JP2013195538A - Photosensitive coloring composition, color filter, and liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive coloring composition which has a high resistance value even at a high pigment concentration, excellent dispersibility and sufficient developing characteristics without causing foreign matters during application.SOLUTION: There is provided a photosensitive coloring composition which includes a pigment (a), a dispersant (b), an organic binder (c), a photopolymerizable monomer (d), a photopolymerization initiator (e) and a solvent (f), wherein the pigment (a) is carbon black coated with a resin, the dispersant (b) is an acrylic block polymer having vinylpyridine as a constituent monomer and the organic binder (c) is an alkali-soluble resin having an ethylenically unsaturated bond.

Description

  The present invention relates to a photosensitive coloring composition, a color filter, and a liquid crystal display device. More specifically, the present invention relates to a photosensitive coloring composition having a high volume resistance, excellent dispersibility, no foreign matter or the like during application, and sufficient development characteristics. The present invention also relates to a cured product of this photosensitive coloring composition and its use.

  Conventionally, as a method for producing a color filter using a pigment, a dyeing method, an electrodeposition method, an ink jet method, a pigment dispersion method and the like are known.

  In the case of producing a color filter by a pigment dispersion method, a photosensitive colored resin composition in which a binder resin, a photopolymerization initiator, a photopolymerizable monomer, etc. are added to a colored resin composition obtained by dispersing a pigment with a dispersant or the like. An object is coated on a glass substrate, dried, exposed using a mask, and developed to form a colored pattern, which is then heated to fix the pattern and form pixels. These steps are repeated for each color to form a color filter.

  The color filter usually has pixels of each color such as red, green, and blue, and a black matrix is usually formed between the pixels. The photosensitive coloring composition used for black matrix image formation has been required to have characteristics such as sufficient light-shielding property, resolution, good adhesion to a substrate, and low development residue. Further, in recent years, it has been required as a performance of the black matrix that it corresponds to the panel system and that the volume resistance of the black matrix is high.

  Patent Document 1 and Patent Document 2 describe increasing the resistance of a black matrix by using carbon black coated with a resin. Patent Documents 3 to 7 describe various dispersants for the purpose of improving dispersibility. However, since the carbon black coated with the resin still has conductivity, the volume resistance value gradually decreases by increasing the concentration, and a sufficient resistance value is not obtained. On the other hand, higher resistance values are required in the market. Further, when carbon black coated with resin is used, there is a tendency that foreign matters aggregated in the nozzle during application tend to be generated.

Japanese Patent Laid-Open No. 09-71733 JP 09-166869 A JP-A-10-213898 JP 2004-054213 A JP 2005-240000 A Special table 2009-543145 gazette JP 2011-074122 A

  The present invention provides a photosensitive coloring composition having a high resistance value even at a high pigment concentration, excellent dispersibility, no foreign matter or the like at the time of application, and sufficient development characteristics, and a cured product using the same. It is an object to provide a color filter and a liquid crystal display device.

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by combining with a specific dispersant when using carbon black coated with a resin.
That is, the gist of the present invention is as follows.

[1] A pigment (a), a dispersant (b), an organic binder (c), a photopolymerizable monomer (d), a photopolymerization initiator (e), and a solvent (f). ) Is a carbon black coated with a resin, the dispersant (b) is an acrylic block copolymer having vinylpyridine as a constituent monomer, and the organic binder (c) is an alkali-soluble compound having an ethylenically unsaturated bond. A photosensitive coloring composition which is a resin.

[2] The dispersant (b) is a resin containing structural units represented by the following general formulas (I), (II), and (III) as structural units: Photosensitive coloring composition.

(In the general formula (II), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 3 carbon atoms, t represents an integer of 5 to 15 and R ³ represents 1 carbon atom. Represents a phenyl group substituted with an alkyl group of ˜25, a phenyl group, or an alkyl group of 1 to 18 carbon atoms.)

(In the general formula (III), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)

[3] The photosensitive coloring composition according to [1] or [2], further comprising a sulfonic acid derivative of phthalocyanine as a dispersion aid.

[4] The photosensitive coloring composition according to any one of [1] to [3], wherein the pigment (a) is contained in an amount of 40 to 60% by weight based on the total solid content in the photosensitive coloring composition. object.

[5] (b) The organic binder (c) contains the following alkali-soluble resin (c-1) and / or alkali-soluble resin (c-2): [1] to [4] The photosensitive coloring composition in any one.
<Alkali-soluble resin (c-1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
<Alkali-soluble resin (c-2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.

[6] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [5].

[7] A color filter formed using the photosensitive coloring composition according to any one of [1] to [5].

[8] A liquid crystal display device produced using the color filter according to [7].

  According to the present invention, there is provided a photosensitive coloring composition which has a high resistance value even at a high pigment concentration, is excellent in dispersibility, does not generate foreign matters during application, and has sufficient development characteristics. By using the colored composition, it is possible to form a pixel having excellent light shielding properties, resolution, good adhesion to a substrate, low development residue, and other high volume resistance.

It is a cross-sectional schematic diagram which shows an example of the organic EL element provided with the color filter of this invention.

Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”. In addition, “(acid) anhydride” and “(anhydrous)... Acid” mean that both an acid and its anhydride are included.
Further, in the present invention, “total solid content” means all components other than the solvent contained in the photosensitive coloring composition or in the ink described later.

Moreover, in this invention, a weight average molecular weight means the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography).
Further, in the present invention, the “amine value” means an amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the weight of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. It is. The measuring method will be described later.

[Photosensitive coloring composition]
The photosensitive coloring composition of the present invention is
Pigment (a),
Dispersant (b),
Organic binder (c),
Photopolymerizable monomer (d),
Photopolymerization initiator (e)
And solvent (f)
As an essential component, preferably further,
Contains a dispersion aid, and if necessary, further contains other compounding components such as adhesion improver, coatability improver, development improver, ultraviolet absorber, antioxidant, surfactant, etc. Each compounding component is used in a state dissolved or dispersed in an organic solvent.

<Pigment (a)>
As the pigment (a) used in the present invention, carbon black coated with a resin is used.

  In the present invention, carbon black coated with a resin is preferable from the viewpoint of high adhesion to a glass substrate, and is also preferable in terms of improving the volume resistance value. As carbon black coated with resin, for example, carbon black described in JP-A No. 09-71733 can be suitably used.

As carbon black to be subjected to a coating treatment with a resin, the total content of Na and Ca is preferably 100 ppm or less.
That is, carbon black is usually made from raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulated water, Na mixed from furnace materials of the reactor, Ca, K, Mg, Al. , Fe and the like are contained in the order of percent. Of these, Na and Ca are generally contained in a few hundred ppm or more, but if many of these are present, they penetrate into the transparent electrode (ITO) and other electrodes, causing electrical shorts. There is a case.

  As a method for reducing the content of ash containing these Na and Ca in carbon black, these contents are used as much as possible as raw material oil, fuel oil (or gas) and reaction stop water when producing carbon black. Examples include a method of carefully selecting a small amount and a method of minimizing the addition amount of an alkaline substance for adjusting the structure. As another method, there is a method in which Na or Ca is dissolved and removed by washing carbon black produced from a furnace with water or hydrochloric acid.

  Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid or hydrogen peroxide solution, when a solvent that is hardly soluble in water is added, the carbon black moves to the solvent side and completely separates from water. Most of Na and Ca present in carbon black are dissolved and removed in water and acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, there may be a case where a carbon black production process alone or a water or acid dissolution method alone with carefully selected raw materials may be possible. The total amount of Na and Ca can be easily made 100 ppm or less.

  The carbon black used for the resin coating is preferably so-called acidic carbon black having a pH of 6 or less. Such carbon black is suitable because it has a small dispersed diameter (agglomerated diameter) in water, and can cover even fine units. Furthermore, the carbon black used for the resin coating preferably has a particle size of 40 nm or less and a dibutyl phthalate (DBP) absorption of 140 ml / 100 g or less. If the particle size is larger than 40 nm and the DBP absorption is larger than 140 ml / 100 g, the dispersibility when made into a paste is excellent, but the coating film may not have sufficient density, and the film thickness is about 1 to 2 μm. It is because there is a possibility that it may become scarce.

Although there is no particular limitation on the method of preparing the carbon black coated with the resin, for example, after appropriately adjusting the blending amount of the carbon black and the resin,
1. After mixing and stirring a resin solution obtained by mixing a resin and a solvent such as cyclohexanone, toluene, xylene and the like, and a suspension obtained by mixing carbon black and water, carbon black and water are separated, A method in which the composition obtained by removing water and heating and kneading is formed into a sheet, pulverized and then dried;
2. A method in which the resin solution and suspension prepared in the same manner as above are mixed and stirred to granulate carbon black and the resin, and then the obtained granular material is separated and heated to remove the remaining solvent and water;
3. Carboxylic acid such as maleic acid and fumaric acid is dissolved in the above exemplified solvent, carbon black is added, mixed and dried, the solvent is removed to obtain carboxylic acid-impregnated carbon black, and then a resin is added thereto. Dry blending method;
4). A reactive group-containing monomer component constituting the resin to be coated and water are stirred at a high speed to prepare a suspension. After polymerization, the suspension is cooled to obtain a reactive group-containing resin from the polymer suspension. A method in which carbon black is added and kneaded, carbon black and reactive groups are reacted (carbon black is grafted), cooled and pulverized;
Etc. can be adopted.

  The type of resin used to coat carbon black is not particularly limited, but synthetic resins are common, and resins with benzene nuclei in the structure function more as amphoteric active surfactants. Is preferable from the viewpoint of dispersibility and dispersion stability.

Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene. Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyether sulfone, polyphenylene sulfone, polyarylate, and polyether ether ketone can be used.
These may be used alone or in combination of two or more.

  The coating amount of the resin on the carbon black is preferably 1 to 30% by weight with respect to the total amount of the carbon black and the resin. When the coating amount of the resin with respect to carbon black is less than 1% by weight, there is a possibility that only dispersibility and dispersion stability similar to those of untreated carbon black can be obtained. On the other hand, if it exceeds 30% by weight, the adhesiveness between the resins is strong, and it becomes a dumpling-like lump, which may prevent the dispersion from proceeding.

  The carbon black formed by coating with a resin can be used as a black matrix shading material according to a conventional method, and a color filter having this black matrix as a constituent element can be prepared by a conventional method. When such carbon black is used, a black matrix having a high light shielding rate, a low surface reflectance, and a thin film thickness can be achieved at a low cost. This is presumably because the dispersibility and dispersion stability of carbon black was significantly improved compared to the resin and solvent that make up the black matrix liquid. As a result, it is difficult to disperse to 0.1 μm or less, and even if dispersed, the stability is poor and the aggregation increases with time.) It is also presumed that by coating the carbon black surface with a resin, Ca and Na can be contained in the carbon black.

  Only one type of carbon black coated with a resin may be used, or two or more types of coated carbon black, coating resin, and resin-coated carbon black having different coating amounts may be used.

  In the present invention, pigments other than carbon black can also be used together with carbon black subjected to resin coating treatment. As other pigments, for example, pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment can be used. In addition to the organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments are also used. Is possible.

  Specific examples of pigments that can be used in combination are shown below by pigment numbers. Note that terms such as “CI Pigment Red 2” mentioned below mean a color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

These pigments of each color may be used alone or in combination of two or more.
In order to obtain the above-mentioned effects more effectively by using the resin-coated carbon black, in the present invention, the ratio of the resin-coated carbon black in the pigment (a) is 30% by weight or more, particularly 50 to 100% by weight. Preferably there is.

<Dispersant (b)>
The dispersant used in the present invention is an acrylic block copolymer having vinylpyridine as a constituent monomer.

In particular, the dispersant (b) is a structural unit represented by the following general formulas (I), (II), and (III) (hereinafter, “structural unit (I)”, “structural unit (II)”, It is preferably a resin containing “sometimes referred to as“ structural unit (III) ”.

(In the general formula (II), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 3 carbon atoms, t represents an integer of 5 to 15 and R ³ represents 1 carbon atom. Represents a phenyl group substituted with an alkyl group of ˜25, a phenyl group, or an alkyl group of 1 to 18 carbon atoms.)

(In the general formula (III), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)

  Specifically, the monomer that gives the structural unit represented by the general formula (I) is preferably 2-vinylpyridine or pyridium ion, 4-vinylpyridine or pyridium ion, and 2-vinylpyridine or 4-vinyl. Pyridine is more preferred.

In the general formula (II), t is preferably an integer of 7 to 12, and R ³ is preferably an alkyl group having 1 to 4 carbon atoms.

In the general formula (III), R ⁵ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an n-butyl group.

  An acrylic block copolymer having vinyl pyridine as a constituent monomer used in the present invention, particularly a dispersant containing the structural units (I) to (III), has a higher resistance value than a general urethane-based dispersant. Excellent effect. This is because, during dispersion, pyridine contained in the constituent monomer of the dispersant has a high adsorptivity to the surface of the carbon black, so the surface is easily covered with the dispersant and has the effect of reducing the conductivity of the carbon black. Guessed.

  In addition, the acrylic block copolymer having vinyl pyridine as a constituent monomer used in the present invention, particularly the acrylic block copolymer containing the structural units (I) to (III), has an affinity for the pigment surface. It has an excellent polymer segment and a polymer segment excellent in affinity to solvents and resins, and has a molecular structure that is more suitable for stabilizing the dispersion of pigments, and therefore has an adaptability to a wide range of pigment types. In particular, in the resin containing the structural units (I) to (III), the structural unit (I) is configured as a polymer segment having excellent affinity for the solvent and the resin as a polymer segment having excellent affinity for the pigment surface. Unit (II) works.

  The ratio of the structural units (I), (II), and (III) in the dispersant (b) used in the present invention is preferably 5 to 25 mol%, more preferably 10 to 20 mol% of the structural unit (I). The structural unit (II) is preferably 5 to 25 mol%, more preferably 10 to 20 mol%, and the structural unit (III) is preferably 60 to 80 mol%, more preferably 65 to 75 mol%. If the proportion of the structural unit (I) is too small, the pigment dispersibility improvement effect due to the affinity to the pigment surface may not be sufficiently obtained. If the proportion of the structural unit (II) is too small, the solvent In addition, the pigment dispersibility improvement effect due to the affinity for the resin may not be sufficiently obtained. Moreover, when there are too many any structural units, the ratio of another structural unit will become relatively small, and the target effect may not be acquired.

  The amine value of the dispersant (b) of the present invention is preferably 1 to 100 mgKOH / g, and more preferably 1 to 50 mgKOH / g. When the amine value of the dispersant (b) is small, the adsorptivity of the dispersant (b) to the carbon black is low, and when the amine value is large, the polarity becomes high, which tends to cause aggregation and deterioration of storage stability.

Here, the amine value of the dispersant is represented by the weight of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO4 acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.
Amine value [mgKOH / g] = (561 × V) / (W × S)
[However, W: Weighing amount of dispersant sample [g], V: Titration amount at the end of titration [mL], S: Solid content concentration [wt%] of the dispersant sample. ]

  A typical commercially available acrylic block copolymer having vinylpyridine as a constituent monomer used in the present invention is EFKA4320 (amine value: about 28 mgKOH / g, manufactured by Ciba Specialty Chemicals).

  The acrylic block copolymer having vinyl pyridine as a dispersant (b) as a constituent monomer may be used alone or in combination of two or more.

Moreover, in the photosensitive coloring composition of this invention, you may use another dispersing agent together with the acrylic block copolymer which has said vinyl pyridine as a structural monomer. Specific examples of the dispersant that can be used in combination are trade names of EFKA-4046, -4047 (manufactured by BASF), Disperbyk-111, -161, -162, -163, -166, -167, -182,- 2000, -2001 (manufactured by Big Chemie), disparon (manufactured by Enomoto Kasei), SOLPERSE-22000, -24000, -28000 (manufactured by Lubrizol).
These other dispersants may be used alone or in combination of two or more.

  In the photosensitive coloring composition of the present invention, a pigment derivative may be used in combination as a dispersion aid.

  As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Examples thereof include phthalocyanine derivatives.

  Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.

  Specific examples of pigment derivatives include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. Of these, sulfonic acid derivatives of phthalocyanine are preferable. These may be used alone or in combination of two or more.

  Examples of commercially available sulfonic acid derivatives of phthalocyanine include S5000 and S12000 (both manufactured by Lubrizol).

<Organic binder (c)>
The organic binder (c) used in the present invention is an alkali-soluble resin having an ethylenically unsaturated bond, preferably an alkali-soluble resin having a carboxyl group and an ethylenically unsaturated bond, and among them, an epoxy having a carboxyl group ( A (meth) acrylate resin is desirable.

Examples of the epoxy (meth) acrylate resin having a carboxyl group include the following alkali-soluble resins (c-1) and / or alkali-soluble resins (c-2).
<Alkali-soluble resin (c-1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
<Alkali-soluble resin (c-2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.

  As an epoxy resin used as a raw material of the alkali-soluble resin (c-1) and / or the alkali-soluble resin (c-2), for example, a bisphenol A type epoxy resin (for example, “Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd., “ Epicoat 1001 "," Epicoat 1002 "," Epicoat 1004 ", etc.), epoxy obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin (for example," NER-1302 "(epoxy equivalent) manufactured by Nippon Kayaku Co., Ltd.) 323, softening point 76 ° C.), bisphenol F type resin (for example, “Epicoat 807”, “EP-4001”, “EP-4002”, “EP-4004”, etc., manufactured by Yuka Shell Epoxy)), bisphenol F Between alcoholic hydroxyl groups and epichlorohydrin of type epoxy resin (For example, “NER-7406” manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, manufactured by Yuka Shell Epoxy Co., Ltd.) "YX-4000"), phenol novolac type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Yuka Shell Epoxy Co., Ltd., manufactured by Dow Chemical Co., Ltd. "DEN-438"), (o, m, p-) cresol novolac type epoxy resin (for example, "EOCN-102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), Glycidyl isocyanurate (for example, “TEPIC” manufactured by Nissan Chemical Co., Ltd.), trisphenol methane type epoxy resin ( For example, “EPPN-501”, “EPN-502”, “EPPN-503” manufactured by Nippon Kayaku Co., Ltd.), fluorene epoxy resin (for example, cardo epoxy resin “ESF-300” manufactured by Nippon Steel Chemical Co., Ltd.), An alicyclic epoxy resin (“Celoxide 2021P”, “Celoxide EHPE” manufactured by Daicel Chemical Industries, Ltd.), an epoxy resin obtained by glycidylation of a phenol resin by reaction of dicyclopentadiene and phenol (for example, “XD manufactured by Nippon Kayaku Co., Ltd.) -1000 "," EXA-7200 "manufactured by Dainippon Ink, Inc.," NC-3000 "," NC-7300 "manufactured by Nippon Kayaku Co., Ltd.), and the like can be suitably used.

Among these, epoxy resins represented by the following general formulas (c1) to (c4) are more preferable.

(In the general formula (c1), X represents a linking group represented by the following general formula (c1-1), (c1-2) or (c1-3), provided that one or more linking groups are present in the molecular structure. (Including an adamantane structure, a represents an integer of 2 or 3.)

(In the above general formulas (c1-1) and (c1-2), R ^{11 to} R ¹⁴ and R ^{15 to} R ¹⁷ are each independently an adamantyl group optionally having a substituent, a hydrogen atom, and a substituent. In the general formula (c1-3), R ^{13a to} R ^13h are each an alkyl group having 1 to 12 carbon atoms which may have a group, or a phenyl group which may have a substituent. , Each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group, and Y has a substituent. And represents a divalent linking group containing an adamantane structure.)

(In the general formula (c2), b represents an average value and represents a number of 0 to 10. R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. , A phenyl group, a naphthyl group, or a biphenyl group, wherein a plurality of R ²¹ present in one molecule may be the same or different.

(In the above general formula (c3), c represents an average value and represents a number from 0 to 10. R ³¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. , A phenyl group, a naphthyl group, or a biphenyl group, wherein a plurality of R ³¹ present in one molecule may be the same or different.

（上記一般式（ｃ４）において、ｄ及びｅはそれぞれ独立に０〜４の整数を表し、Ｒ^４１及びＲ^４２はそれぞれ独立してアルキル基又はハロゲン原子を表す。Ｒ^４３及びＲ^４４はそれぞれ独立してアルキレン基を表す。ｘ及びｙはそれぞれ独立して０以上の整数を表す。）

(In the above general formula (c4), d and e each independently represent an integer of 0 to 4, R ⁴¹ and R ⁴² each independently represent an alkyl group or a halogen atom. R ⁴³ and R ⁴⁴ each independently And x and y each independently represents an integer of 0 or more.)

  Examples of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meta ) Monocarboxylic acid such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano substituent of acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- ( (Meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (meth) a Acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) acryloyl Loxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid (meth), acrylic acid with ε-caprolactone, β-propiolactone, γ-butyrolactone, Monomers added with lactones such as δ-valerolactone, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate with (anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) Monomers added with acid (anhydride) such as maleic acid, (meth) acrylic acid dimer, etc. And the like.

  Of these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.

As a method of adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the epoxy resin, a known method can be used. For example, reacting an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group with an epoxy resin at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. it can. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, and the like can be used. .
In addition, the epoxy resin, the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone or in combination of two types. You may use the above together.

  The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. More preferably, it is in the range of 0.7 to 1.1 equivalents. If the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the amount of unsaturated groups introduced is insufficient, and the subsequent polybasic acid and / or anhydride thereof The reaction with is also insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, when the amount used is large, α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  Polybasic acids and / or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthal Examples thereof include one or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

  Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or their anhydrides. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

  A known method can be used for addition reaction of polybasic acid and / or anhydride thereof, and α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid having carboxyl group to epoxy resin. The target product can be obtained by continuing the reaction under the same conditions as in the ester addition reaction. The addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the resulting epoxy (meth) acrylate resin having a carboxyl group is in the range of 10 to 150 mgKOH / g, The degree is preferably in the range of 20 to 140 mgKOH / g. If the acid value of the epoxy (meth) acrylate resin having a carboxyl group is less than the above range, the alkali developability tends to be poor, and if it exceeds the above range, the curing performance tends to be inferior.

  In addition, it is good also as what introduce | transduced polyfunctional alcohol, such as a trimethylol propane, a pentaerythritol, a dipentaerythritol, and introduce | transduced the multibranched structure at the time of addition reaction of this polybasic acid and / or its anhydride.

  An epoxy (meth) acrylate resin having a carboxyl group is usually a polybasic acid in a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group. And / or an anhydride thereof, or a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group with a polybasic acid and / Or its anhydride and polyfunctional alcohol are mixed and then heated. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol is not particularly limited. Any hydroxyl group present in the mixture of the reaction product of the epoxy resin and the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group and the polyfunctional alcohol by heating. To the polybasic acid and / or its anhydride.

  The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the epoxy (meth) acrylate resin having a carboxyl group is usually 1000 or more, preferably 1500 or more, and usually 10,000 or less, preferably It is 8000 or less, more preferably 6000 or less. If the weight average molecular weight is small, the solubility in the developer is high, and if it is too large, the solubility in the developer is low.

  The epoxy (meth) acrylate resin having a carboxyl group may be used singly or as a mixture of two or more resins.

  Moreover, as long as the organic binder (c) used by this invention does not impair the performance of this invention, you may substitute a part of the above-mentioned epoxy (meth) acrylate resin which has a carboxyl group. That is, you may use together the epoxy (meth) acrylate resin which has a carboxyl group, and another binder resin. In this case, the proportion of the epoxy (meth) acrylate resin having a carboxyl group in the organic binder (c) is preferably 50% by weight or more, particularly preferably 80% by weight or more.

As long as the performance of the present invention is not impaired, other binder resins that can be used in combination with the epoxy (meth) acrylate resin having a carboxyl group are not limited, and can be selected from resins that are usually used in photosensitive color compositions for color filters. good. Examples thereof include binder resins described in JP 2007-271727 A, JP 2007-316620 A, JP 2007-334290 A, and the like.
In addition, all other binder resins may be used alone or in combination of two or more.

<Photopolymerizable monomer (d)>
In the present invention, a photopolymerizable monomer (d) (photopolymerizable compound) is further used to increase sensitivity and the like.

  Examples of the photopolymerizable monomer (d) used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as “ethylenic monomer”). Can do. Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, a monoester of polyhydric or monohydric alcohol, etc. Can be mentioned.

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule.
Examples of such polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatics Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. In the same way, itaconic acid ester instead of itaconate, Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to and the like.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.

  The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

  In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted. Urethane (meth) acrylates as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate Allyl esters such as: vinyl group-containing compounds such as divinyl phthalate are useful.

  Among these, it is preferable to use an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid as the photopolymerizable monomer (d). In particular, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate are preferable.

  These photopolymerizable monomers (d) may be used alone or in combination of two or more.

<Photopolymerization initiator (e)>
The photopolymerization initiator (e) is a component having a function of directly absorbing light and causing a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical. If necessary, additives such as accelerators and sensitizing dyes may be added and used.

  Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, and hexaarylbi compounds described in JP-A-2000-56118. Imidazole derivatives; N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in JP-A-10-39503, N-aryl-α-amino acid salts, Radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester derivatives described in JP 2000-80068 A, JP 2006-36750 A, and the like. .

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-di-fluoro-3- (pyro-1-yl) -phen-1-yl] and the like. Can be mentioned.

  Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole. Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like.

  Examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

  Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.

  Examples of α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. It is.

  Examples of the oxime ester derivatives include the following compounds (in the following, “Me” represents “methyl group”).

  Other benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, benzophenone derivatives such as 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenol Nylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1 Acetophenone derivatives such as propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (p- Methoxyph Acridine derivatives such as benzyl) acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; and anthrone derivatives such as benzanthrone.

  Among these photopolymerization initiators, oxime ester derivatives (oxime ester compounds) are particularly preferable from the viewpoint of sensitivity.

  A photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type.

  Examples of the accelerator include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, complex such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole. A mercapto compound having a ring or an aliphatic polyfunctional mercapto compound is used. Accelerators may be used alone or in combination of two or more.

  If necessary, the photopolymerization initiator can be mixed with a sensitizing dye according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. These sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and 3-ketocoumarin compounds described in Kaihei 3-239703 and 5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, 54-155292, JP 45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-6988, JP-A-57-168088. No. 5, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818. Mention may be made of a dye or the like having a skeleton.

  Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-di Tilaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, ( p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. P-dialkylaminophenyl group-containing compounds. Of these, 4,4'-dialkylaminobenzophenone is most preferred.

  A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

<Organic solvent (f)>
As the organic solvent (f), it is preferable to select an organic solvent having a boiling point in the range of 100 to 300 ° C. More preferably, it is a solvent having a boiling point of 120 to 280 ° C.

  Examples of such organic solvents include the following.

  Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Monoe Ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;

  Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;

  Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;

  Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;

  Alkyl acetates such as cyclohexanol acetate;

  Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

  Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;

  Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;

  aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;

  Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

  Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;

  Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;

  Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

  Halogenated hydrocarbons such as butyl chloride and amyl chloride;

  Ether ketones such as methoxymethylpentanone;

  Nitriles such as acetonitrile and benzonitrile;

  Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like.

  These organic solvents may be used alone or in combination of two or more.

  When a pixel or black matrix of a color filter is formed by photolithography, the boiling point of the organic solvent is 100 to 200 ° C. (under a pressure of 101.25 [hPa]. Hereinafter, all of the boiling points are the same). It is preferable to select one. More preferably, it has a boiling point of 120 to 170 ° C.

  Of the above organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.

  In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained later tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by weight to 30% by weight, and more preferably 5% by weight to 20% by weight.

  It is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”). By using such a high boiling point solvent in combination, the colored resin composition becomes difficult to dry, but it has an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation and solidification of a coloring material at the tip of the slit nozzle. Among these various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable because of such high effects.

  The content of the high boiling point solvent in the organic solvent is preferably 3% by weight to 50% by weight, more preferably 5% by weight to 40% by weight, and particularly preferably 5% by weight to 30% by weight. If the amount of the high boiling point solvent is too small, for example, a coloring material may precipitate and solidify at the tip of the slit nozzle to cause a foreign matter defect, and if it is too much, the drying temperature of the composition will be slowed down. There is a concern that the filter manufacturing process may cause problems such as tact defects in the vacuum drying process and pin marks of prebaking.

The high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is separately contained. It doesn't have to be.
Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.

<Other compounding components of photosensitive coloring composition>
In addition to the above-mentioned components, the photosensitive coloring composition of the present invention includes adhesion improvers such as silane coupling agents and phosphoric acid group-containing compounds, thiols, coatability improvers, development improvers, ultraviolet absorbers, and antioxidants. An agent, a surfactant and the like can be appropriately blended.
In particular, in the photosensitive coloring composition of the present invention, a silane coupling agent, a phosphoric acid group-containing compound, thiols and the like are preferably used in order to improve adhesion to the substrate.

(1) Silane Coupling Agent As the type of silane coupling agent, various types such as epoxy, (meth) acrylic, and amino can be used singly or in combination of two or more.

  Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Epoxyglycans such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and ureidosilanes such as 3-ureidopropyltriethoxysilane, Although isocyanate silanes, such as 3-isocyanate propyl triethoxysilane, are mentioned, Especially preferably, the silane coupling agent of epoxy silanes is mentioned.

(2) Phosphate group-containing compound As the phosphate group-containing compound, (meth) acryloyl group-containing phosphates are preferable, and those represented by the following general formulas (f1), (f2), and (f3) are preferable.

(In the general formulas (f1), (f2), and (f3), R ⁵¹ represents a hydrogen atom or a methyl group, p and p ′ are integers of 1 to 10, and q is 1, 2 or 3.)

  These phosphoric acid group-containing compounds may be used alone or in combination of two or more.

(3) Surfactant As the surfactant, for example, various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among these, nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based and silicon-based surfactants are effective in terms of coatability.

  Examples of such surfactants include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), and KP340 (Shin-Etsu Silicone). F-470, F-475, F-478, F-559 (Dainippon Ink & Chemicals), SH7PA (Toray Silicone), DS-401 (Daikin), L-77 Nippon Unicar Co., Ltd.), FC4430 (Sumitomo 3M Co., Ltd.) and the like.

  In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.

(4) Thiols Thiols can be added to the photosensitive coloring composition of the present invention in order to increase sensitivity and improve adhesion to the substrate.

Types of thiols include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate , Butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, Ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), trimethylolpropane tris 3-mercapto butyrate), pentaerythritol tetrakis (3-mercapto butyrate), pentaerythritol tris (3-
Mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), 1,3,5-tris ( Thiol compounds such as 3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, and various of these may be used alone. Or 2 or more types can be mixed and used.

<Ingredient compounding amount in photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the content of the pigment (a) can be usually selected in the range of 1 to 70% by weight with respect to the total solid content in the photosensitive coloring composition. In this range, 10 to 70% by weight is more preferable, 20 to 60% by weight is preferable, and 40 to 60% by weight is more preferable. If the content of the pigment (a) is too small, the film thickness with respect to the color density becomes too large, which may adversely affect the gap control during liquid crystal cell formation. When there is too much content of a pigment (a), volume resistance will fall. In addition, sufficient image formability may not be obtained.

  The content of the dispersant (b) is usually 50% by weight or less, preferably 30% by weight or less, usually 1% by weight or more, preferably 3% by weight or more, based on the total solid content of the photosensitive coloring composition. is there. Further, the content of the dispersant (b) is usually 5% by weight or more, particularly 10% by weight or more, and usually 200% by weight or less, particularly 80% by weight or less based on the pigment (a). . If the content of the dispersant (d) is too small, sufficient dispersibility may not be obtained. If the content is too large, the proportion of other components is relatively reduced, resulting in a decrease in color density, sensitivity, film formability, and the like. Tend to.

Moreover, although it is possible to use together with other dispersing agents with the acrylic block copolymer which has the said vinyl pyridine as a structural monomer as a dispersing agent (b), in this case, the compounding ratio of other dispersing agents is The amount is usually 1 to 80% by weight, preferably 1 to 30% by weight, based on the total amount of the dispersant.
In addition, it is possible to use the dispersing agent (b) and a dispersing aid such as a pigment derivative together. In this case, the blending ratio of the dispersing aid such as the pigment derivative is that of the photosensitive coloring composition of the present invention. The total solid content is usually 1% by weight or more, usually 10% by weight or less, and particularly preferably 5% by weight or less.

  The content of the organic binder (c) is usually 5% by weight or more, preferably 10% by weight or more, and usually 85% by weight or less, preferably based on the total solid content of the photosensitive coloring composition of the present invention. 80% by weight or less. When the content of the organic binder (c) is remarkably small, the solubility of the unexposed portion in the developer is lowered, and it becomes easy to induce development failure. On the other hand, when the content of the organic binder (c) is too large, the permeability of the developer into the exposed area tends to be high, and the sharpness and adhesion of the pixel may be lowered.

  The content of the photopolymerizable monomer (d) is usually 90% by weight or less, preferably 80% by weight or less, based on the total solid content of the photosensitive coloring composition. When there is too much content of a photopolymerizable monomer (d), the permeability of the developing solution to an exposed part will become high, and it may become difficult to obtain a favorable image. In addition, the minimum of content of a photopolymerizable monomer (d) is 1 weight% or more normally with respect to the total solid of a photosensitive coloring composition, Preferably it is 5 weight% or more.

  The content of the photopolymerization initiator (e) is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 0.8% by weight, based on the total solid content of the photosensitive coloring composition of the present invention. 7% or more, usually 30% by weight or less, preferably 20% by weight or less. When the content of the photopolymerization initiator (e) is too small, the sensitivity may be lowered. On the other hand, when the content is too large, the solubility of the unexposed portion in the developer is lowered, and development failure tends to be induced.

When using an accelerator with a photoinitiator (e), content of an accelerator is 0 weight% or more normally with respect to the total solid of the photosensitive coloring composition of this invention, Preferably it is 0.02 weight%. Above, it is usually 10% by weight or less, preferably 5% by weight or less, and the accelerator is a proportion of 0.1 to 50% by weight, particularly 0.1 to 10% by weight, based on the photopolymerization initiator (e). It is preferable to use in.
When the blending ratio of the photopolymerization initiator component comprising the photopolymerization initiator (e) and the accelerator is extremely low, the sensitivity to the exposure light may be lowered. The solubility in the liquid may be reduced, leading to poor development.
The blending ratio of the sensitizing dye in the photosensitive coloring composition of the present invention is usually 0 to 20% by weight, preferably 0 to 15% by weight, more preferably in the total solid content in the photosensitive coloring composition. 0 to 10% by weight.

  In the photosensitive coloring composition, the amount of the organic binder (c) relative to the pigment (a) is usually 20 to 500% by weight, preferably 30 to 300% by weight, more preferably 50 to 200% by weight. is there. If the content of the organic binder (c) with respect to the pigment (a) is too low, the solubility of the unexposed part in the developer is lowered, and it is easy to induce development failure. If it is extremely high, the desired pixel film thickness is obtained. It becomes difficult to be.

  Further, when a silane coupling agent and / or a phosphoric acid group-containing compound is used as the adhesion improver, the content thereof is usually 0.1 to 5% by weight, preferably based on the total solid content in the photosensitive coloring composition. Is 0.2 to 3% by weight, more preferably 0.4 to 2% by weight. If the content of the silane coupling agent and / or the phosphoric acid group-containing compound is less than the above range, the effect of improving the adhesion cannot be sufficiently obtained. It may become.

  Moreover, when using surfactant, the content is 0.001 to 10 weight% normally with respect to the total solid in a photosensitive coloring composition, Preferably it is 0.005-1 weight%, More preferably, it is 0. 0.01 to 0.5 wt%, most preferably 0.03 to 0.3 wt%. If the surfactant content is less than the above range, the smoothness and uniformity of the coating film may not be expressed. If the content is too high, the smoothness and uniformity of the coating film may not be expressed, and other characteristics deteriorate. There is a case.

  Moreover, when using a thiol compound, the content is 0.1 to 10 weight% normally with respect to the total solid in a photosensitive coloring composition, Preferably it is 0.5 to 5 weight%. If the content of the thiol compound is too small, the sensitivity may be lowered, and if it is too much, the storage stability may be deteriorated.

  In addition, the photosensitive coloring composition of this invention is prepared using the above-mentioned organic solvent so that the solid content concentration may become 5 to 50 weight% normally, Preferably it is 10 to 30 weight%.

<Method for producing photosensitive coloring composition>
The photosensitive coloring composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method.

  Usually, the pigment (a) is preferably dispersed in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the pigment (a) is finely divided by the dispersion treatment, the resist coating characteristics are improved. Further, the pigment (a) contributes to the improvement of the light shielding ability.

  The dispersion treatment is usually performed by using an epoxy (meth) acrylate resin having a carboxyl group of the pigment (a), the organic solvent (f), the dispersant (b), the dispersion aid, and the organic binder (c) and / or others. It is preferable to carry out in a system in which part or all of the binder resin is used in combination. (Hereinafter, the mixture to be subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as “ink”.) In particular, when the dispersant (b) is used, the obtained ink and resist are increased over time. It is preferable because viscosity is suppressed (excellent in dispersion stability).

  In addition, when a dispersion treatment is performed on a liquid containing all components to be blended in the photosensitive coloring composition, a highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing the above-described components.

  When the pigment (a) is dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. In the dispersion treatment conditions, the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the resist is in the range of 100 to 200. When the glossiness of the resist is low, the dispersion treatment is not sufficient, and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, and the like. . Further, when the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

  Next, the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered by a filter or the like.

[Color filter]
Next, a color filter using the photosensitive coloring composition of the present invention will be described according to its production method.

(1) Transparent substrate (support)
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly (meta ) Thermosetting resin sheets such as acrylic resins, or various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

  For transparent substrates and black matrix forming substrates, to improve surface properties such as adhesion, corona discharge treatment, ozone treatment, silane coupling agents, thin film formation treatment of various resins such as urethane resins, etc. May be performed.

  The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

(2) Black matrix A color matrix of the present invention can be produced by providing a black matrix on a transparent substrate, and usually forming red, green, and blue pixel images, and the photosensitive coloring composition of the present invention. The product is used as at least one resist forming coating solution of black, red, green, and blue. For the black resist, on the transparent glass surface on the transparent substrate, on the resin black matrix forming surface formed on the transparent substrate for red, green, and blue, each process of coating, heat drying, image exposure, development and thermosetting is performed. The pixel image of each color is formed. A black matrix can be formed in the same manner as described below for forming red, green, and blue pixel images.

(3) Pixel formation
(3-1) Application of photosensitive coloring composition The photosensitive coloring composition of the present invention is applied on a transparent substrate and dried, and then a photomask is overlaid on the coating film. A pixel image is formed by exposure, development, and thermosetting or photocuring as necessary to produce a black matrix. Subsequently, a color filter image can be formed by performing the same operation about the photosensitive coloring composition of three colors of red, green, and blue, respectively.

  The photosensitive coloring composition for the color filter can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, or a spray coating method. In particular, the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.

  If the thickness of the coating film is too thick, pattern development becomes difficult, and it may be difficult to adjust the gap in the liquid crystal cell forming process. May become impossible. The thickness of the coating film is preferably in the range of 0.2 to 20 μm, more preferably in the range of 0.5 to 10 μm, and still more preferably in the range of 0.5 to 5 μm, as the film thickness after drying. It is a range.

(3-2) Drying of coating film The drying of the coating film after applying the photosensitive coloring composition to the substrate is preferably carried out by a drying method using a hot plate, IR oven, or convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected in a range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.

  The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, if the drying temperature is too high, the organic binder (c) may be decomposed to induce thermal polymerization and cause poor development. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.

(3-3) Exposure Image exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive coloring composition and irradiating an ultraviolet or visible light source through this mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

(3-4) Development The color filter according to the present invention is an aqueous solution containing an organic solvent or a surfactant and an alkaline compound after image-exposing a coating film made of a photosensitive coloring composition with the above-mentioned light source. An image can be formed on a substrate by development using a film. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent may be used alone or in combination with an aqueous solution.

  There are no particular limitations on the conditions for the development treatment, and usually the development temperature is in the range of 10 to 50 ° C., particularly 15 to 45 ° C., particularly preferably 20 to 40 ° C. Any of a developing method, an ultrasonic developing method and the like can be used.

(3-5) Thermosetting treatment The color filter substrate after development is subjected to thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

(3-6) Formation of transparent electrode The color filter is used as a part of components such as color displays and liquid crystal display devices by forming transparent electrodes such as ITO on the image as it is. In order to enhance the property and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[Liquid Crystal Display]
The liquid crystal display device of the present invention is manufactured using the above-described color filter of the present invention.

  A liquid crystal display device usually forms an alignment film on a color filter, spreads spacers on the alignment film, and then bonds to a counter substrate to form a liquid crystal cell, injects liquid crystal into the formed liquid crystal cell, Complete by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to the gap (gap) with the counter substrate is used, and usually a spacer having a size of 2 to 8 μm is preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

  The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of reduced pressure in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The warming hold during decompression is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

[Organic EL display]
An organic EL display can be produced using the color filter of the present invention.

  When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 1, first, a pattern (that is, the pixel 20 and adjacent) formed on the transparent support substrate 10 by the colored resin composition. A color filter in which a resin black matrix (not shown) provided between the pixels 20 is formed is manufactured, and the organic light-emitting body 500 is formed on the color filter via the organic protective layer 30 and the inorganic oxide film 40. By laminating, the organic EL element 100 can be manufactured. In addition, at least one of the pixel 20 and the resin black matrix is manufactured using the photosensitive coloring composition of the present invention. As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. A method described in, for example, “Organic EL display” (Ohm, Inc., August 20, 2004, light emission, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 manufactured in this manner, etc. Thus, an organic EL display can be produced.

  The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

  Next, although a manufacture example, a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.

<Production Example 1: Preparation of coated carbon black>
Carbon black was produced by a normal oil furnace method. However, ethylene bottom oil with a small amount of Na, Ca, and S was used as the raw material oil, and combustion was performed using gas fuel. Furthermore, pure water treated with an ion exchange resin was used as the reaction stop water. 540 g of the obtained carbon black was stirred at 5,000 to 6,000 rpm for 30 minutes together with 14500 g of pure water using a homomixer to obtain a slurry. The slurry was transferred to a container with a screw type stirrer, and 600 g of toluene in which 60 g of epoxy resin “Epicoat 828” (manufactured by Japan Epoxy Resin) was dissolved was added little by little while mixing at about 1,000 rpm. In about 15 minutes, the entire amount of carbon black dispersed in water was transferred to the toluene side, and became particles of about 1 mm.
Next, after draining with a 60 mesh wire net, it put into the vacuum dryer, and it dried at 70 degreeC for 7 hours, and removed toluene and water.
The resin coating amount of the obtained coated carbon black is 10% by weight with respect to the total amount of carbon black and resin.

<Production Example 2: Preparation of coated carbon black ink>
With respect to 20 parts by weight of the coated carbon black prepared in Production Example 1, 4.4 parts by weight of the dispersant shown in Table 1 and 1 part by weight of S12000 (Lubrisol, phthalocyanine acidic derivative) as a pigment derivative of the dispersion aid In addition, propylene glycol monomethyl ether acetate (PGMEA) was added so that the solid content concentration was 25% by weight.
This was sufficiently stirred with a stirrer and premixed. Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As beads, 0.5 mmφ zirconia beads were used, and 60 g of dispersion and 180 g of beads were added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare inks 1 to 3.

The dispersant used for each ink is as follows.
EFKA4320: acrylic block copolymer dispersant (made by BASF, resin containing the structural units (I) to (III), structural unit (I): 15 mol%, structural unit (II): 15 mol%, configuration (Unit (III): 70 mol%)
EFKA4046: Urethane dispersant (BASF)
DB2000: acrylic block copolymer dispersant (manufactured by Big Chemie, acrylic block copolymer not containing vinylpyridine as a constituent monomer)

<Evaluation of ink>
(1) Measurement of glossiness In order to judge the quality of the dispersion state of each ink obtained in Production Example 2, the glossiness was measured by the following method. The better the dispersion state, the smaller the particle size of the carbon black, so that irregular reflection is suppressed and a high gloss value is obtained. That is, the higher the glossiness, the better the dispersion state.
Each ink was applied onto a glass substrate by a spin coater and dried on a hot plate at 100 ° C. for 150 seconds. This sample was measured for 20-degree specular gloss by a gloss meter (Hick Chemie).
The results are shown in Table 1. As shown in Table 1, the result of ink 1 was higher than that of inks 2 and 3.

(2) Measurement of dispersed particle size Inks 1 to 3 were further diluted 2000 times with PGMEA, and the average value of the dispersed particle size was determined by a dynamic light scattering method using a light scattering particle size analyzer FPAR1000 (manufactured by Otsuka Electronics). It was measured.
The results are shown in Table 1. As shown in Table 1, compared to inks 1 and 2, ink 3 had a coarse dispersion particle size and dispersibility was slightly inferior.

<Synthesis Example 1: Synthesis of alkali-soluble resin (C)>

50 g of epoxy compound having the above structure (epoxy equivalent 264), 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of paramethoxyphenol were attached to a thermometer, a stirrer and a cooling pipe. The reaction was continued at 90 ° C. with stirring until the acid value was 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by weight of the above epoxy acrylate solution, 0.76 parts by weight of trimethylolpropane (TMP), 3.3 parts by weight of biphenyltetracarboxylic dianhydride (BPDA), 3.5 parts by weight of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution became transparent, it was diluted with methoxybutyl acetate and prepared to have a solid content of 50% by weight. The acid value was 131 mgKOH / g, and the polystyrene-soluble weight average molecular weight (Mw) of 2600 was measured with GPC. Resin (C) was obtained. This alkali-soluble resin (C) corresponds to an alkali-soluble resin having an ethylenically unsaturated bond of the organic binder (c) of the present invention.

<Synthesis Example 2: Synthesis of Photopolymerization Initiator (E)>
(Diketone body)
Ethylcarbazole (5 g, 25.61 mmol) and o-naphthoyl chloride (5.13 g, 26.89 mmol) are dissolved in 30 ml of dichloromethane, cooled to 2 ° C. with an ice-water bath and stirred, and then AlCl ₃ (3. 41 g, 25.61 mmol) was added. Further, after stirring at room temperature for 3 hours, a 15 ml dichloromethane solution of crotonoyl chloride (2.81 g, 26.89 mmol) was added to the reaction solution, then AlCl ₃ (4.1 g, 30.73 mmol) was added, and another 1 hour 30 hours. Stir for minutes. The reaction solution was poured into 200 ml of ice water, 200 ml of dichloromethane was added, and the organic layer was separated. The collected organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a diketone body as a white solid (10 g).

(Oxime body)
Diketone (3.00 g, 7.19 mmol), NH ₂ OH · HCl (1.09 g, 15.81 mmol), and sodium acetate (1.23 g, 15.08 mmol) were mixed with 30 ml of isopropanol and refluxed for 3 hours. .
After completion of the reaction, the reaction mixture was concentrated, 30 ml of ethyl acetate was added to the resulting residue, washed with 30 ml of saturated aqueous sodium hydrogen carbonate solution and 30 ml of saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain 1.82 g of a solid. This was purified by column chromatography to obtain 2.22 g of an oxime compound as a pale yellow solid.

(Oxime ester)
The oxime (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) were added to 20 ml of dichloromethane, and the mixture was ice-cooled. Triethylamine (1.77 g, 17.5 mmol) was added dropwise, and 1 Reacted for hours. After confirming disappearance of the raw material by thin layer chromatography, water was added to stop the reaction. The reaction solution was washed twice with 5 ml of saturated aqueous sodium hydrogen carbonate solution and twice with 5 ml of saturated brine, and dried over anhydrous sodium sulfate. After filtration, the organic layer was concentrated under reduced pressure, and the resulting residue was purified by column chromatography (ethyl acetate / hexane = 2/1) to obtain 0.79 g of a light yellow solid photopolymerization initiator (E). Obtained.

¹ H NMR (CDCl ₃ ): σ 1.17 (d, 3H), 1.48 (t, 3H), 1.53 (s, 3H), 1.81 (s, 3H), 2.16 (s, 3H), 2.30 (s, 3H), 3.17-3.32 (m, 2H), 4.42 (q, 2H), 4.78-4.94 (br, 1H), 7.45. -7.59 (m, 5H), 7.65 (dd, 1H), 7.95 (m, 2H), 8.04 (m, 2H), 8.14 (dd, 1H), 8.42 ( d, 1H), 8.64 (d, 1H)
This oxime ester body corresponds to the photopolymerization initiator (e) in the present invention.
The structure of the photopolymerization initiator (E) is shown below.

<Example 1>
(Preparation of resist (photosensitive coloring composition))
Each component shown in Table 2 was added in the proportions shown in Table 2, and stirred and dissolved with a stirrer to prepare Resist 1 having a solid content concentration of 17% by weight.

(Evaluation of resist)
(1) Peeling test As an evaluation of the easiness of generation of foreign matter generated at the nozzle of the die coater, evaluation was performed by the method described in JP-A-2007-268525.
After immersing the glass piece in the resist for 4 seconds, the glass piece was taken out and air-dried for 56 seconds. The glass piece was dipped again and removed, and this operation was repeated 250 times in total. Thereafter, the glass piece was air-dried again, and when it was dry, the resist surface of the immersion part was observed with an optical microscope and evaluated according to the following criteria.
○: No foreign matter remains on the dry surface.
(Triangle | delta): The foreign material which the pigment aggregated on the dry surface generate | occur | produced.
X: A large amount of foreign matter is generated on the dry surface.

(2) Volume resistivity The prepared resist was applied on a glass substrate having a chromium vapor-deposited film with a spin coater, and dried on a hot plate at 80 ° C. for 150 seconds. Subsequently, the resin black matrix was formed by heating in an oven at 230 ° C. for 210 minutes. The film thickness of the resin black matrix film was measured with a stylus type film thickness meter (“α-step” manufactured by Tencor Corporation) and found to be 1.5 μm. Using this sample's chromium film as the main electrode and a gold film formed by vapor deposition on the resin black matrix as the counter electrode, using an ultrahigh resistance ammeter (advantest R8340A), the current value at an applied voltage of 1 V DC Was measured to determine the volume resistivity.

(3) Development residue The prepared resist was applied to a glass substrate with a spin coater and dried on a hot plate at 80 ° C. for 150 seconds. Thereafter, the photosensitive layer was removed by spray development at a temperature of 23 ° C. using an aqueous KOH solution having a concentration of 0.05% by weight. A portion of the glass surface after development was wiped off with ethyl alcohol, and the presence or absence of a resist residue was visually observed under a white light source and evaluated according to the following criteria.
○: Nothing remains on the glass surface.
Δ: A slight residue remains on the glass surface, and a difference from the wiped portion is observed.
X: A residue remains remarkably on the glass surface.

  The evaluation results are shown in Table 3.

<Comparative Example 1>
In Example 1, the ink 1 was changed to the ink 2, and other than that, the resist 2 was prepared with the same composition as the resist 1 and evaluated in the same manner. The results are shown in Table 3.

<Comparative example 2>
In Example 1, the ink 1 was replaced with the ink 3, and a resist 3 was prepared with the same composition as that of the resist 1 except that it was evaluated. The results are shown in Table 3.

  As shown in Table 3, in the photosensitive coloring composition of the present invention using an acrylic block copolymer having vinylpyridine as a constituent monomer as a dispersant, the peel test is also good and the volume resistivity is high, No development residue was generated. On the other hand, with the conventional dispersants as in Comparative Examples 1 and 2, sufficient performance could not be obtained.

DESCRIPTION OF SYMBOLS 10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic light emitter

Claims (8)

  Including pigment (a), dispersant (b), organic binder (c), photopolymerizable monomer (d), photopolymerization initiator (e), and solvent (f), and pigment (a) is a resin Carbon black coated with a dispersant, the dispersant (b) is an acrylic block copolymer having vinylpyridine as a constituent monomer, and the organic binder (c) is an alkali-soluble resin having an ethylenically unsaturated bond The photosensitive coloring composition characterized by the above-mentioned. The photosensitive coloring matter according to claim 1, wherein the dispersant (b) is a resin containing structural units represented by the following general formulas (I), (II), and (III) as structural units. Composition.

(In the general formula (II), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 3 carbon atoms, t represents an integer of 5 to 15 and R ³ represents 1 carbon atom. Represents a phenyl group substituted with an alkyl group of ˜25, a phenyl group, or an alkyl group of 1 to 18 carbon atoms.)

(In the general formula (III), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)   The photosensitive coloring composition according to claim 1, further comprising a sulfonic acid derivative of phthalocyanine as a dispersion aid.   The photosensitive coloring composition according to any one of claims 1 to 3, wherein the pigment (a) is contained in an amount of 40 to 60% by weight based on the total solid content in the photosensitive coloring composition. (B) The organic binder (c) contains the following alkali-soluble resin (c-1) and / or alkali-soluble resin (c-2), according to any one of claims 1 to 4. Photosensitive coloring composition.
<Alkali-soluble resin (c-1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
<Alkali-soluble resin (c-2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.   Hardened | cured material formed by hardening | curing the photosensitive coloring composition in any one of Claims 1 thru | or 5.   A color filter formed using the photosensitive coloring composition according to claim 1.   A liquid crystal display device produced using the color filter according to claim 7.

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