JP2019168578A - Color composition for color filter and color filter - Google Patents

Abstract

To provide a color composition for a color filter having high sensitivity, high developing speed and excellent viscosity stability and a color filter formed by using the color composition for a color filter.SOLUTION: A color composition for a color filter is composed of pigment (A), dispersant (B), moisture content regulation resin (L), binder resin (D) (excluding the case of the pigment, dispersant or moisture content regulation resin), and solvent (S). The moisture content regulation resin (L) is composed of copolymer of an ethylenically unsaturated monomer (F) containing a fluorinated alkyl group and/or a poly(perfluoroalkylene ether) chain and another ethylenically unsaturated monomer (N), moisture content of the color composition is 0.3-2.0 wt.% based on the total weight of the color composition, and electric conductivity at 25°C of the color composition is 100-1000 nS/cm.SELECTED DRAWING: None

Description

  An object of the present invention is to provide a color filter coloring composition having excellent viscosity stability, high sensitivity, and high development speed, and a color filter using the same.

The pigment used for the color filter is very fine, and in particular, recently, high contrast is required, and it is necessary to use a finer pigment.
However, as shown in Patent Document 1, in all steps where the processing liquid is in contact with the outside air, such as a step of refining the pigment, a step of mixing various other materials, and a step of applying to the glass substrate, Moisture contained in the pigment is mixed into the pigment solution, but if the amount of moisture increases excessively, problems such as increase in viscosity caused by aggregation of pigments and dispersants and decomposition or alteration of components contained in the solution was there.

JP 2008-003127 A

  An object of the present invention is to provide a color filter coloring composition having high sensitivity, high development speed and excellent viscosity stability, and a color filter formed using the color filter coloring composition. To do.

That is, the present invention includes a pigment (A), a dispersant (B), a moisture content adjusting resin (L), a binder resin (D) (except for the case of the pigment, dispersant, or moisture content adjusting resin), and A color filter coloring composition comprising a solvent (SL),
The water content adjusting resin (L) includes an ethylenically unsaturated monomer (F) containing a fluorinated alkyl group and / or a poly (perfluoroalkylene ether) chain, and another ethylenically unsaturated monomer ( N) and a copolymer of
And the water content of the coloring composition is 0.3 to 2.0% by weight based on the total weight of the coloring composition,
Further, the present invention relates to a colored composition for a color filter, wherein the conductivity of the colored composition at 25 ° C. is 100 to 1000 nS / cm.

  Moreover, this invention relates to the said coloring composition for color filters characterized by the other ethylenically unsaturated monomer (N) containing the monomer which has an adamantyl group.

  In the present invention, the dispersant (B) further includes an adsorbent (C) having a pigment adsorbing group, and the adsorbent (C) having the pigment adsorbing group is a pigment derivative or base having a basic group. A dye derivative (Q) having at least one basic substituent selected from the group consisting of an anthraquinone derivative having a basic substituent, a triazine derivative having a basic substituent, and an acridone derivative having a basic substituent, and / or Alternatively, the present invention relates to the coloring composition for a color filter, comprising a vinyl resin (S) having a basic group or a pigment derivative having an acidic group.

  The present invention also relates to the above color filter coloring composition, further comprising a dye.

  The present invention also relates to the above color filter coloring composition, further comprising a photopolymerizable monomer and a photopolymerization initiator.

  The present invention also relates to a color filter comprising a filter segment formed on the substrate from the color filter coloring composition.

  The colored composition of the present invention has high sensitivity because the water content is 0.3 to 2.0% by weight based on the total weight of the colored composition, has a high development speed, and excellent viscosity stability. ing.

  Hereinafter, the present invention will be described in detail.

<Conductivity>
The organic solvent mainly used in the present invention has an electrical conductivity at 25 ° C. of 1 mS / cm or less. By using a colored composition containing the moisture content adjusting resin of the present invention and other components, the colored composition The conductivity at 25 ° C. is 100 to 1000 nS / cm. This conductivity is closely related to moisture. If there is too much moisture, the components in the colored composition are decomposed to become, for example, contaminated ions. As a result, the conductivity exceeds 1000 nS / cm, which is not preferable.

<Moisture content>
The water content of the colored composition of the present invention can be measured by a known method such as the Karl Fischer method. The Karl Fischer method uses a Karl Fischer reagent (comprising a solvent such as iodine, sulfur dioxide, base, and alcohol) that selectively and quantitatively reacts with water as shown in the following formula (1). It is a method of measuring the rate. This method includes a coulometric titration method and a volumetric titration method, but either method may be used.
I ₂ + SO ₂ + 3Base + ROH + H ₂ O → 2Base, HI + Base, HSO ₄ R (1)

In the colored composition of the present invention, the water content immediately before coating on the substrate is 0.3 to 2.0% by weight, preferably 0.3 to 2.0% based on the total weight of the colored composition (100% by weight). The amount is 1.5% by weight, more preferably 0.6 to 1.5% by weight.
A colored composition having a moisture content exceeding 2.0% by weight thickens with time, and causes coating failure when applied to a substrate. In addition, a coloring composition having a water content of less than 0.3% by weight does not sufficiently improve sensitivity and development speed.
The amount of water in the colored composition may be controlled by intentionally adding water to the colored composition at the time of preparation of the colored composition or during storage after preparation, or the colored composition may be added to the glass substrate. In the step of applying, the coloring composition that cannot be applied and has remained may be recovered and applied in the step of recovering the colored composition.
Further, when the water content increases, there are a method in which a molecular sieve, which is a porous material, is put in and dehydrated, or a method in which it is left in an atmosphere of a dry inert gas or the like.

<Pigment (A)>
As a pigment contained in the coloring composition for a color filter of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferred, and organic pigments are usually used. Hereinafter, typical pigments that can be used in the coloring composition for a color filter of the present invention are listed.

  Examples of red pigments that can be used in the present invention include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208,209,210,216,220,221,224,226,242,246,254,255,264,269,270,272,273,274,276,277,278,279,280,2 1,282,283,284,285,286,287 the like, but not particularly limited thereto.

  Examples of the orange pigment that can be used in the present invention include C.I. I. Pigment Orange 38, 43, 71, 73, etc. are mentioned, but it is not particularly limited to these.

  Examples of yellow pigments that can be used in the present invention include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176 177,179,180,181,182,185,187,188,193,194,198,199,213,214,218,219,220,221 the like, but not particularly limited thereto.

  Examples of the green pigment that can be used in the present invention include C.I. I. Pigment Green 7, 10, 36, 37, 58 and the like can be mentioned, but not limited thereto.

  Examples of blue pigments that can be used in the present invention include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. It is not limited.

  Purple pigments that can be used in the present invention 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, 27, 29, 30, 31, 32, 37, 39, 40, 42, 44, 47, 49, 50 and the like can be mentioned, but not limited thereto.

  Examples of inorganic pigments that can be used in the present invention include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt Examples thereof include metal oxide powders such as green, amber, titanium black, synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powder, and metal powder. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.

<Dye>
The coloring composition of the present invention can use a dye as a colorant in combination with the pigment (A). As the dye, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes and the like can be used. Moreover, it may be in the form of lake pigments obtained by rake-forming these derivatives or dyes.

Furthermore, in the case of an acid dye having an acid group such as sulfonic acid or carboxylic acid, or in the form of a direct dye, an inorganic salt of an acid dye, an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, Alternatively, use a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or salt formation using a resin component having these functional groups, or use it as a salt-forming compound after sulfonamidation. Therefore, it is possible to obtain a colored composition having excellent fastness, which is preferable.
A salt-forming compound of an acid dye and a compound having an onium base is also preferable because of excellent fastness. More preferably, the compound having an onium base is a resin having a cationic group in the side chain.

  In the case of a basic dye, it can be used after salt formation using an organic acid, perchloric acid or a metal salt thereof. Among them, a salt forming compound of a basic dye is preferable because of its resistance and excellent compatibility with pigments, and further, a basic dye and organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus, which are counter components that function as counter ions. It is possible to use a salt-forming compound obtained by salting an anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye. It is more preferable.

  Moreover, when it has a polymerizable unsaturated group in a pigment | dye frame | skeleton, it can be set as the dye excellent in tolerance, and it is preferable.

  Examples of the chemical structure of the dye include azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthraquinones) Pyridone dyes), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes Dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes Indigo dyes, mention may be made thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and a dye structure derived from a dye selected from those metal complex dyes.

  Among these pigment structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium from the viewpoint of color characteristics such as hue, color separation, and color unevenness Preferred are dye structures derived from dyes selected from dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, phthalocyanine A pigment structure derived from a pigment selected from the system dyes is more preferable. For specific pigment compounds that can form a pigment structure, “New Edition Dye Handbook” (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), “Color Index” (The Society of Dyers and Colorists), “Dye Handbook” (Okawara et al.) Ed; Kodansha, 1986).

[Xanthene dyes]
The xanthene dyes that can be preferably used in the present invention are red and purple, and preferably have any form of oil-soluble dyes, acid dyes, direct dyes, and basic dyes. In addition, a lake pigment in which these dyes are raked may be used.
Among these, it is preferable to use a xanthene oil-soluble dye and a xanthene acid dye because of excellent hue.

A red or purple color means C.I. I. Solvent Red, C.I. Oil soluble dyes such as I. solvent violet, C.I. I. Basic Red, C.I. Basic dyes such as I. basic violet, C.I. I. Acid Red, C.I. Acid dyes such as I. acid violet, C.I. I. Direct Red, C.I. I. Direct dyes such as direct violet, and the like.
Here, the direct dye has a sulfonic acid group (—SO ₃ H, —SO ₃ Na) in the structure, and in the present invention, the direct dye is regarded as an acid dye.

Further, the xanthene basic dye is preferably used after being salted using an organic acid or perchloric acid. As the organic acid, organic sulfonic acid or organic carboxylic acid is preferably used. Of these, naphthalenesulfonic acid such as tobias acid and perchloric acid are preferably used in terms of resistance.
In addition, xanthene-based acid dyes are used as salt-forming compounds by chlorination using quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., and resin components having these functional groups. In view of resistance, it is preferable to use it as a sulfonamide compound after sulfonamidation.

  Among these, a salt component of a xanthene acid dye and / or a sulfonic acid amide compound of a xanthene acid dye is preferable because of excellent hue and resistance, and further, a counter component that functions as a counter ion. It is more preferable to use a compound prepared by using a quaternary ammonium salt compound and a sulfonic acid amide compound obtained by sulfonamidating a xanthene acid dye.

  Among xanthene dyes, rhodamine dyes are preferable because they are excellent in color developability and resistance.

  Hereinafter, the form of the xanthene dye used in the present invention will be specifically described in detail.

[Xanthene oil-soluble dye]
Xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and C.I. I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solven Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10 and the like.
Among them, CI solvent red 35, CI solvent red 36, CI solvent red 49, CI solvent red 109, CI solvent red, which are rhodamine-based oil-soluble dyes having high color development Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.

[Xanthene-based basic dyes]
Examples of xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B) and the like. Among these, C.I. I. Basic Red 1, C.I. I. Basic violet 10 is preferably used.

[Xanthene acid dyes]
Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

These acidic dyes are preferably salt-forming compounds of acidic dyes and nitrogen-containing compounds, such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., and their functionalities. It is preferable to form a salt using a resin component having a group to form a salt forming compound of a xanthene-based acidic dye because high heat resistance, light resistance, and solvent resistance can be imparted.
Further, it may be a salt-forming compound of an acid dye and a compound having an onium base, and among them, the compound having an onium base is a resin having a cationic group in the side chain, thereby reducing the brightness and resistance. It can be set as the outstanding coloring composition.

  Primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tridodecylamine, tetra Examples include aliphatic unsaturated primary amines such as decylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, cured tallow alkylamine, allylamine, aniline, and benzylamine. .

  Secondary amine compounds include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkyl. Amine, di-cured tallow alkylamine, distearylamine, etc.

  Examples of the tertiary amine compound include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine and the like.

  The quaternary ammonium salt compounds include tetramethylammonium chloride, tetraethylammonium chloride, monostearyltrimethylammonium chloride, distearyldimethylammonium chloride, tristearylmonomethylammonium chloride, cetyltrimethylammonium chloride, trioctylmethylammonium chloride, dioctyldimethylammonium chloride. , Monolauryltrimethylammonium chloride, dilauryldimethylammonium chloride, trilaurylmethylammonium chloride, triamylbenzylammonium chloride, trihexylbenzylammonium chloride, trioctylbenzylammonium chloride, trilaurylbenzylammonium chloride Id, benzyl dimethyl stearyl ammonium chloride, and benzyl dimethyl octyl ammonium chloride, dialkyl (alkyl C14 -C18) dimethyl ammonium chloride (hydrogenated tallow), and the like.

  Specific examples of the quaternary ammonium salt compound products include, for example, Cotamin 24P, Cotamin 86P Conk, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50 manufactured by Kao Corporation, and Lion Corporation's Arcade 210- 80E, 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75, 2HP flakes, and the like. Among them, Cotamine D86P (distearyldimethylammonium chloride), Arcard 2HT-75 (dialkyl (alkyl is C14- C18) dimethylammonium chloride).

[Resin having a cationic group in the side chain]
The resin having a cationic group in the side chain will be described. The resin having a cationic group in the side chain for obtaining a salt-forming compound is not particularly limited as long as it has at least one onium base in the side chain, but a suitable onium salt structure is available. From the viewpoint of the above, ammonium salts, iodonium salts, sulfonium salts, diazonium salts, and phosphonium salts are preferable, and in consideration of storage stability (thermal stability), they are ammonium salts, iodonium salts, and sulfonium salts. It is more preferable. More preferred is an ammonium salt.

  The resin having a cationic group in the side chain is an alkali resin containing a structural unit represented by the following general formula (1), and the cationic group in the general formula (1) is an anionic group of the xanthene acid dye. A salt-forming compound can be obtained by forming a salt.

General formula (1)

[In the general formula (1), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁵² to R ⁵⁴ each independently represent a hydrogen atom, an optionally substituted alkyl group, an alkenyl group which may be substituted or an optionally substituted aryl group, the R ⁵² to R ⁵⁴ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ⁵⁵ —, —COO—R ⁵⁵ —, and R ⁵⁵ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

[Salt formation]
A salt-forming compound of an acid dye and a nitrogen-containing compound or a resin having a cationic group in the side chain can be produced by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 11-72969.
For example, a xanthene acid dye may be used, and after the xanthene acid dye is dissolved in water, a quaternary ammonium salt compound may be added and subjected to chlorination while stirring. Here, the sulfonic acid group (—SO ₃ H), sodium sulfonate group (—SO ₃ Na) part in the xanthene acid dye and the ammonium group (NH ₄ ⁺ ) part of the quaternary ammonium salt compound are combined. A salt compound is obtained. In addition, instead of water, methanol and ethanol are also solvents that can be used for the chlorination.

In addition, the salt-forming compound used in the present invention is prepared by stirring or vibrating an aqueous solution in which a resin having a cationic group in the side chain represented by the general formula (1) and an acidic dye are dissolved, or the general formula (1 It can be easily obtained by mixing an aqueous solution of a resin having a cationic group in the side chain represented by (4) and an aqueous solution of an acidic dye under stirring or vibration. In the aqueous solution, the ammonium group of the resin and the anionic group of the acidic dye are ionized and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, the salt composed of the counter anion of the resin and the counter cation of the acidic dye is water-soluble and can be removed by washing or the like. As for the resin having a cationic group in the side chain to be used and the acid dye, only a single type or a plurality of types having different structures may be used.
In addition, with other acidic dyes, a salt-forming compound with a nitrogen-containing compound or a resin having a cationic group in the side chain can be obtained in the same manner as the xanthene dye.

[Sulphonic acid amide compound]
The acidic dye used in the present invention may be a sulfonic acid amide compound obtained by reacting a sulfonic acid amide compound with an anionic dye.
The sulfonic acid amide compound of an acid dye that can be preferably used for the acid dye of the present invention is obtained by chlorinating an acid dye having —SO ₃ H and —SO ₃ Na by a conventional method to convert —SO ₃ H into —SO ₂ Cl. This compound can be produced by reacting with an amine having a —NH ₂ group.
Specific examples of amine compounds that can be preferably used in sulfonamidation include 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, and 3-ethoxypropyl. It is preferable to use amine, cyclohexylamine or the like.
An example using a xanthene acid dye is C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 289 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 289.
In addition, C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 52 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 52 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 52.
Moreover, also in other acidic dyes, a sulfonic acid amide compound can be obtained in the same manner as xanthene dyes.

  Examples of such xanthene dyes include JP2010-032999A, JP2011-138094A, JP2011-227313A, JP2011-242752A, JP2012-107192A, No. 2013-033194, Japanese Patent Application No. 2011-71888, Japanese Patent Application No. 2013-72263, Japanese Patent Application No. 2013-81209, Japanese Patent Application Laid-Open No. 2014-173064, Japanese Patent Application No. 2013-53028, Japanese Patent Application No. 2013. No. -52186, JP 2014-196392 A, JP 2014-196393 A, JP 2014-201714 A, JP 2014-201715 A, JP 2013-050693 A, JP 2013-178478 A. Publication, JP2013-203356 Distribution, it is possible to use a known technique described in WO 2013/011687 pamphlet or the like.

[Dipyrromethene dye]
The dipyrromethene dye is a dye having a partial structure derived from a dipyrromethene dye as a partial structure of the dye part, and preferably a dipyrromethene compound and a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound. However, a metal complex compound in which the structure represented by the general formula (2) is coordinated to a metal atom or a metal compound (hereinafter, appropriately referred to as “dipyrromethene metal complex compound”) is preferable.

[Dipyrromethene metal complex compound]
The metal complex compound (dipyrromethene metal complex compound) in which the structure represented by the general formula (2) is coordinated to a metal atom or a metal compound will be described.

General formula (2)

In the general formula (2), R ^{61 to} R ⁶⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁶⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Represents.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or 2 Valent metal chlorides are included. Examples of the metal or metal compound include ZnCl, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, and B, as well as AlCl3, InCl3, FeCl3, and TiCl2. Further, metal chlorides such as SnCl2, SiCl2, and GeCl2, metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) 2 are also included.
Among these, as a metal or a metal compound, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, and the like from the viewpoint of stability of the complex, spectral characteristics, heat resistance, light resistance, manufacturing suitability, and the like. Ni, Co, TiO, B, or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO is most preferred.

  Examples of such dipyrromethene dyes include Japanese Patent No. 5085256, Japanese Unexamined Patent Application Publication No. 2008-292970, Japanese Unexamined Patent Application Publication No. 2010-85758, Japanese Unexamined Patent Application Publication No. 2010-84309, Japanese Patent Application No. 2010-43530, and Japanese Unexamined Patent Application Publication No. 2013. Known techniques described in JP-A-0800010, JP2013-210596A, International Publication No. 2013/141156, etc. can be used.

  Here, as the dipyrromethene dye in the colorant used in the present invention, a dipyrromethene dye having an absorption maximum in the vicinity of 500 to 600 nm is preferable and the absorption in the vicinity of 525 to 575 nm is preferable from the viewpoint of improving the brightness and contrast ratio of the color filter. A dipyrromethene dye having a maximum is more preferable, and a dipyrromethene dye having an absorption maximum in the vicinity of 540 to 560 nm is particularly preferable.

Examples of such dipyrromethene dyes include Illustrative Compound I-1 (absorption maximum 558.2 nm) described in Japanese Patent No. 5085256, III-45 (absorption maximum 546.7 nm), and the like.

[Triphenylmethane dye]
Examples of the triphenylmethane dye skeleton include a diaminotriphenylmethane dye skeleton, a triaminotriphenylmethane dye skeleton, and a rosic acid dye skeleton having an OH group.
Triaminotriphenylmethane-based dye skeletons are preferable in that they are excellent in color tone and more excellent in fastness to sunlight than others. Among them, a diphenylnaphthylmethane dye skeleton that is a basic dye is particularly preferable.

[Triphenylmethane basic dye]
The triphenylmethane basic dye develops color when the NH ₂ or OH group located in the para position with respect to the central carbon takes a quinone structure by oxidation.
Is divided into three types below the number of NH _2, OH groups, but is preferred in that coloring Among them are good blue be in the form of basic dyes bird aminoaryl methane, red, green.
a) Diaminotriphenylmethane basic dye b) Triaminotriphenylmethane basic dye c) Rosolic acid basic dye having OH group Triaminotriphenylmethane basic dye, diaminotriphenylmethane basic dye The dye has a clear color tone and is excellent in sunlight fastness than the other dyes and is preferable.

  Since the blue triphenylmethane basic dye has a spectral characteristic having a high transmittance at 400 to 440 nm, it can have high brightness, particularly when used for forming a blue filter segment. This is preferable because it is possible.

Specific examples of triphenylmethane basic dyes include C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green) and the like.
Above all, from the point of brightness, C.I. I. Basic Blue 7 is preferably used.

  Further, in the case of a triphenyl basic dye, it can be used after being salted using an organic acid, perchloric acid or a metal salt thereof. Among them, a salt forming compound of a basic dye is preferable because of its resistance and excellent compatibility with pigments, and further, a basic dye and organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus, which are counter components that function as counter ions. It is possible to use a salt-forming compound obtained by salting an anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye. It is more preferable.

  Specifically, organic acids such as heteropoly acids, organic sulfonic acids such as aliphatic sulfonic acids and aromatic sulfonic acids, organic sulfuric acids such as aliphatic sulfuric acids and aromatic sulfuric acids, organic carboxylic acids such as aromatic carboxylic acids and fatty acids, Or it has the form of an acid dye. Alternatively, a metal salt thereof may be used. A salt-forming compound with a resin having an acid group is also preferable.

[Salt formation]
These salt forming compounds of a basic dye and an anionic counter can be synthesized by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 2003-215850.
For example, after the triarylmethane basic dye is dissolved in water, an organic sulfonic acid or (sodium organic sulfonate) solution is added, and the chlorination treatment may be performed while stirring. Here, a salt-forming compound in which the amino group (—NHC ₂ H ₅ ) portion in the triarylmethane basic dye and the sulfonic acid group (—SO ₃ H) portion of the organic sulfonic acid are combined is obtained.
Here, the organic sulfonic acid can be dissolved in an alkali solution such as sodium hydroxide before the salt-forming treatment and used as a form of sodium sulfonate (—SO ₃ Na). In the present invention, a sulfonic acid group (—SO ₃ H) and a functional group (—SO ₃ Na) which is sodium sulfonate are also synonymous.

  Examples of such triphenylmethane dyes include JP-A No. 2002-014222, JP-A No. 2003-246935, JP-A No. 2003-246935, JP-A No. 2008-304766, and JP-A No. 2010-256598. Japanese Patent Application No. 2011-200560, Japanese Unexamined Patent Application Publication No. 2011-186043, Japanese Unexamined Patent Application Publication No. 2012-173399, Japanese Unexamined Patent Application Publication No. 2012-233303, Japanese Unexamined Patent Application Publication No. 2012-098522, Japanese Patent Application No. 2012-288970, Known techniques described in Japanese Patent Application No. 2012-200469, Japanese Patent Application Laid-Open No. 2014-196262, International Publication No. 2010/123071, Pamphlet of International Publication No. 2011/162217, International Publication No. 2013/108591, etc. Use It can be.

[Cyanine dyes]
Any cyanine dye can be used without limitation as long as it is a compound having a dye moiety containing a cyanine skeleton in the molecule.
Examples of cyanine dyes include C.I. I. Basic Yellow 11, 12, 13, 14, 21, 22, 23, 24, 28, 29, 33, 35, 40, 43, 44, 45, 48, 49, 51, 52, 53, C.I. I. Basic Red 12, 13, 14, 15, 27, 35, 36, 37, 45, 48, 49, 52, 53, 66, 68, C.I. I. Basic violet 7, 15, 16, 20, 21, 39, 40, C.I. I. Basic orange 27, 42, 44, 46, C.I. I. Basic blue 62, 63, etc. may be mentioned.
In addition, cyanine dyes described in JP2014-224970A, JP2013-261614A, and the like can also be used.

[Anthraquinone dyes]
An anthraquinone dye is a dye having an anthraquinone skeleton in the molecule.
Examples of the anthraquinone dye include C.I. I. Solvent Yellow 117, 163, 1
67, 189, C.I. I. Solvent Orange 77, 86, C.I. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, C.I. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, C.I. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, C.I. I. Solvent Green 3, 28, 29, 32, 33, C.I. I. Acid Red 80, C.I. I. Acid Green 25, 27, 28, 41, C.I. I. Acid Violet 34, C.I. I. Acid Blue 25, 27, 40, 45, 78, 80, 112, C.I. I. Disperse Yellow 51, C.I. I. Disperse violet 26, 27, C.I. I. Disperse Blue 1, 14, 56, 60, C.I. I. Direct Blue 40, C.I. I. Modern Red 3, 11, C.I. I. Modern Blue 8 etc. are mentioned. Further, anthraquinone dyes described in JP-A-9-291237, WO2003 / 080734, WO2006 / 024617, JP2011-174987, JP2013-53273, and the like are used. It can be used as a known technique. The anthraquinone dye is preferably soluble in an organic solvent, and more preferably a blue, violet or red anthraquinone dye. As an anthraquinone dye, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 45, C.I. I. Acid Blue 80, C.I. I. Solvent Blue 104, and C.I. I. Solvent blue 122 is preferable from the viewpoint of brightness and contrast.

<Dispersant (B)>
The following are mentioned as a dispersing agent (B) used for this invention.
As a dispersant, it has a colorant affinity part that has the property of adsorbing to the added colorant, and a part that is compatible with the colorant carrier, and adsorbs to the added colorant to stabilize dispersion in the colorant carrier. Specifically, it may be any one that functions to convert, specifically, polycarboxylic acid ester such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, Formed by reaction of polycarboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester or their modified products, poly (lower alkyleneimine) and polyester having free carboxyl group Oil-based dispersants such as amides and their salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- ( A) Water-soluble resins such as acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide addition A compound, a phosphate ester type, etc. are used, and these can be used individually or in mixture of 2 or more types.
As a polymer dispersing agent having a basic functional group, a nitrogen atom-containing graft copolymer, a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, etc. in the side chain is contained. Examples include acrylic block copolymers and urethane polymer dispersants.

As the commercially available dispersant, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, manufactured by Big Chemi Japan, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti- Terra-U, 203, 204, or BYK-P104, P104S, 220S, LPN6919, or Lactimon, Lactimon-WS or Bykumen, etc., SOLPERSE-3000, 9000, manufactured by Nippon Lubrizol Corporation 3000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4 00,5010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of Ajisupa -PA111, PB711, PB821, PB822, PB824, and the like.
The dispersant is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the colorant.

<Adsorbent (C)>
The dispersant (B) may further contain an adsorbent (C). The adsorbent (C) itself has an adsorbing ability to the pigment and has an effect of adsorbing the pigment dispersant to the pigment. Examples of the adsorbent (C) adsorbed on the pigment surface include a dye derivative having a basic substituent, a dye derivative having an acidic substituent, and a resin having a basic group.

  As a pigment derivative having a basic substituent or an acidic substituent, the organic pigment, benzimidazolone compound, acridone compound, anthraquinone compound or triazine compound has a basic substituent, an acidic substituent, or a substituent. The compound etc. which introduce | transduced the phthalimidomethyl group which may be included are mention | raise | lifted.

<Dye derivative (Q) having a basic substituent>
A pigment derivative having a basic group is a compound in which a basic substituent is introduced into an organic pigment. Examples of the organic dye include azo series such as diketopyrrolopyrrole, azo, disazo, polyazo, anthraquinone, quinacridone, perinone, perylene, isoindoline, isoindolinone, quinophthalone, selenium, Examples include dyes such as metal complex systems. In addition, organic dyes constituting the dye derivatives include light yellow compounds such as anthraquinone, acridone, naphthalene, and triazine that are not generally called dyes. These can be used alone or in admixture of two or more.

  Examples of the basic group include substituents having an amine moiety, an imine moiety, an ammonium moiety, an amide moiety, an imide moiety, a urethane bond moiety, and the like. Especially, it is preferable that it is at least 1 basic group chosen from the group shown by following General formula (3), Formula (4), Formula (5), and Formula (6).

General formula (3):

General formula (4)

General formula (5)

General formula (6)

In general formula (3)-general formula (6),
X is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, or a direct bond;
v is an integer from 1 to 10,
R ₁ and R ₂ are each independently an alkyl group that may be substituted, an alkenyl group that may be substituted, a phenyl group that may be substituted, or R ₁ and R ₂ together. An optionally substituted heterocyclic residue containing additional nitrogen, oxygen or sulfur atoms,
R ₃ is an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group;
R ₄ , R ₅ , R ₆ , and R ₇ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. ,
Y is —NR ₈ —Z—NR ₉ —, or a direct bond;
R ₈ and R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group,
Z is an alkylene group which may be substituted, an alkenylene group which may be substituted, or a phenylene group which may be substituted;
T is a substituent represented by the general formula (7) or a substituent represented by the general formula (8),
Q is a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (7), or a general formula (8).

General formula (7):

General formula (8):

In general formula (7) and general formula (8),
X is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, or a direct bond;
v is an integer from 1 to 10,
R ₁ and R ₂ are each independently an alkyl group that may be substituted, an alkenyl group that may be substituted, a phenyl group that may be substituted, or R ₁ and R ₂ together. An optionally substituted heterocyclic residue containing additional nitrogen, oxygen or sulfur atoms,
R ₃ is an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group;
R ₄ , R ₅ , R ₆ , and R ₇ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. ,
Y is —NR ₈ —Z—NR ₉ —, or a direct bond;
R ₈ and R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group,
Z is an optionally substituted alkylene group, an optionally substituted alkenylene group, or an optionally substituted phenylene group.

Examples of the amine component used for forming the substituent represented by the general formula (3) to the general formula (6) include:
Dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N- tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, Dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, , N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutyl Aminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoe Ruamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-rupetidin, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonicopetinate, ethyl isonicopetinate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N -Aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N Butyl piperazine, N- methyl homopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, and 1-cyclopentyl piperazine and the like.

The organic dye constituting the pigment derivative having a basic group is, for example,
Diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthraquinones, anthrapyrimidines, flavantrons, anthanthrone, indanthrone, pyranthrone, violanthrone, and quinacridone dyes And dyes such as dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, and metal complex dyes.

An anthraquinone derivative having a basic group and an acridone derivative having a basic group are
It may have a substituent such as an alkyl group such as a methyl group and an ethyl group, an amino group, a nitro group, a hydroxyl group, an alkoxy group such as a methoxy group and an ethoxy group, or a halogen such as chlorine.

The triazine constituting the triazine derivative having a basic group is
Alkyl group (methyl group, ethyl group, butyl group, etc.), amino group, alkylamino group (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group) Etc.), halogen (chlorine, bromine, etc.), phenyl group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.), and phenylamino group (alkyl group) 1, 3,5-triazine optionally having a substituent such as an amino group, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, or a halogen.

The pigment derivative, anthraquinone derivative and acridone derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, after introducing a substituent represented by the formula (9) to the formula (12) into an organic dye, anthraquinone or acridone, the substituent represented by the formula (3) to the formula (6) is reacted with the above substituent. Amine component to be formed, for example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazine It can be obtained by reacting 2-ylamino] aniline or the like.

General formula (9):
-SO ₂ Cl

General formula (10):
-COCl

General formula (11):
-CH ₂ NHCOCH ₂ Cl

Formula (12):
—CH ₂ Cl

  At the time of reaction of the general formulas (9) to (12) and the amine component, a part of the general formulas (9) to (12) may be hydrolyzed so that chlorine is substituted with a hydroxyl group. In that case, the general formula (9) and the general formula (10) become a sulfonic acid group and a carboxylic acid group, respectively, but both may be free acids, and may be a 1 to 3 valent metal or the above monoamine. It may be a salt.

  Further, when the organic dye is an azo dye, the substituent represented by the formulas (3) to (6) is introduced into the diazo component or the coupling component in advance, and then the coupling reaction is performed, thereby performing the azo pigment. Derivatives can also be produced.

  The triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component that forms a substituent represented by formula (3) to formula (6) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N- It can be obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  In the coloring composition for a color filter of the present invention, the blending amount of the pigment derivative having a basic group is preferably 1 to 50% by weight, more preferably 3 to 30% by weight, most preferably based on the weight of the pigment. Preferably it is 5 to 25% by weight. If the pigment derivative having a basic group is less than 1% by weight, the effect of addition is difficult to obtain, and if it exceeds 50% by weight, heat resistance and light resistance may be deteriorated.

  Specific examples of the pigment derivative having a basic group of the present invention are shown below with compound numbers, but are not limited thereto.

・ Compound (1)
[In the compound (1), CuPc is a copper phthalocyanine residue. ]

Compound (2)
[In the compound (2), CuPc is a copper phthalocyanine residue. ]

Compound (3)

Compound (4)

Compound (5)

Compound (6)

Compound (7)

Compound (8)

<Dye derivative (R) having an acidic substituent>
The coloring composition for a color filter of the present invention further includes a dye derivative having an acidic functional group, an anthraquinone derivative having an acidic functional group, an acridone derivative having an acidic functional group, and a triazine derivative having an acidic functional group. A derivative having one or more kinds of acidic functional groups selected (hereinafter sometimes abbreviated as a derivative having an acidic functional group) can be used.

  The derivative having an acidic functional group used in the present invention will be described. The derivative having an acidic substituent used in the present invention is at least one derivative selected from the group of derivatives represented by the following general formula (13), the following general formula (14), and the following general formula (15). Can be used. Derivatives having an acidic substituent are classified into derivatives having no charge represented by the following general formula (13) and derivatives having a charge represented by the following general formulas (14) and (15).

General formula (13):
PZ ¹
(In General Formula (13), P is an organic pigment residue, a heterocyclic residue which may have a substituent, or an aromatic residue which may have a substituent, and Z ¹ is A sulfonic acid group or a carboxyl group.)

General formula (14):
(PZ ² ) [N ⁺ (R ⁵ , R ⁶ , R ⁷ , R ⁸ )]
(In the general formula (14), P is an organic dye residue, a heterocyclic residue which may have a substituent, or an aromatic residue which may have a substituent, and R ⁵ is , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Z ² is SO ₃ ^— or COO. ^- it can be).

Formula (15):
(P−Z ² ) _{x My} ⁺
(In the general formula (15), P is an organic pigment residue, heterocyclic residue which may have a substituent, or have a substituent an aromatic residues, M y ⁺ is , Metal ions such as lithium, sodium, potassium, magnesium, calcium, barium, iron, cobalt, nickel, copper, zinc, or aluminum ions, y is the valence of the ions, and x is x = y ÷ is a value obtained by the formula (Z number of ^2), Z ² is, SO ₃ ^- or COO ^- and is).

Examples of the organic dye residue represented by P in the general formulas (13) to (15) include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthraquinone, and anthra Anthraquinone dyes such as pyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone dye, dioxazine dye, perinone dye, perylene dye, thioindigo dye, isoindoline dye, isoindolinone System dyes, quinophthalone dyes, selenium dyes, metal complex dyes, and the like.

Moreover, as the heterocyclic residue and aromatic ring residue represented by P in the general formulas (13) to (15),
For example, thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone , And acridone. These heterocyclic residues and aromatic ring residues are alkyl groups (such as methyl, ethyl, and butyl groups), amino groups, alkylamino groups (such as dimethylamino groups, diethylamino groups, and dibutylamino groups), Nitro group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group,
An amino group, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, and a halogen group and the like, and a phenylamino group (an alkyl group, an amino group, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group) And may be substituted with a halogen or the like).

P in the pigment derivatives represented by the general formulas (13) to (15) does not necessarily match the chemical structure of the pigment used in the colored resin composition and the chemical structure of the organic dye residue. However, in consideration of the hue of the ink to be finally produced, when used for dispersion of green, it is used for dispersion of blue, green, or yellow pigment derivatives, and yellow pigments. For yellow pigment derivatives, red, orange or yellow pigment derivatives for use in dispersing red pigments, blue or purple pigment derivatives for use in dispersing blue pigments As described above, it is possible to produce a pigment dispersion excellent in hue by using a pigment having a hue close to that of the pigment to be dispersed or a colorless pigment.

Z ¹ in the general formula (13) may be present in the range of 0.5 to 8.0, preferably 0.7 to 3.0, with respect to P in the general formula (13).

Z ² in the general formula (14) may be present in the range of 0.5 to 8.0, preferably 0.7 to 3.0, with respect to P in the general formula (14). According to the number of Z ² at the same time ^{[N + (R 5, R} 6
, R ⁷ , R ⁸ )] may be present in the same number.

Z ² in the general formula (15) may be present in the range of 0.5 to 8.0, preferably 0.7 to 3.0, with respect to P in the general formula (15). At the same time, the number of x may be appropriately changed according to the number of Z ² and the ionic valence y of M.

  Specific examples of the dye derivative having an acidic functional group of the present invention are shown below with compound numbers, but are not limited thereto.

Compound (9)

Compound (10)

Compound (11)

Compound (12)

Compound (13)

<Binder resin (D)>
The binder resin (D) disperses, dyes, or penetrates the colorant, and examples thereof include a thermoplastic resin. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (deterioration of spectral characteristics) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  Since the binder resin has good film formability and various resistances, it is preferably used in an amount of 20 parts by mass or more with respect to 100 parts by mass of the total mass of the colorant, the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 1000 parts by mass or less.

  Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group.
Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by a method such as the following (i) (ii) (iii).

[Method (i)]
As the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group to There is a way to introduce.

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an unsaturated ethylenic monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of unsaturated ethylenic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

[Method (iii)]
As the method (iii), an unsaturated ethylenic double bond can be introduced by copolymerizing a side chain type cyclic ether-containing monomer with one or more other monomers.
The side chain type cyclic ether-containing monomer is, for example, an unsaturated compound containing at least one skeleton selected from the group consisting of a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a lactone skeleton.
Examples of the tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, (meth) acrylic acid tetrahydrofuran-3-yl ester, and the like;
Examples of the furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, and 1-furan. 2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-ene -3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6- (2-furyl) -6-methyl-1-hepten-3-one, and the like;
Examples of the tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, and tetrahydropyran 2-methacrylate. 2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, and the like;
Examples of the pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone and 4- (1,5-dioxa-6-oxo-7-octenyl) -6. -Methyl-2-pyrone and the like;
Examples of the lactone skeleton include 2-propenoic acid 2-methyl-tetrahydro-2-oxo-3-furanyl ester, 2-propenoic acid 2-methyl-7-oxo-6-oxabicyclo [3.2.1] oct-2- Yl ester, 2-propenoic acid 2-methyl-hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-7-yl ester, 2-propenoic acid 2-methyl-tetrahydro-2-oxo- 2H-pyran-3-yl ester, 2-propenoic acid (tetrahydro-5-oxo-2-furanyl) methyl ester, 2-propenoic acid hexahydro-2-oxo-2,6-methanofuro [3,2-b]- 6-yl ester, 2-propenoic acid 2-methyl-2- (tetrahydro-5-oxo-3-furanyl) ethyl ester, 2-propenoic acid 2-methyl ester Ru-decahydro-8-oxo-5,9-methano-2H-furo [3,4-g] -1-benzopyran-2-yl ester, 2-propenoic acid 2-methyl-2-[(hexahydro-2- Oxo-3,5-methano-2H-cyclopenta [b] furan-6-yl) oxy] ethyl ester, 2-propenoic acid 3-oxo-3-[(tetrahydro-2-oxo-3-furanyl) oxy] propyl And 2-propenoic acid 2-methyl-2-oxy-1-oxaspiro [4.5] dec-8-yl ester.
Among these, tetrahydrofurfuryl (meth) acrylate is preferable from the viewpoint of coloring, pigment dispersibility, and availability. These side chain type cyclic ether-containing monomers may be used alone or in combination of two or more.

<Photopolymerizable monomer (M)>
Photopolymerizable monomers that can be used in the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce transparent resins, and these may be used alone or in combination of two or more. Can do. The amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (100% by weight), and more preferably 10 to 300% by weight from the viewpoint of photocurability and developability. preferable.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator (O)>
In the blue coloring composition for a color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator or the like is added to add a solvent developing type or an alkali developing type. It can adjust with the form of a coloring resist material. The blending amount when using the photopolymerization initiator is preferably 5 to 200% by weight based on the total amount of the colorant, and 10 to 150% by weight from the viewpoint of photocurability and developability. More preferred.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Enyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) ) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds An imidazole compound; or a titanocene compound.

These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 5 to 200% by weight based on the total amount of the colorant in the blue coloring composition for a color filter (100% by weight), from the viewpoint of photocurability and developability. More preferably, it is 10 to 150% by weight.
<Sensitizer>
Furthermore, the blue coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophen Non, 4,4′-diethylaminobenzophenone and the like.

More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the colored composition (100% by weight). From the viewpoint of developability, it is more preferably 5 to 50% by weight.

<Moisture content adjustment resin (L)>
The water content adjusting resin of the present invention comprises an ethylenically unsaturated monomer (F) containing a fluorinated alkyl group and / or a poly (perfluoroalkylene ether) chain, and another ethylenically unsaturated monomer (N ) And a water content adjusting resin comprising a copolymer. In addition to the effect of the moisture content adjusting resin, there are also effects such as improving the coating property of the composition on the transparent substrate and the drying property of the colored film.

  The other ethylenically unsaturated monomer (N) preferably has an adamantyl group.

  Examples of the reaction method include a polymerization method using a polymerization initiator in an organic solvent. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid and the like can be used as necessary.

As a side chain which has the fluorinated alkyl group which the said compound has, what is represented by the following general formula (L1) can be illustrated preferably, for example.
General formula (L1)
[In the general formula (L1), R represents a hydrogen atom or a methyl group, and L represents the following formula (L-1) to
(L-10) represents any one group, and Rf represents any one group of the following formulas (Rf-1) to (Rf-7). ]

(In the formulas (L-1) and (L-3) to (L-7), n represents an integer of 1 to 8. m in the formulas (L-8) to (L-10) is 1). Represents an integer of -8, and n represents an integer of 0-8.
Rf ″ in the above formulas (L-6) and (L-7) represents any one group of the following formulas (Rf-1) to (Rf-7). )

N in the above formulas (Rf-1) to (Rf-4) is, for example, an integer of 1 to 6, and preferably an integer of 4 to 6. M in the formula (Rf-5) is, for example, an integer of 1 to 18, n is an integer of 0 to 5, and the sum of m and n is 1 to 23. Preferably, m is an integer of 1 to 5, n is an integer of 0 to 4, and the sum of m and n is 4 to 5. M in the above formula (Rf-6) is, for example, an integer of 1-6, n is an integer of 1-3, l is an integer of 1-20, p is an integer of 0-5, And the sum of the product of m, p and n and l is 2 to 71. Preferably, m is an integer of 1 to 3, n is an integer of 1 to 3, l is an integer of 1 to 6, p is an integer of 0 to 2, and m, p and n The sum of the products of l and l is 2-23.

Among the side chains (b) having the fluorinated alkyl group, the side chain having a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded exhibits excellent smoothness. The number of carbon atoms to which fluorine atoms are directly bonded is preferably 4.
Side chains having -6 fluorinated alkyl groups are more preferred.

  Examples of the poly (perfluoroalkylene ether) chain include those having a structure in which divalent fluorocarbon groups having 1 to 3 carbon atoms and oxygen atoms are alternately connected. The divalent fluorocarbon group having 1 to 3 carbon atoms may be one kind or a mixture of a plurality of kinds, and specifically, those represented by the following structural formula (A1) Can be mentioned.

(In the structural formula (A1), X is the following structural formulas (A1-1) to (A1-5), and all X in the structural formula (A1) may have the same structure, In addition, a plurality of structures may be present randomly or in a block shape, and n is an integer of 1 or more representing a repeating unit.

Among these, the perfluoromethylene structure represented by the structural formula (A1-1) and the structure from the viewpoint that a coating film excellent in antifouling property can be obtained by particularly improving the wipeability of the coating film surface. Those coexisting with the perfluoroethylene structure represented by the formula (A1-2) are particularly preferred. Moreover, the value of n in the said structural formula (A1) has the preferable range of 3-100, The range of 6-70 is more preferable, The range of 12-50 is more preferable.

In addition, it is preferable that the water content can be more appropriately controlled when the other ethylenically unsaturated monomer (N) has an adamantyl group.
The ethylenically unsaturated monomer having an adamantyl group is a compound having an adamantane structure and a (meth) acryloyl group. The (meth) acryloyl group may be bonded to any carbon atom in the adamantane structure. Further, part or all of the hydrogen atoms bonded to the carbon atoms constituting the adamantane structure may be substituted with fluorine atoms, alkyl groups, or the like.

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

  Specific examples include Surflon S-242, S-243, S-420, S-611, S-651, and S-386 manufactured by AGC Seimi Chemical Co., Ltd., MegaFuck F-253 and F-477 manufactured by DIC Corporation. F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS- 21, FC-4430, FC-4432, manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, EF-PP32C1, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd., FONTENT 602A manufactured by Neos Co., Ltd., and the like.

[Leveling agent]
Although the water content adjusting resin of the present invention also functions as a leveling agent, other leveling agents that can be used in combination are silicone surfactants or other types, but nonionic surfactants, cationic surfactants (surfactants, surfactants, Various surfactants, such as an anionic surfactant, are mentioned.

Examples of silicone surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains and terminals.
Specific examples include BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-330, BYK-331, BYK-manufactured by BYK-Chemie. 333, BYK-342, BYK-345 / 346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510, BYK-3570, Toray Dow Corning, FZ-7001, FZ-7002, FZ-2110, FZ-2122, FZ-2123], FZ-2191, FZ-5609, Shin-Etsu Chemical Co., Ltd. X-22-4952, X-22 -4272, X-22-6266, KF-351A, K354L, KF- 55A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, etc. KF-6004 and the like.

  Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristol ether, polyoxyethylene octyldodecyl Ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl Ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sol Tan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monolaurate, sorbitan esquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, Polyoxyethylene orbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbite tetraoleate, glycerol monostearate, glycerol monooleate Ate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol di Teareto, polyethylene glycol monomethyl oleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl amines, alkyl alkanol amides, alkyl betaine such as alkyl imidazoline and alkyl dimethyl amino acetic acid betaine.

  Specific examples include Emulgen 103, Emulgen 104P, Emulgen 106, Emulgen 108, Emulgen 109P, Emulgen 120, Emulgen 123P, Emulgen 130K, Emulgen 147, Emulgen 150, Emulgen 210P, Emulgen 220P, Emulgen 306P, Emulgen 320P, manufactured by Kao Corporation. Emulgen 350, Emulgen 404, Emulgen 408, Emulgen 409PV, Emulgen 420, Emulgen 430, Emulgen 705, Emulgen 707, Emulgen 709, Emulgen 1108, Emulgen 1118S-70, Emulgen 1135S-70, Emulgen 1150S-60, Emulgen 2020G-HA Emulgen 2025G, Emulgen LS-106, Emulgen LS-110, Et Rugen LS-114, Emulgen MS-110, Emulgen A-60, Emulgen A-90, Emulgen B-66, Emulgen PP-290, Latemul PD-420, Latemuru PD-430, Latemuru PD-430S, Latemuru PD450, Rheodor SP -L10, Rheodor SP-P10, Rheodor SP-S10V, Rheodor SP-S20, Rheidol SP-S30V, Rheodor SP-O10V, Rheodor SP-O30V, Rheodor Super SP-L1, Rheodor AS-10V, Rheodor AO-10V, Rheodor AO-15V, Rheodor TW-L120, Rheodor TW-L106, Rheodor TW-P120, Rheodor TW-S120V, Rheodor TW-L106V, Rheodor TW-S320V, Rheodor TW-O120V, Rheodor TW-O106V, Rheidol TW-IS399C, Rheodor Super TW-L120, Rheodor 430V, Rheodor 440V, Rheodor 460V, Rheodor MS-50, Rheodor MS-60, Rheodor MO-60, Rheodor MS-165V, Emanon 1112, Emanon 3199V, Emanon 3299V, Emanon 3299RV, Emanon 4110, Emanon CH-25, Emanon CH-40, Emanon CH-60 (K), Amete 102, Amete 105, Amete 105A, Amete 302, Amete 320, Amine PK -02S, aminone L-02, homogenol L-95, ADEKA Corporation Adeka Pluronic L-23, 31, 44, 61, 62, 6 4, 71, 72, 101, 121, Adeka Pluronic TR-701, 702, 704, 913R and the like.

Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, and their ethylene oxide adducts.
As specific examples, Acetamine 24, 26, Cotamin 24P, 86P Conch manufactured by Kao Corporation, KP341 manufactured by Shin-Etsu Chemical Co., Ltd., (meth) acrylic acid (co) polymer polyflow No. manufactured by Kyoeisha Chemical Co., Ltd. 75, no. 90, no. 95 etc. are mentioned.

  Anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine , Lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

  Specific examples include Neos Inc.'s Footgent 100, 150, Adeka Corporation Adeka Hope YES-25, Adeka Coal TS-230E, PS-440E, EC-8600, and the like.

The addition amount of the water content adjusting resin in the photosensitive coloring composition of the present invention is preferably 0.001 to 2.0% by mass, more preferably 0.005 to the total solid content of the composition of the present invention. 1.0% by mass. By being in this range, the subject of the present invention can be achieved more preferably.
The photosensitive coloring composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.
<Solvent (SL)>
In the coloring composition for a color filter of the present invention, a pigment is sufficiently dispersed in a pigment carrier and applied on a transparent substrate such as glass so that a dry film thickness is 0.2 to 5 μm to form a filter segment. A solvent can be included to facilitate the process.

As a solvent, for example,
1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3- Propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy- 3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N- Dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chloro Ruene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene Glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol Monomethyl ether, ethylene glycol Monoethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, di Propylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Methyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene Glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate , Acetic acid Propyl, or dibasic acid esters and the like, used alone or in combination.
The organic solvent mainly used in the present invention preferably has a conductivity at 25 ° C. of 1 nS / cm or less.

  When the colored composition is cured by ultraviolet irradiation, an active energy ray polymerizable initiator or the like is added to the colored composition for color filter.

<Coloring composition for color filter>

  The colored composition for color filter of the present invention can be classified into a colored composition for color filter (paste) and a colored composition for color filter (resist).

  The coloring composition (paste) for the color filter of the present invention is mixed with various solvents, resins, additives, etc., if necessary, and dispersed with a horizontal sand mill, vertical sand mill, annular bead mill, attritor, etc. A colored composition (paste) for a color filter obtained by dispersing the composition in a varnish can be prepared.

  It can also be produced by mixing several types of pigments separately dispersed on a pigment carrier.

  The coloring composition for a color filter of the present invention is a coarse particle of 5 μm or more, preferably a coarse particle of 1 μm or more, more preferably a coarse particle of 0.5 μm or more by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove the mixed dust.

The color filter coloring composition (resist) can be prepared as a solvent developing type or alkali developing type color filter coloring resist (resist). A colored composition (resist) for a solvent development type or alkali development type color filter generally comprises a thermoplastic resin, a thermosetting resin or a photosensitive resin, an ethylenically unsaturated monomer, a photopolymerization initiator, A pigment is dispersed in a composition containing an organic solvent.

  The photopolymerization initiator may be added at the stage of preparing the color filter coloring composition (resist), or may be added later to the prepared color filter coloring composition (resist).

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention is provided with a filter segment or a black matrix formed from the coloring composition for a color filter of the present invention on a transparent substrate, and a general color filter includes at least one red filter segment, At least one green filter segment and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” means “parts by weight”.

A method for measuring parameters described in the examples will be described.
<Number average molecular weight>
The molecular weight of the resin of the present invention is measured in polystyrene using HLC-8220GPC (manufactured by Tosoh Corporation) as a device, TSK-GEL SUPER HZM-N connected in series as a column, and THF as a solvent. The number average molecular weight of
<Moisture content measurement method>
The water content (mg) was measured using a Karl Fischer titrator (volumetric titration type moisture measuring device KF-06 manufactured by Mitsubishi Chemical Corporation), and the moisture content (%) was calculated by the following formula.
Moisture content (%) = [water content (mg) / measured sample amount (mg)] × 100
<Conductivity measurement method>
Measurement was performed using Scientific Conductivity Meter Models 645 and 627.
<Sensitivity evaluation>
The colored compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 6 were spin-coated on a glass substrate using a spin coater so that the dry film thickness was 1.2 μm. Pre-baked for 2 seconds. Next, after cooling the substrate to room temperature, ultraviolet rays were exposed through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the substrate is spray-developed using an aqueous sodium carbonate solution at 23 ° C., washed with ion-exchanged water and air-dried, post-baked at 230 ° C. for 30 minutes in a clean oven, and striped on the substrate. Colored pixels were formed.
The sensitivity of the colored composition was evaluated by the minimum irradiation exposure amount at which the pattern of the formed colored pixel was finished according to the image size of the photomask. The rank of evaluation is as follows.
○: less than 100mJ / cm ² △: 100 or more, 150mJ / cm ² less than ×: 150mJ / cm ² or more

<Development speed evaluation>
The colored compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 6 were spin-coated on a glass substrate using a spin coater so that the dry film thickness was 1.0 μm. Dried for minutes.
2 ml of a 2% by weight aqueous potassium hydroxide solution was dropped onto the coating film, and the time until the coating thickness was dissolved was measured to evaluate the development rate of the colored composition. The rank of evaluation is as follows.
○: Less than 10 seconds Δ: More than 10 seconds, less than 15 seconds ×: More than 15 seconds

  Prior to the examples, a method for producing the moisture adjusting resin (L), the dispersant (B), the binder resin (D), and the fine pigment (A) will be described.

<Manufacture of water content adjustment resin (L) liquid>
(Manufacture of water content adjustment resin (L-1) liquid)
A reaction vessel purged with nitrogen was charged with 117 parts by weight of methyl ethyl ketone, 50 parts by weight of 2-propanol, 4.69 parts by weight of 2,2′-bipyridyl, and 1.49 parts by weight of cuprous chloride, and stirred at 20 ° C. for 30 minutes. . Thereafter, 78.1 parts by mass of 2-hydroxyethyl methacrylate and 2.93 parts by mass of ethyl 2-bromoisobutyrate were added and reacted at 20 ° C. for 16 hours in a nitrogen stream. Next, 45.8 parts by mass of methyl ethyl ketone, 19.5 parts by mass of 2-propanol, and 40 parts by mass of 2- (nonafluorobutyl) ethyl methacrylate represented by the following formula were added, and the mixture was heated to 60 ° C. and reacted for 8 hours. It was. Furthermore, 91.6 parts by mass of methyl ethyl ketone, 39 parts by mass of 2-propanol, and 80 parts by mass of 2- (nonafluorobutyl) ethyl methacrylate were added and reacted for 26 hours. This reaction mixture was dissolved in methanol and purified by reprecipitation with water / methanol to obtain a block polymer. 60 parts by mass of this block polymer was dissolved in 80 parts by mass of methyl ethyl ketone, 10 parts by mass of 2-ethylhexanoic acid tin solution (0.2% by mass of methyl ethyl ketone), and 0.1% by mass of a polymerization inhibitor (p-methoxyphenol). The temperature was raised to 60 ° C. While introducing dry air into the liquid, 44.1 parts by mass of a 50% by mass methylethylketone solution of 2-acryloyloxyethyl isocyanate was added dropwise, reacted for 1 hour, further reacted at 80 ° C. for 3 hours, and a fluorine content of 20% by mass. A solution of a fluorine-containing radical polymerizable copolymer which is a% block copolymer was obtained. Furthermore, propylene glycol monomethyl ether acetate was added to the obtained polymer solution to obtain a solution containing 20% by mass of the fluorine radical polymerizable copolymer.

(Manufacture of water content adjustment resin (L-2 to 13) liquid)
Using methyl isobutyl ketone as the solvent and t-butyl poroxy-2-ethyl hexalate as the polymerization initiator, the side chain or poly (perfluoroalkylene ether) chain having a fluorinated alkyl group described in Table 1 and its terminal A polymerization reaction was performed using a compound having a polymerizable unsaturated group and a polymerizable unsaturated monomer having an adamantyl group having a reactive functional group to obtain a fluorine-containing resin solution.
After cooling to room temperature, about 2 g of the fluororesin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether so that the nonvolatile content in the fluororesin solution was 20% by weight. Acetate was added to obtain L-2 to 13 shown in Table 1.

Abbreviations in Table 1 are shown below.
“—PFPE—” in the formula represents a poly (perfluoroalkylene ether) chain.

<Production of Dispersant (B) Liquid>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 45.0 parts of methyl methacrylate, 15.0 parts of methacrylic acid, and 40.0 parts of ethyl acrylate, and replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C. and dissolved in 1.0 part of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile in 45.3 parts of cyclohexanone. The solution was added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. At this time, the number average molecular weight was 9,500. Next, 8.0 parts of Ricacid BT-100 (manufactured by Shin Nippon Chemical Co., Ltd.), 69.2 parts of cyclohexanone, and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added. And reacted at 120 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. If necessary, part of the solvent is removed by distillation under reduced pressure, then propylene glycol monomethyl ether acetate is added to adjust the non-volatile content to 50%, and a comb-like dispersant (B) liquid having a number average molecular weight of 25000 is obtained. It was.

<Example of production of binder resin (D) liquid>
(Preparation of binder resin (D-1) solution)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether so that the nonvolatile content was 20% in the previously synthesized resin solution. Acetate was added to prepare a binder resin (D-1) solution. The weight average molecular weight (Mw) was 26000.

(Preparation of binder resin (D-2) solution)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20%. Thus, a binder resin (D-2) was prepared. The weight average molecular weight (Mw) was 18000.

(Preparation of binder resin (D-3) solution)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a binder resin (D-3) solution. The weight average molecular weight (Mw) was 19000.

(Preparation of binder resin (D-4) solution)
A separable flask with a cooling tube was prepared as a reaction tank, and 40 parts of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, 40 parts of methacrylic acid, Prepared by thoroughly stirring and mixing 1 20 parts of methyl methacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation), and 40 parts of propylene glycol monomethyl ether acetate, As a chain transfer agent dripping tank, 8 parts of n-dodecanethiol and 3 2 parts of propylene glycol monomethyl ether acetate were well stirred and mixed.
The reaction vessel was charged with 3 95 parts of propylene glycol monomethyl ether acetate, purged with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropwise addition was performed over 1 35 minutes while maintaining the temperature at 90 ° C. After 60 minutes from the end of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 5/95 (volume ratio) mixed gas was started. Then, 70 parts of glycidyl methacrylate, 2,2′-methylenebis (4-methyl-6-t-butylphenol) 0. 4 parts, triethylamine 0. 8 parts were charged and allowed to react at 1 10 ° C. for 12 hours. Thereafter, 150 parts of propylene glycol monomethyl ether acetate was added and cooled to room temperature. About 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. Propylene glycol monomethyl ether acetate was added so that the content was 20% by weight to obtain a binder resin (D-4) solution. The weight average molecular weight of the resin was 18000, and the acid value per solid content was 2 mgKOH / g.

<Manufacture of finer pigments>
(Fine refined pigment (A-1): PG58)
Green pigment C.I. I. 500 parts of Pigment Green 58 (“First Gain Green A110” manufactured by DIC Corporation), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green refined pigment (A-1) was obtained.

(Fine refined pigment (A-2): PR177)
Anthraquinone red pigment C.I. I. 100 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 5 parts of a pigment derivative (Compound 7), 800 parts of crushed salt and 180 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho), 70 The mixture was kneaded at 5 ° C. for 5 hours. The mixture was poured into 4000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained red refined pigment (A-2).

(Fine refined pigment (A-3): PR254)
Diketopyrrolopyrrole red pigment C.I. I. 100 parts of Pigment Red254 ("Irgafore Red B-CF" manufactured by BASF), 10 parts of a pigment derivative (Compound 8), 1000 parts of crushed salt, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) made of stainless steel. And kneading at 70 ° C. for 8 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained red refined pigment (A-3).

(Fine refined pigment (A-4): PB15: 6)
Copper phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“Lionol Blue ES” manufactured by Toyocolor Co., Ltd.) 100 parts, pigment derivative (Compound 2) 5 parts, crushed salt 1000 parts, and diethylene glycol 100 parts 1 gallon kneader (manufactured by Inoue Seisakusho) And kneaded at 50 ° C. for 12 hours. The mixture was added to 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts refined pigment (A-4).

(Fine refined pigment (A-5): PY138)
Quinophthalone yellow pigment C.I. I. 100 parts of Pigment Yellow 138 (“Pariotol Yellow K0961HD” manufactured by BASF), 3 parts of a pigment derivative (Compound 3), 800 parts of crushed salt and 180 parts of diethylene glycol were charged in a stainless 1 gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 4 ° C. for 4 hours. The mixture was added to 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts refined pigment (A-5).

(Fine refined pigment (A-6): PY150)
Metal complex yellow pigment C.I. I. 500 parts of Pigment Yellow 150 (LANXESS "E4GN"), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C for 6 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a yellow refined pigment (A-6) was obtained.

<Dye production method>
(Resin 1 having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2′-azobis (2,4-dimethylvaleronitrile) ) And 25.1 parts of methyl ethyl ketone were made uniform, charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 having a cationic group in the side chain having 47% by weight of an ammonium group as the resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

(Dye 01 (AR52-JK))
In the following procedure, C.I. I. Dye 01 (AR52-JK), which is a salt-forming compound composed of Acid Red 52 and Resin 1 having a cationic group in the side chain, was produced.
The resin 1 having a cationic group in a side chain of 30 parts in terms of solid content was added to 2000 parts of water, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. Dye 1 (AR52-JK), which is a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in the side chain, was obtained. At this time, C.I. in Dye 1 (AR52-JK). I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

(Dye 02 (AR289-JK))
In the following procedure, C.I. I. Dye 02 (AR289-JK), which is a salt-forming compound composed of Acid Red 289 and Resin 1 having a cationic group in the side chain, was produced.
The resin 1 having a cationic group in a side chain of 30 parts in terms of solid content was added to 2000 parts of water, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 was dissolved was prepared and added dropwise little by little to the resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. Dye 2 (AR289-JK), which is a salt-forming compound of Acid Red 289 and Resin 1 having a cationic group in the side chain, was obtained. At this time, C.I. in Dye 2 (AR289-JK). I. The content of the effective pigment component derived from Acid Red 289 was 27% by weight.

<Preparation of Color Filter Coloring Composition (Paste)>
[Production Example 1]
<Coloring Composition for Color Filter (Paste) (X-1)>
After uniformly stirring and mixing a mixture having the following composition, it was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm It filtered with the filter and the coloring composition (paste) (X-1) for color filters was produced.
Pigment A (A-1) 10.0 parts Dispersant B liquid 3.0 parts Binder resin liquid D (D-1) liquid 16.0 parts Propylene glycol monomethyl ether acetate 70.5 parts Pure water 0 .5 parts

[Production Examples 2 to 17, Comparative Production Examples 1 and 2]
<Coloring Composition for Color Filter (Paste) (X-2 to 19)>
According to the manufacture example 1 with the material shown in Table 2, and its weight part, the coloring composition (paste) (X-2-19) for color filters was created.
In Comparative Production Example 2 (paste: X-19), a molecular sieve was added and the sample left for 24 hours was filtered to prepare a sample.

<Adsorbent Q-1>
Compound 7

<Adsorbent Q-2>
Compound 3

<Adsorbent Q-3>
Compound 5

(Solvent: SL)
SL-1: Propylene glycol monomethyl ether acetate SL-2: Isoamyl acetate SL-3: Ethyl 3-ethoxypropionate

<Coloring composition for color filter (resist adjustment)>
[Example 51]
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a colored composition for color filter (Y-1).
-Color filter coloring composition (paste) (X-1) 50.0 parts-Binder resin (D-1) 15.0 parts-Photopolymerizable monomer (M-1) 3.0 parts (Toagosei "Aronix M-402" dipentaerythritol hexaacrylate)
Photopolymerization initiator (O) 1.8 parts ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime ) ("Irgacure OXE02" manufactured by BASF)
・ Sensitizer 0.2 part (“EAB-F” 4,4′-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Co., Ltd.)
Propylene glycol monomethyl ether acetate 29.0 parts Moisture content adjusting agent (L-1 in Table 1) liquid: 1.0 part of 20% liquid

[Examples 52 to 85, Comparative Examples 3 and 4]
<Coloring composition for color filter (resist) (Y-2 to 37)>
The color filter coloring composition (paste) (Y-2 to 37), the acrylic resin solution, and the solvent were blended as shown in Table 3 in the same manner as in Example 51, and the corresponding color filter coloring composition (resist ) (Y-2 to 37) were obtained.
For Comparative Example 4 (resist: Y-37), a molecular sieve was added and the sample left for 24 hours was filtered to prepare a sample.

Photopolymerizable compound (M)
Photopolymerizable compound (M-1): dipentaerythritol hexaacrylate
("Aronix M-402" manufactured by Toagosei Co., Ltd.)
Photopolymerizable compound (M-2): General formula (16) m = 1, a = 3, b = 3
Caprolactone-modified dipentaerythritol hexaacrylate
(“KAYARAD DPCA-30” manufactured by Nippon Kayaku Co., Ltd.)

General formula (16)

Photopolymerizable compound (M-3): Succinic anhydride adduct of a mixture of pentaerythritol triacrylate and dipentaerythritol triacrylate (“Aronix M-520” manufactured by Toagosei Co., Ltd., acid value: 30 mgKOH / g)
(Solvent: SL)
SL-1: Propylene glycol monomethyl ether acetate SL-2: Isoamyl acetate SL-3: Ethyl 3-ethoxypropionate

<Evaluation of Color Filter Coloring Composition (Resist)>
About the obtained coloring composition (resist) (Y-1 to 37) for color filters, the test regarding a viscosity, storage stability, a sensitivity, and a development speed was done with the following method. The results of the evaluation test are shown in Table 4 below.

<Sensitivity evaluation>
The colored composition was spin-coated on a glass substrate using a spin coater so that the dry film thickness was 1.2 μm, and prebaked at 120 ° C. for 120 seconds. Next, after cooling the substrate to room temperature, ultraviolet rays were exposed through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the substrate is spray-developed using an aqueous sodium carbonate solution at 23 ° C., washed with ion-exchanged water and air-dried, post-baked at 230 ° C. for 30 minutes in a clean oven, and striped on the substrate. Colored pixels were formed.
The sensitivity of the colored composition was evaluated by the minimum irradiation exposure amount at which the pattern of the formed colored pixel was finished according to the image size of the photomask. The rank of evaluation is as follows.
○: less than 100mJ / cm ² △: 100 or more, 150mJ / cm ² less than ×: 150mJ / cm ² or more

<Development speed evaluation>
The coloring composition was spin-coated on a glass substrate using a spin coater so that the dry film thickness was 1.0 μm, and dried at 70 ° C. for 20 minutes.
2 ml of a 2% by weight aqueous potassium hydroxide solution was dropped onto the coating film, and the time until the coating thickness was dissolved was measured to evaluate the development rate of the colored composition. The rank of evaluation is as follows.
○: Less than 10 seconds Δ: More than 10 seconds, less than 15 seconds ×: More than 15 seconds

<Measurement of viscosity characteristics>
The viscosity of the green coloring composition for color filter (resist) was measured at a rotation speed of 20 rpm using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.).
The rank of evaluation is as follows.
◎: Viscosity 2.8 or more and less than 3.0: Very good level ○: Viscosity 3.2 or more and less than 3.4: Good level Δ: Viscosity 3.4 or more and less than 3.5: Inferior to ○ Practical level ×: Viscosity 3.5 or more: Unsuitable level for practical use XX: Unevaluable

(Storage stability)
About the coloring composition (resist) for color filters obtained by the Example and the comparative example, the storage stability was evaluated by the following method.
E type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.) It was measured under the condition of a rotational speed of 50 rpm at 25 ° C. From the values of the initial viscosity and the viscosity with time, the change rate with time was calculated by the following formula, and the storage stability was evaluated in three stages.
[Change in viscosity with time] = | ([initial viscosity] − [viscosity with time]) / [initial viscosity] | × 100
○: Change rate of less than 5% △: Change rate of 5% to 10% ×: Change rate of 10% or more

Claims (6)

Pigment (A), dispersant (B), moisture content adjusting resin (L), binder resin (D) (except for the case of the pigment, dispersant, or moisture content adjusting resin), and solvent (SL) A coloring composition for a color filter comprising:
The water content adjusting resin (L) includes an ethylenically unsaturated monomer (F) containing a fluorinated alkyl group and / or a poly (perfluoroalkylene ether) chain, and another ethylenically unsaturated monomer ( N) and a copolymer of
And the water content of the coloring composition is 0.3 to 2.0% by weight based on the total weight of the coloring composition,
Furthermore, the electrical conductivity at 25 degrees C of this coloring composition is 100-1000 nS / cm, The coloring composition for color filters characterized by the above-mentioned.   The colored composition for a color filter according to claim 1, wherein the other ethylenically unsaturated monomer (N) includes a monomer having an adamantyl group.   The dispersant (B) further includes an adsorbent (C) having a pigment adsorbing group, and the adsorbent (C) having the pigment adsorbing group is a pigment derivative having a basic group, an anthraquinone having a basic substituent. A dye derivative (Q) having at least one basic substituent selected from the group consisting of a derivative, a triazine derivative having a basic substituent, and an acridone derivative having a basic substituent, and / or a basic group The colored composition for a color filter according to claim 2, comprising a vinyl resin (S) having a pigment or a pigment derivative having an acidic group.   The coloring composition for a color filter according to any one of claims 1 to 3, further comprising a dye.   Furthermore, the coloring composition for color filters in any one of Claims 1-4 containing a photopolymerizable monomer and a photoinitiator.   A color filter comprising a filter segment formed from the colored composition for color filter according to claim 1 on a substrate.