition amount is more than 0.8 equivalent, the solubility of the developer in the unexposed area is dissolved. Or the coating film hardness tends to be low, and a practical color filter is difficult to obtain.

  When adding an epoxy compound having an unsaturated group to the main chain, it is preferable to use a catalyst. Specifically, triethylamine, dimethylbutylamine, dimethylbenzylamine, diethylbenzylamine, ethylenediamine, dimethylaminopyridine, etc. A quaternary ammonium salt such as tertiary amine, dodecyltrimethylammonium chloride, triethylbenzylammonium chloride, tetramethylammonium chloride, tetraethylammonium bromide, tetramethylurea, tetramethylguanidine, pyridine, triphenylphosphine alone, or They can be used in combination. Of these, dimethylbenzylamine is particularly preferred from the viewpoint of the ease of the addition reaction.

  The acrylic polymer having an unsaturated group in the side chain produced by such a method can be further purified by an ion exchange method or reprecipitation. As a method of reprecipitation, the binder resin solution can be precipitated by mixing with water or various organic solvents to form a powder product.

  The average molecular weight Mw (measured by gel permeation chromatography and converted using a standard polystyrene calibration curve) of the binder resin in the present invention is preferably 3,000 to 200,000, more preferably 9000 to 100,000. is there. If it is less than 3,000, sufficient cured film strength cannot be obtained, and if it exceeds 200,000, developability deteriorates, which is not preferable. Moreover, in order to obtain moderate alkali developability, the acid value is preferably 50 to 200 (mgKOH / g), more preferably 70 to 150 (mgKOH / g).

  As the dispersant, a known one can be used, and it is sometimes called a pigment derivative or a polymer dispersant. Examples of the pigment derivative include a modified alkylamine of a pigment skeleton, a carboxylic acid derivative, and a sulfonic acid derivative. As a synergist, the pigment derivative is effective for wetting the pigment and stabilizing the fine pigment. Among these pigment derivatives, sulfonic acid derivatives of organic pigments are highly effective for stabilizing fine pigments and are preferably used. The polymer dispersant is not particularly limited as long as it is usually used for a color filter, and is not limited to polyester, polyalkylamine, polyallylamine, polyimine, polyamide, polyurethane, polyacrylate, polyimide, polyamideimide, etc. Various polymers such as these polymers or copolymers thereof can be used alone or in admixture. Among these polymer dispersants, those having an amine value and an acid value are preferable, and specifically, those having an amine value in terms of solid content of 5 to 200 and an acid value of 1 to 100 are preferable. By using these dispersants, the storage stability of the pigment dispersion and thus the photosensitive coloring composition is improved, so that it is preferably used.

  After preparing the pigment dispersion by such a method, preparing a diluted varnish mixed with an acrylic resin, a reactive monomer, a photopolymerization initiator, a polymerization inhibitor, other additives, etc., and mixing with the pigment dispersion, A photosensitive coloring composition can be obtained.

As the acrylic resin, those described above can be used, and when they are previously contained in the pigment dispersion, they may be the same or different.
As a reactive monomer, it is preferable to contain what is represented by following Structural formula (1).

(Wherein, n represents an integer of 1 to 4, -R ¹ represents -H or -CH _3, -X- is _{-O -, - O (CH 2} CH 2) m O-, or -O (CH ₂ CH ₂ CH ₂ ) _m O—, wherein —Y— is an alkylene group having 1 to 8 carbon atoms, and a phenylene group, a cyclohexylene group, and a part of the cyclohexylene group, each of which may be substituted. Represents a group selected from the group consisting of a group that is an unsaturated bond, provided that m represents an integer of 1 to 8.)
These reactive monomers represented by the structural formula (1) include dipentaerythritol penta (meth) acrylate, ethylene oxide modified products of dipentaerythritol penta (meth) acrylate, propylene oxide modified products, dipentaerythritol penta (Meth) acrylate oligomers, succinic anhydride, 1-dodecenyl succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene anhydride Maleic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, Acid anhydrides such as water chlorendic acid, trimellitic anhydride, N, N-dimethylbenzylamine, triethylamine, tributylamine, triethylenediamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium bromide It can be obtained by reacting at 60 to 110 ° C. for 1 to 20 hours in the presence of a catalyst such as zinc oxide.

  Two or more types of reactive monomers can be mixed and used. In addition to the above, for example, bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipine Acid 1,6-hexanediol (meth) acrylic acid ester, propylene oxide phthalate anhydride (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin-modified epoxy di (meth) acrylate, alkyd-modified (meth) Oligomers such as acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, Methylolpropane tri (meth) acrylate, tetratrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Penta (meth) acrylate, bisphenoxyethanol full orange acrylate, dicyclopentanedienyl diacrylate, or an alkyl modified product, an alkyl ether modified product, an alkyl ester modified product, or the like thereof can be used.

  When these reactive monomers are used as a mixture of two or more, the acid value of the whole reactive monomer is preferably 5 to 50 mgKOH / g, more preferably 10 to 40 mgKOH / g. If the acid value is lower than 5 mgKOH / g, it is not preferable because the affinity for the alkaline developer is low and causes a development residue. If the acid value is higher than 50 mgKOH / g, the affinity for the developer is too high. This is not preferable because chipping or peeling of the pattern is likely to occur.

  Among these reactive monomers, those represented by the structural formula (1) are preferably contained in an amount of 10 to 95% by mass, more preferably 20 to 90% by mass. Within these ranges, a high-definition pattern can be formed with a wide development margin by appropriately mixing reactive monomers.

  As photopolymerization initiators, inorganic photopolymerization initiators such as benzophenone compounds, acetophenone compounds, thioxanthone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, triazine compounds, phosphorus compounds or titanates A publicly known thing can be used.

For example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl Ketal, α-hydroxyisobutylphenone, thioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (4-methyl) benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butano -1, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1 , 2-Benzanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4- (P-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine and the like.
Further, those represented by the following structural formula (2) are also preferably used since an improvement in sensitivity can be expected.

(In the formula, Ar represents an optionally substituted aryl group, and R ² represents an alkyl group having 1 to 6 carbon atoms)
Specifically, 2-methylbenzyl group as Ar, ethanone an ethyl group as ^{R 2,} 1- [9- ethyl-6- (2-methylbenzoyl) -9H- carbazol-3-yl)] -, 1 -(O-acetyloxime) (“CGI242” manufactured by Ciba Specialty Chemicals Co., Ltd.).
Further, it is preferable to add a sensitizing aid such as an aromatic or aliphatic tertiary amine because the sensitivity can be further improved. Moreover, these photoinitiators can also be used in combination of 2 or more types. Although there is no limitation in particular as the addition amount of a photoinitiator, Preferably it is 2-30 mass% with respect to the photosensitive coloring composition total solid, More preferably, it is 5-25 mass%.
The polymerization inhibitor used in the present invention is a hydroquinone type represented by the following structural formula (3) and a catechol type represented by (4).

(In the formula, R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alicyclic group)
More specifically, as represented by the formula (3), hydroquinone, tert-butylhydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2,5-bis Examples include (1,1-dimethylbutyl) hydroquinone, and examples of the compound represented by the formula (4) include catechol and tert-butylcatechol.
The addition amount of these polymerization inhibitors is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, based on the solid content excluding the pigment. If the amount added is less than 0.1% by mass, the effect of reducing the thickness of the pixel is small, which is not preferable. If the amount exceeds 3% by mass, the pattern is likely to peel off due to a decrease in sensitivity, which is not preferable. Two or more of these polymerization inhibitors can be mixed and used. Here, the solid content excluding pigment refers to the solid content excluding pigments and pigment derivatives, excluding organic solvents, acrylic resins, polymer dispersants, reactive monomers, photopolymerization initiators, and other additions It is the total amount of the resin component and the low molecular weight compound including the agent. Specifically, the photosensitive coloring composition is treated in a centrifuge having a gravitational acceleration of 2000 to 40,000 times for 1 to 60 minutes, for example, at a weight acceleration of 20,000 times for 10 minutes, and the pigment component is precipitated. Then, the solution from which the sediment has been removed is heated at 40 ° C. to 200 ° C. for 10 minutes to 24 hours, for example, at 150 ° C. for 60 minutes, to evaporate and dry the organic solvent component under normal pressure or reduced pressure. Can be measured.

Other hindered phenols, phosphorus-based, sulfur-based, and amine-based polymerization inhibitors or antioxidants tend to be thicker than the mask size and fail to form high-definition patterns as designed. In addition, it is not preferable because degradation of electrical reliability presumed to be caused by decomposition products and unreacted materials remaining in the coating film is observed. In general, polymerization inhibitors and antioxidants are used in different ways, but there are actually polymerization inhibitors that play the role of antioxidants, and the difference in names is not important. The photosensitive coloring composition of this invention contains the polymerization inhibitor of the said specific structure.
Polymerization inhibitors generally have the effect of inhibiting or stopping polymerization caused by radicals generated by heat, light, radical initiators, etc., and generally prevent gelation of thermosetting resins and stop polymerization during polymer production. Used for etc.

  In the photosensitive coloring composition of the present invention, the photopolymerization initiator reacts with the light irradiated in the exposure step, and radicals are generated to start curing of the coating film. Due to the generated radicals, the polymerization reaction proceeds via the reactive monomer in the photosensitive coloring composition and the unsaturated group of the acrylic resin, and only the vicinity of the exposed portion is cured.

  In the exposure process, the mask may be contaminated with coating film components before curing or dust mixed on the coating film when passing through the process, so it is preferable to set an exposure gap between the mask and the coating film. . A wider exposure gap can avoid contamination of the mask, and is usually 50 μm or more, preferably 100 μm or more, and more preferably 200 μm or more. However, when the exposure gap is widened, the light at the time of exposure irradiates a region spread on a plane more than the actual mask size on the coating film by diffracting the mask. As a result, the size of the pixel is larger than that of the design. However, the configuration of the present invention is particularly preferable in the case of forming a high-definition pattern that can significantly reduce the thickness of the pixel.

  The photosensitive coloring composition of the present invention may contain other additives. Examples thereof include organic solvents, polymer compounds other than acrylic resins, adhesion improvers and surfactants, organic acids, organic amino compounds, and curing agents.

As the organic solvent, known solvents such as those described in the pigment dispersion can be used, and they may be the same as or different from those contained in the pigment dispersion.
As the polymer compound, various materials such as acrylic resin, alkyd resin, melamine resin, polyvinyl alcohol, polyester, polyether, polyamide, polyamideimide, polyimide, polyimide precursor, and the like can be used.

  The adhesion improving agent can be preferably added for the purpose of improving the adhesion of the coating film to the substrate. For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- Examples include silane coupling agents such as chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  The surfactant can be added for the purpose of improving the coating property of the photosensitive coloring composition and the uniformity of the surface of the colored layer, or for the purpose of improving the dispersibility of the pigment. The amount of the surfactant added is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, based on the pigment. If the added amount is less than this range, the effect of improving the coating property, the uniformity of the colored film surface, or the pigment dispersibility is small, and if it is too much, the coating property is poor or the pigment is aggregated. Since there are cases, it is not preferable. Specifically, anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryldimethylamine oxide, laurylcarboxymethylhydroxy Examples include amphoteric surfactants such as ethylimidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate, fluorine-based surfactants, and silicon-based surfactants. .

  The photosensitive coloring composition obtained by such a method is also preferably subjected to removal of impurities such as coarse particles and dust using a centrifuge, a filter or the like.

  In the photosensitive coloring composition of the present invention, the pigment is usually used in the range of 5 to 80% by mass, preferably 10 to 60% by mass in the total solid content of the photosensitive coloring composition. If the amount of the pigment is less than 5%, the color purity is low, which is not preferable.

  Next, the example of the manufacturing method of the color filter using the photosensitive coloring composition of this invention is demonstrated. As a method of applying the photosensitive coloring composition on the substrate, a method of applying to the substrate by a spin coater, a bar coater, a blade coater, a roll coater, a die coater, a screen printing method, or the like, or immersing the substrate in the coloring composition Various methods, such as a method and spraying a coloring composition on a substrate, can be used.

  In addition, as such a substrate, a transparent substrate such as soda glass, non-alkali glass, borosilicate glass, or quartz glass, or a semiconductor substrate such as silicon or gallium-arsenide is usually used, but is not particularly limited thereto. When applying the photosensitive coloring composition of the present invention on such a substrate, if the substrate surface is treated with an adhesion aid such as a silane coupling agent, the adhesion between the colored film and the substrate can be improved. it can.

  After applying the photosensitive coloring composition of the present invention on the substrate as described above, the organic solvent is removed by air drying, reduced pressure drying, heat drying or the like to form a coating film. In particular, after providing a vacuum drying step, additional heating and drying in an oven or a hot plate eliminates coating defects caused by convection and improves the yield. The drying under reduced pressure is preferably performed in the range of normal temperature to 100 ° C., 5 seconds to 10 minutes, atmospheric pressure 500 to 5 Pa, more preferably atmospheric pressure 100 to 10 Pa. Heat drying is preferably performed using an oven, a hot plate or the like at a temperature of 50 to 120 ° C. for 10 seconds to 30 minutes. Thereafter, an oxygen barrier film may be provided on the coating film as necessary.

Next, exposure is performed. A mask is placed on the coating film of the photosensitive coloring composition and selectively exposed to ultraviolet rays or the like using an ultrahigh pressure mercury lamp, a chemical lamp, a high pressure mercury lamp or the like. Exposure is represented by the time-integrated values of irradiance at 365 nm, but are not particularly limited, is preferably ^{10mJ / cm 2 ~200mJ / cm 2} , more preferably 20mJ ^/ cm ² ~100mJ ^/ cm 2 . If it is less than 10 mJ / cm ^2, the pattern of the transparent resin layer may be peeled off during development due to insufficient curing, and if it is greater than 200 mJ / cm ^2, it is preferable because the tact time becomes long and the production efficiency is poor. Absent.

  The photosensitive coloring composition of the present invention is preferable because the influence of the diffracted light of the mask that occurs when the exposure gap is widened can be remarkably reduced. When the collimation angle that is an index indicating the parallelism of the irradiation light of the exposure apparatus is θ and the exposure gap that is the distance between the mask lower surface and the coating film upper surface is H, the width of the exposure region is 2 × H with respect to the mask width. × tan θ is known to be wide. That is, the greater the exposure gap H, the greater the influence of diffracted light, making it difficult to form pixels with the designed line width. Using the photosensitive coloring composition of the present invention, the difference between the line width when exposed at an exposure gap of 100 μm and the line width when exposed at an exposure gap of 300 μm through a photomask having a line width of 50 μm is set to 5 μm or less. This is preferable because a high-definition pattern as designed can be formed.

  Next, development is performed with an alkaline developer. Although it does not specifically limit as an alkaline substance used for an alkaline developing solution, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n- Primary amines such as propylamine, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH) , Quaternary ammonium salts such as choline, triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol and other alcohol amines, pyrrole, piperidine, 1,8-dia Bicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, organic alkalis such as cyclic amines such as morpholine, and the like.

  The concentration of the alkaline substance in the developer is not particularly limited, but is usually 0.01 to 50% by mass, preferably 0.05 to 5% by mass. The developer is preferably an aqueous aqueous developer in terms of working environment and waste developer treatment. In the case of using an aqueous alkaline aqueous developer, a water-soluble organic solvent such as ethanol, γ-butyrolactone, dimethylformamide, or N-methyl-2-pyrrolidone may be appropriately added to the developer.

The development method uses an immersion method, a spray method, a paddle method or the like, but is not particularly limited. Moreover, you may add the washing process by a pure water etc. suitably after image development.
Here, it is preferable to use an alkaline developer added with 0.01 to 1% by mass of a surfactant such as a nonionic surfactant as the developer because a better pattern can be obtained.

  The coating film pattern of the obtained colored composition then becomes a colored pixel patterned by heat treatment. The heat treatment is usually performed in air, in a nitrogen atmosphere, or in a vacuum at 150 to 300 ° C, preferably 180 to 250 ° C, continuously or stepwise for 0.25 to 5 hours. Done.

When a colored pattern is sequentially formed for an arbitrary number of colors by the above method, a color filter for a liquid crystal display device having a pixel composed of a colored layer provided in a desired pattern can be produced. Here, the patterning order of the coloring composition is not limited. Although the number of colors is arbitrary, three colors of RGB or four colors including a resin black matrix are preferable.
Moreover, a black matrix, a protective film, a transparent conductive film, etc. can be formed as needed. The position where these are formed, the order of formation, the formation method, and the like are not particularly limited. As an example, a black matrix is formed on a substrate, a colored layer is formed thereon, a protective film is further formed thereon, and a transparent conductive film is formed thereon.

EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, the scope of the present invention is not restrict | limited at all by this.
(Pattern preparation method)
The photosensitive coloring composition is spin-coated (Mikasa Co., Ltd., 1H-D2 type) on a non-alkali glass (manufactured by Nippon Electric Glass Co., Ltd., OA10: 50 mm × 70 mm, thickness 0.7 mm) substrate surface. Then, the film was dried by heating (prebaking) for 10 minutes in an inert oven (manufactured by Davai Speck Co., Ltd., PERFECTOVEN PV-210) at 90 ° C. to form a coating film having a thickness of 2.00 μm. Then, after cooling this substrate to room temperature, using an exposure machine (Union Optics Co., Ltd., UV exposure machine PEM-6M, collimation angle θ = 2 °, i-line (365 nm) illuminance = 40 mW / cm ² ), Through a photomask (manufactured by HOYA Co., Ltd., negative mask, stripe design line width 50 μm), predetermined exposure with ultraviolet rays including wavelengths of j-line: 313 nm, i-line: 365 nm, h-line: 405 nm, and g-line: 436 nm Exposed in quantity.

  Next, an aqueous solution at 23 ° C. containing 0.05% by mass of potassium hydroxide and 1.67% by mass of Emulgen A-60 (manufactured by Kao Corporation) was used as a developing solution, and the substrate was used as an automatic developing device (Mikasa Corporation). ), AD-2000), and after developing for a predetermined time, washed with pure water and air-dried. Furthermore, heat drying (post-baking) was performed for 30 minutes in an inert oven (manufactured by Davai Espec Co., Ltd., HIGHTEMPOVEN PV-110) at 220 ° C., and each color filter was produced on the substrate.

(Evaluation methods)
1. Sensitivity According to the pattern preparation method described above, exposure is performed with a maximum exposure amount of 200 mJ / cm ² through a photomask with a 50 μm stripe pattern, an exposure gap of 300 μm, and the exposure amount is reduced as needed. The minimum exposure amount in a range where no peeling occurred was defined as the minimum required exposure amount. The smaller the minimum required exposure amount, the higher the sensitivity and the better.
◯: The minimum required exposure amount is 40 mJ / cm ² or less.
△: Minimum required exposure amount 40 mJ / cm ² greater than 100 mJ / cm ² less than one.
X: The minimum required exposure amount is 100 mJ / cm ² or more.

2. Exposure Margin According to the above pattern production method, exposure was performed with an exposure gap of 100 μm and 300 μm through a photomask with a 50 μm stripe pattern at an exposure amount of 50 mJ / cm ² . The development time is 60 seconds, and the shape of the formed color filter pattern is observed with an optical microscope (BH3-MJL manufactured by Olympus Sales Co., Ltd. and XD200 manufactured by KS Olympus Co., Ltd.) and the pixel width is measured. Went. The pixel width in the case of the exposure gap of 100 μm and the pixel width in the case of the exposure gap of 300 μm were compared, and the difference was obtained. A pixel whose change in pixel width due to the difference in exposure gap is small is suitable for producing a high-definition pattern with a wide exposure margin.
A: The difference in pixel width between the exposure gap of 100 μm and 300 μm is 3 μm or less.
Δ: Difference in pixel width between exposure gaps of 100 μm and 300 μm is greater than 3 and less than 5 μm.
X: The difference of the pixel width of exposure gap 100 micrometers and 300 micrometers is 5 micrometers or more.

2. Development Margin According to the above pattern production method, exposure was performed with an exposure gap of 300 μm through a photomask with a 50 μm stripe pattern at an exposure amount of 50 mJ / cm ² . The development time was 60 seconds and 120 seconds, and the shape of the formed color filter pattern was observed using a light microscope (BH3-MJL manufactured by Olympus Sales Co., Ltd. and XD200 manufactured by KS Olympus Co., Ltd.) The pixel width was measured. The pixel width when the development time was 60 seconds and the pixel width when the development time was 120 seconds were compared, and the difference was obtained. A small change in pixel width due to a difference in development time is suitable for producing a high-definition pattern with a wide development margin.
A: The difference in pixel width between the development time of 60 seconds and the exposure time of 120 seconds is 3 μm or less.
Δ: Difference in pixel width between the development time of 60 seconds and the exposure time of 120 seconds is greater than 3 and less than 5 μm.
X: The difference in pixel width between the development time of 60 seconds and the exposure time of 120 seconds is 5 μm or more.

(Measurement of acid value)
The acrylic resin or reactive monomer was precisely weighed and dissolved in a purified water / acetone mixed solvent, and then titrated with 0.1N KOH aqueous solution using phenolphthalein as an indicator to measure the acid value. In addition, when the reactive monomer was a mixture of two or more kinds, a mixture prepared in advance was prepared, and the acid value of the entire reactive monomer was obtained.

(Synthesis example of acrylic resin)
In a 1000 cc four-necked flask, 150 g of 3-methoxy-3-methyl-butanol was charged, kept at 90 ° C., sealed with nitrogen, stirred and stirred with 30 g of methyl methacrylate, 30 g of styrene, and 40 g of methacrylic acid with n-dodecyl mercaptan. 1.1 g and 1.2 g of 2,2′-azobisisobutyronitrile were mixed and added dropwise using a dropping funnel over 30 minutes. Thereafter, the reaction was continued for 4 hours, then the nitrogen sealing was stopped, and 0.1 g of hydroquinone monomethyl ether and 0.4 g of dimethylbenzylamine were added. Reaction was performed by adding 33 g of glycidyl methacrylate dropwise over 30 minutes and further stirring at 90 ° C. for 3 hours. After returning to room temperature, it is re-precipitated by dropping it into a mixed solvent of purified water / acetone, filtered and dried to obtain a powdery acrylic resin (polymer A) having an average molecular weight Mw of 40,000 and an acid value of 115 mgKOH / g. )

Example 1
14 parts by weight of an 80/20 (weight ratio) mixture of Pigment Red 254 and Pigment Red 177 as a pigment, and 9 parts by weight of “Disperbyk” 2001 (produced by Big Chemie Japan Co., Ltd., 46% by mass) as a polymer dispersant; After 4 parts by weight of polymer A and 73 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) were mixed as an organic solvent, the mixture was dispersed using a mill-type disperser filled with zirconia beads. Obtained.
Next, with respect to 100 parts by weight of this pigment dispersion, 10 parts by weight of polymer A as a reactive monomer is a reaction product of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate and succinic anhydride, In formula (1), -R ¹ is -H, n = 1, -X- is -O-, and -Y- is an ethylene group having an acid value of 30 TO-1382 (Toagosei Co., Ltd.) )), 12 parts by weight of Etanone represented by the structural formula (2) as Ar as a 2-methylbenzyl group as Ar and an ethyl group as R ² as a photopolymerization initiator , 1- [ 9-ethyl-6- (2- methylbenzoyl) -9H- carbazol-3-yl)] -, 1- (O- acetyloxime) a (Ciba Specialty Chemicals Corp. CGI242, hereinafter referred to as CGI242) 6 parts by weight of 2- (4-methyl) benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (CGI113 manufactured by Ciba Specialty Chemicals Co., Ltd., hereinafter referred to as CGI113) Parts, 3-methacryloxypropyltrimethoxysilane (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as KBM503) as a weight improver, 1.7 parts by weight as a surfactant, Megafac R-08 (Dainippon Chemical Industry ( Co., Ltd., hereinafter referred to as R-08), 0.1 parts by weight, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor , Hereinafter referred to as DOHQ) 0.2 parts by weight (0.5% by mass with respect to the solid content excluding the coloring material), and 100 parts by weight of PGMEA as an organic solvent are mixed for photosensitive coloring. The Narubutsu was prepared. Table 1 shows the evaluation results of pattern sensitivity, exposure margin, and development margin. Good results were obtained for all evaluation items, and high-definition patterns could be produced with a wide process margin.

Example 2
As a polymerization inhibitor, tert-butylcatechol (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as TBC) is 0.4 parts by weight (1% by mass with respect to the solid content excluding the coloring material), and TO- is used as the reactive monomer. Example 1 except that 6 parts by weight of 1382 and 6 parts by weight of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (“Kayacure” DPHA manufactured by Nippon Kayaku Co., Ltd., hereinafter referred to as DPHA) were added. Thus, a photosensitive coloring composition was prepared. In addition, the acid value of the whole reactive monomer at this time was 15. The evaluation results are shown in Table 1. Good results were obtained for all evaluation items, and high-definition patterns could be produced with a wide process margin.

Example 3
0.04 parts by weight of TBC as a polymerization inhibitor (0.1% by mass based on solid content excluding colorant), and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as a reactive monomer and succinic anhydride In the structural formula (1), -R ¹ is -H, n = 1, -X- is -O-, and -Y- is an ethylene group. A photosensitive coloring composition was prepared in the same manner as in Example 1 except that 2.4 parts by weight of Toagosei Co., Ltd. and 9.6 parts by weight of DPHA were added. In addition, the acid value of the whole reactive monomer at this time was 13. The evaluation results are shown in Table 1. The sensitivity was good. Although the exposure margin and the development margin were slightly thick at the exposure gap of 300 μm and slightly narrowed at the development time of 120 seconds, the results were almost satisfactory.

Reference example 1
2,5-bis (1,1, -dimethylbutyl) hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as DHHQ) as a polymerization inhibitor is 0.8 parts by weight (based on the solid content excluding the coloring material) 2% by mass), sensitized in the same manner as in Example 1 except that 8.4 parts by weight of TO-1382 as a reactive monomer, 3.6 parts by weight of DPHA, and 8 parts by weight of CGI113 as a photopolymerization initiator were added. The coloring composition was adjusted. In addition, the acid value of the whole reactive monomer at this time was 21. The evaluation results are shown in Table 1. Although the sensitivity was slightly inferior, the exposure margin and the development margin were satisfactory, and a high-definition pattern could be produced with a wide process margin.

Example 4
14 parts by weight of a 65/35 (weight ratio) mixture of Pigment Green 36 and Pigment Yellow 150 as a pigment, 9 parts by weight of “Disperbyk” 2001 as a polymer dispersant, 4 parts by weight of Polymer A, and 73 weights of PGMEA as an organic solvent After mixing the parts, the mixture was dispersed using a mill type disperser filled with zirconia beads to obtain a pigment dispersion.
Next, with respect to 100 parts by weight of this pigment dispersion, 10 parts by weight of polymer A as a reactive monomer is a reaction product of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate and succinic anhydride, In formula (1), -R ¹ is -H, n = 1, -X- is -O-, and -Y- is an ethylene group having an acid value of 27 TO-2348 (Toagosei Co., Ltd.) )), 12 parts by weight of CGI242 as a photopolymerization initiator, 1.7 parts by weight of KBM503 as an adhesion improver, 0.1 part by weight of R-08 as a surfactant, TBC0 as a polymerization inhibitor .6 parts by weight (1.5% by mass with respect to the solid content excluding the coloring material) and 100 parts by weight of PGMEA as an organic solvent were mixed to prepare a photosensitive coloring composition. Table 1 shows the evaluation results of pattern sensitivity, exposure margin, and development margin. Good results were obtained for all evaluation items, and high-definition patterns could be produced with a wide process margin.

Reference example 2
Pigment Blue 15: 6 as pigment and 96/4 (weight ratio) mixture of Pigment Violet 23, 14 parts by weight as polymer dispersant “Disperbyk” 2001, 4 parts by weight of polymer A, as organic solvent, After mixing 73 parts by weight of PGMEA, the mixture was dispersed using a mill type disperser filled with zirconia beads to obtain a pigment dispersion.
Next, 10 parts by weight of polymer A, 12 parts by weight of TO-1382 as a reactive monomer, and 2-methyl-1- [4- (methylthio) phenyl as a photopolymerization initiator with respect to 100 parts by weight of this pigment dispersion ] 2-morpholinopropan-1-one ("Irgacure" 907 manufactured by Ciba Specialty Chemicals Co., Ltd., hereinafter referred to as IC907), 6 parts by weight, 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., " Kayacure “DETX-S” (hereinafter referred to as “DETX”) 2 parts by weight, KBM503 as an adhesion improver 1.7 parts by weight, surfactant R-08 0.1 parts by weight, polymerization inhibitor TBC 0.1 parts by weight A photosensitive coloring composition was prepared by mixing 100 parts by weight of PGMEA as an organic solvent (0.25% by mass with respect to the solid content excluding the coloring material). The evaluation results are shown in Table 1. When the development time was as long as 120 seconds, the line width was slightly narrowed, but a high-definition pattern could be produced with a wide process margin.

Example 5
Mill type disperser filled with 20 parts by weight of a 50/50 (weight ratio) mixture of carbon black and titanium black as a light-shielding agent, 10 parts by weight of polymer A and 70 parts by weight of PGMEA as an organic solvent, and then filled with zirconia beads To obtain a pigment dispersion.
Next, 10 parts by weight of TO-2348, 10 parts by weight of CGI242 as a photopolymerization initiator, 1.5 parts by weight of KBM503 as an adhesion improver, and R-- as a surfactant with respect to 100 parts by weight of this pigment dispersion 0.1 parts by weight of 08, 0.1 parts by weight of TBC as a polymerization inhibitor (0.3% by mass with respect to the solid content excluding the coloring material), and 100 parts by weight of PGMEA as an organic solvent were mixed to form a photosensitive coloring composition. A product was prepared. The sensitivity and development margin were good. Although the exposure gap was slightly thick at 300 μm, the result was almost satisfactory.

Comparative Example 1
As in Example 1, except that 0.04 parts by weight of DHHQ as a polymerization inhibitor (0.1% by mass with respect to the solid content excluding the colorant) and 12 parts by weight of DPHA having an acid value of 0 as a reactive monomer were added. Thus, a photosensitive coloring composition was prepared. Although the sensitivity was good, there was a large variation in pixel width when the exposure gap and development time were changed, and it was difficult to produce a high-definition pattern.

Comparative Example 2
2 parts by weight of TBC as a polymerization inhibitor (5% by mass based on solid content excluding colorant), 12 parts by weight of DPHA having an acid value of 0 as a reactive monomer, and 8 parts by weight of CGI 113 as a photopolymerization initiator were added. Except for the above, a photosensitive coloring composition was prepared in the same manner as in Example 1. The sensitivity was insufficient, and peeling of the pattern surface was observed.

Comparative Example 3
A photosensitive coloring composition was prepared in the same manner as in Example 6 except that no polymerization inhibitor was added and 12 parts by weight of TO-1382 was added as a reactive monomer. The sensitivity was slightly insufficient, and film roughness on the pattern surface was observed. In addition, when the exposure gap is widened, the pixel width becomes large, and it is difficult to produce a high-definition pattern.

Claims (5)

In a photosensitive coloring composition for a color filter containing at least a pigment, an acrylic resin, a reactive monomer, a photopolymerization initiator, a polymerization inhibitor, and an organic solvent, the polymerization inhibitor is a hydroquinone or catechol polymerization inhibitor. And the reactive monomer contains a compound represented by the following structural formula (1), and further contains a compound represented by the following structural formula (2) as a photopolymerization initiator. Photosensitive coloring composition for color filters.

(Wherein, n represents an integer of 1 to 4, -R ¹ represents -H or -CH _3, -X- is _{-O -, - O (CH 2} CH 2) m O-, or -O (CH ₂ CH ₂ CH ₂ ) _m O—, wherein —Y— is an alkylene group having 1 to 8 carbon atoms, and a phenylene group, a cyclohexylene group, and a part of the cyclohexylene group, each of which may be substituted. Represents a group selected from the group consisting of a group that is an unsaturated bond, provided that m represents an integer of 1 to 8.)

(In the formula, Ar represents an optionally substituted aryl group, and R ² represents an alkyl group having 1 to 6 carbon atoms) 2. The photosensitive coloring composition for a color filter according to claim 1, wherein the reactive monomer has an acid value of 5 to 50 mg KOH / g as a whole. The photosensitive coloring composition for a color filter according to claim 1 or 2, wherein the polymerization inhibitor is contained in an amount of 0.1 to 3% by mass based on the solid content excluding the pigment. The photosensitive coloring composition for a color filter according to any one of claims 1 to 3, comprising a compound represented by the following structural formula (3) or (4) as the polymerization inhibitor.

(Wherein R ³ , R ⁴ , R ⁵ And each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alicyclic group). In the color filter which has the pixel which consists of a colored layer provided in the desired pattern form for each color by arbitrary colors, this colored layer is by the photosensitive coloring composition for color filters in any one of Claims 1-4. A color filter comprising a colored film to be formed.