TWI672341B - Coloring composition, method for producing colored composition, color filter, ink composition for inkjet, and ink composition for printing - Google Patents

Abstract

The present invention provides a coloring composition excellent in dispersion stability, a method for producing a colored composition, a color filter, an ink composition for inkjet, and a composition for printing ink. The colored composition of the present invention contains: a pigment body having a metal oxide on at least a part of the surface of the organic pigment; and a resin having at least one group selected from the group consisting of an acidic group and a basic group.

Description

Coloring composition, method for producing colored composition, color filter, ink composition for inkjet, and ink composition for printing

The present invention relates to a colored composition. Further, it relates to a method for producing a colored composition, a color filter, a color filter for inkjet, an ink composition for inkjet, and a composition for printing ink.

Pigment-containing coloring compositions are used in a variety of applications. For example, it is used for the production of a cured film of a color filter or the like, various prints, and the like.

On the other hand, Patent Document 1 discloses that a film is applied to a surface of a pigment by bringing a hydrophilic pigment into contact with a metal alkoxide in an organic solvent compatible with water, and a pigment for applying the film is applied. Drying and/or firing is carried out to produce a coated pigment. [Prior Technical Literature] [Patent Literature]

[Patent Document 1]: JP-A-63-113080

In recent years, color filters are required to have high color characteristics in terms of chromaticity, contrast, and the like. In response to such a demand, it is necessary to disperse the pigment contained in the colored composition in a stable state (preferably, dispersion stability).

However, since the surface state of the pigment is different, the resin used for pigment dispersion differs from the dispersion conditions and the like. For example, as the dispersion time elapses, the pigment particles are loosened or refined to a state close to the primary particles, whereby the dispersibility is improved. However, if the dispersion is further continued, the fine particles are aggregated and the dispersibility is gradually lowered. (Generally thickening) trend. Thus, too short or too long a dispersion time will result in a decrease in dispersibility. Therefore, for each pigment, there is a tendency to take time when a resin or the like is selected or the dispersion time is adjusted.

Further, in order to adjust the spectroscopic or the like, the colored composition may contain a plurality of pigments. A method for producing a colored composition containing a plurality of kinds of pigments is a method of preparing a pigment dispersion liquid by mixing a pigment, a resin, a solvent, or the like with each pigment, and mixing the obtained pigment dispersion liquid; And a method of simultaneously mixing (dispersing) a plurality of kinds of pigments, resins, and solvents. However, in the former method, depending on the combination of the pigment dispersion liquids, aggregation may occur when the pigment dispersion liquid is mixed, or the viscosity may increase, and the dispersion stability may be insufficient. Further, in the latter method, depending on the optimum range of the dispersion conditions of the surface state of the pigment, there are problems in that the dispersion stability is insufficient due to variations in the dispersion balance of the respective pigments, and the production range is narrow.

On the other hand, in Patent Document 1, there is no research or suggestion regarding the dispersion stability of the pigment.

Accordingly, an object of the present invention is to provide a coloring composition excellent in dispersion stability, a method for producing a colored composition, a color filter, an ink composition for inkjet, and a composition for printing ink.

According to the study by the inventors of the present invention, it has been found that a pigment body containing a pigment body having at least a part of a surface of an organic pigment having a metal oxide and a resin having at least one group selected from an acidic group and a basic group is used. The dispersion stability is good and the present invention has been completed. The present invention provides the following. <1> A colored composition comprising: a pigment body having a metal oxide on at least a part of the surface of the organic pigment; and a resin having at least one selected from the group consisting of an acidic group and a basic group. <2> The colored composition according to <1>, wherein the metal oxide is an oxide of one or more elements selected from the group consisting of Si, Al, Zr, and In. <3> The colored composition according to <1>, wherein the metal oxide is an oxide of Si. The colored composition according to any one of <1> to <3> wherein the resin contains a graft copolymer. The colored composition according to any one of <1> to <4>, wherein the pigment body has 1 to 25 parts by mass of the metal oxide based on 100 parts by mass of the organic pigment. <6> The colored composition according to any one of <1> to <5>, which contains two or more kinds of pigment bodies, and two or more types of pigment bodies contain mutually different organic pigments. The colored composition according to any one of <1> to <6>, which contains two or more kinds of pigment bodies, and the metal oxide of each pigment body contains the same metal atom. The colored composition according to any one of <1> to <7> wherein the resin contains two or more kinds of acidic resins or two or more kinds of basic resins. The colored composition according to any one of <1> to <8> wherein the resin contains two or more kinds of resins having a difference in solubility parameter of 6 (J/cm ³ ) ^0.5 or less. The colored composition according to any one of <1> to <9>, further comprising a polymerizable compound. <11> The colored composition according to <10>, further comprising a photopolymerization initiator. The colored composition according to any one of <1> to <11>, further comprising a solvent. <13> A method for producing a colored composition, comprising the step of dispersing two or more kinds of pigment bodies in the presence of a resin, the resin having at least one selected from the group consisting of an acidic group and a basic group, the pigment body At least a portion of the surface of the organic pigment is coated with a metal oxide. <14> A color filter according to any one of <1> to <12>. <15> A coloring composition according to any one of <1> to <12>. <16> A coloring composition according to any one of <1> to <12>, wherein the printing ink composition is used.

According to the present invention, it is possible to provide a coloring composition excellent in dispersion stability, a method for producing a colored composition, a color filter, an ink composition for inkjet, and a composition for printing ink.

Hereinafter, the contents of the present invention will be described in detail. In the label of the group (atomic group) in the present specification, a substituted or unsubstituted labeling system, a group having no substituent, and a group having a substituent are also included. For example, "alkyl" means an alkyl group having not only an alkyl group having no substituent (unsubstituted alkyl group) but also having a substituent (substituted alkyl group). In the present specification, "exposure" is not limited to light exposure, and drawing using a particle beam such as an electron beam or an ion beam is also included in the exposure. Further, examples of the light used for exposure include an open line spectrum of a mercury lamp, an extraordinary ultraviolet light represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, or the like, or radiation. In the present specification, the numerical range represented by "to" means a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the present specification, the total solid content means the total mass of the components after removing the solvent from the overall composition of the coloring composition. In the present specification, "(meth) acrylate" means either or both of acrylate and methyl acrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, "(A) The "allyl" group means either or both of an allyl group and a methallyl group, and "(meth)acryloyl group" means either or both of an acryloyl group and a methacryl group. In the present specification, a polymerizable compound means a compound having a polymerizable functional group. The polymerizable functional group refers to a group that participates in the polymerization reaction. In this specification, the term "step" is not only a term that includes only independent steps, but also a term that refers to an operation that can achieve the desired effect of the step even if it cannot be clearly distinguished from other steps. , is also included in this term. In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene equivalent values obtained by measurement by gel permeation chromatography (GPC). The organic pigment used in the present invention means an insoluble pigment compound which is not easily dissolved in a solvent. Typically, it means a pigment compound which exists as a state in which particles are dispersed in a composition. In addition, the solvent is exemplified by any solvent, and examples thereof include a solvent exemplified in a solvent column to be described later. The organic pigment used in the present invention is preferably, for example, a dissolved amount of 100 g of propylene glycol monomethyl ether acetate at 25 ° C and a dissolved amount of 100 g with respect to water at 25 ° C of 0.1 g or less.

<Coloring Composition> The coloring composition of the present invention contains a pigment body having a metal oxide on at least a part of the surface of the organic pigment, and a resin having at least one selected from the group consisting of an acidic group and a basic group. The coloring composition of the present invention has the above-described configuration, and can be a coloring composition having excellent dispersion stability. Further, in the organic pigment, the deterioration of the organic pigment (oxidation by singlet oxygen or triplet oxygen) tends to progress by ultraviolet irradiation, but in the pigment body, at least a part of the surface of the organic pigment has metal oxidation. Therefore, it is excellent in light resistance. Further, in the pigment body, since at least a part of the surface of the organic pigment has a metal oxide, the surface state of the organic pigment can be made substantially the same regardless of the type of the organic pigment. In this way, the coloring composition excellent in dispersion stability can be obtained by changing the resin or the like used in the dispersion of the pigment body or the dispersion condition of the pigment body without depending on the type of the organic pigment. Further, even if a plurality of pigment bodies are simultaneously dispersed, the difference in dispersion progress of each pigment body is less likely to occur, and a coloring composition excellent in dispersion stability can be obtained. Hereinafter, the present invention will be described in detail.

<<Pellet body>> The coloring composition of the present invention contains a pigment body having a metal oxide on at least a part of the surface of the organic pigment. Examples of the organic pigment having a pigment body include a plurality of conventionally known organic pigments. For example, the following organic pigments are mentioned. However, the invention is not limited to these organic pigments. Color Index (CI) 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, 148, 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, 199, 213, 214, etc., CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38 , 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc., CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10 , 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53 : 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 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, 206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279, CI Pigment Green 7, 10, 36, 37, 58, 59, CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60 , 64, 66, 79, 80, CI Pigment Black 1. Further, as the organic pigment, the azo pigment described in paragraphs 0027 to 0118 of JP-A-2013-040240 can be used. Further, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A-2012-247591 and paragraph 0047 of JP-A-2011-157478.

In the present invention, the pigment body has a metal oxide. Further, in the present invention, the metal oxide is made to contain a semimetal atom oxide in addition to the metal atom oxide. The semimetal atom system represents an atom having an intermediate property between a metal and a nonmetal, and examples thereof include B, Si, Ge, As, and Sb. In the present invention, the metal oxide is preferably an oxide containing one or more elements selected from the group consisting of Si, Al, Zr, and In, and contains an oxidation of one or more elements selected from the group consisting of Si, Al, and Zr. Preferably, the oxide containing Si is more preferable, and the oxide of Si is particularly preferable. According to this scheme, the dispersion stability can be further improved. Further, the light resistance of the organic pigment can be further improved. As the Si oxide may include SiO _2.

It is preferred that the pigment body has 1 to 25 parts by mass of the metal oxide per 100 parts by mass of the organic pigment. The upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less. The lower limit is preferably 1 part by mass or more, more preferably 5 parts by mass or more. When the content of the metal oxide is within the above range, excellent dispersion stability can be obtained.

In the pigment body, it is preferred that the surface of the organic pigment is completely coated with the metal oxide, but a part of the surface of the organic pigment may be exposed. The coverage of the metal oxide is preferably from 50 to 100%, more preferably from 80 to 100%. When the coverage is within the above range, excellent dispersion stability can be obtained. Further, the coverage of the metal oxide is a value measured by a transmission electron microscope (TEM) observation method.

The colored composition of the present invention may contain one type of pigment body or may contain two or more types of pigment bodies. When two or more types of pigment bodies are contained, it is preferable that two or more types of pigment bodies contain mutually different organic pigments. Further, it is preferable that the metal oxide contained in each of the pigment bodies contains the same metal atom, and it is more preferable to contain the same metal atom of 5% by mass or more of the total metal atom of the metal oxide, and it is preferably from 8 to 100% by mass. % is especially good. The composition of the metal oxide can be determined by X-ray photoelectron spectroscopy (ESCA). Further, it is preferred that each of the pigment bodies contains an oxide of Si.

The average particle diameter of the pigment body is preferably from 20 to 500 nm, more preferably from 30 to 100 nm. Further, when the color filter is formed using the colored composition of the present invention, the average particle diameter of the pigment body is preferably from 30 to 80 nm, more preferably from 40 to 60 nm. Further, when the coloring composition of the present invention is used for an ink composition for inkjet or a composition for printing ink, the average particle diameter of the pigment body is preferably from 80 to 500 nm, more preferably from 100 to 200 nm. When the average particle diameter of the pigment body is within the above range, the color rendering property is good, and the affinity with the substrate is good. Further, in the present invention, the average particle diameter of the pigment body means the average value of the particle diameters of one pigment body. Observation by a scanning electron microscope (SEM) or a transmission electron microscope (TEM) measures the particle size of 100 pigment bodies and calculates an average value, whereby the average particle diameter can be obtained.

The content of the pigment body is preferably from 2 to 80% by mass based on the total solid content in the coloring composition. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more. The upper limit is preferably 80% by mass or less. When the coloring composition of the present invention contains two or more kinds of pigment bodies, the total range is preferably in the above range.

The pigment body used in the present invention can be produced, for example, by hydrolyzing and condensing a metal alkoxide on the surface of an organic pigment. That is, a film (metal oxide) of a decomposition product of a metal alkoxide is formed on the surface of the organic pigment by hydrolyzing and condensing the metal alkoxide on the surface of the organic pigment.

Examples of the metal alkoxide include a decyl alkoxide, an alkoxide zirconium, and an aluminum alkoxide. Specific examples of the decyl alkoxide include dimethyl dimethoxy decane, dimethyl diethoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, and methyl benzene. Dimethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, methyl tri-n-propoxy decane, methyl triisopropoxy decane, methyl tri-n-butoxy decane, Triisobutoxy oxane, methyl tri-tert-butoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, hexyl trimethoxy decane, octadecyl trimethoxy decane, eighteen Alkyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl triisopropoxy decane, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane And tetraisopropoxy decane, tetra-n-butoxy decane, tetraisobutoxy decane, tetra-butoxy decane, and the like. Specific examples of the alkoxide zirconium include tetraethoxyzirconium, tetrabutoxyzirconium, and the like. Specific examples of the aluminum alkoxide include triethoxy aluminum, aluminum triisopropoxide, and the like. The metal alkoxide may be used alone or in combination of two or more.

A known method can be used for the hydrolysis reaction and the condensation reaction of the metal alkoxide. Catalysts can be used as needed.

Examples of the catalyst include an acid, an acid, a base, and the like. Examples of the acid include nitric acid, oxalic acid, acetic acid, formic acid, hydrochloric acid, boric acid, and phosphoric acid. Examples of the base include an amine, triethylamine, ethylenediamine, and the like. The amount of the catalyst used is not particularly limited, but is preferably 0.1 to 2.0 parts by mass based on 100 parts by mass of the metal alkoxide. The catalyst may be used alone or in combination of two or more.

In the reaction system to which the hydrolysis reaction and the condensation reaction are added, a solvent may be added as needed. The solvent is not particularly limited as long as it can carry out the hydrolysis reaction and the condensation reaction, but it is preferred to use, for example, water or an organic solvent to be described later.

The conditions (temperature, time) of the hydrolysis reaction and the condensation reaction can be appropriately selected depending on the kind of the material to be used. For example, the reaction temperature is preferably from 100 to 300 ° C, more preferably from 150 to 250 ° C. The reaction time is preferably from 1 to 20 hours, more preferably from 2 to 5 hours. The above reaction is preferably carried out while removing the ethanol formed by hydrolyzing the metal alkoxide.

It is preferred to carry out drying after completion of the above reaction. The drying temperature is preferably 80 ° C or less, more preferably 60 ° C or less. The lower limit is not particularly limited, but is preferably 50° C. or higher, and more preferably 30° C. or higher.

<<Other Coloring Agent>> The coloring composition of the present invention may contain a coloring agent other than the above-described pigment body (hereinafter referred to as "another coloring agent"). Other colorants may preferably be any pigment, dye, or dye.

As the pigment, a plurality of conventionally known inorganic pigments or organic pigments can be used. Examples of the inorganic pigment include a metal oxide, a metal compound represented by a metal salt or the like, or carbon black. Specific examples of the metal compound include metal oxides such as ruthenium, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and ruthenium, and composite oxides of metals. The organic pigment is described in the above pigment body.

The dye is not particularly limited, and a known dye can be used. For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-A No. 2592207, and US Pat. No. 4,808,501 can be used. No. 5,676,920, U.S. Patent No. 5,567,920, U.S. Patent No. 5,505,950, U.S. Patent No. 5,567,920, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. The dye disclosed in Kaikai No. 6-194928 or the like. As the chemical structure, a pyrazole azo type, a pyrromethene type, an anilino azo type, a triarylmethane type, an anthraquinone type, a benzylidene type, an oxaphthalocyanine type, a pyrazolotriazole azo can be used. A dye such as a pyridone azo azo, a cyanine, a phenothiazine or a pyrrolopyrazole azomethine.

In addition, as the other coloring agent, the quinophthalone compound described in paragraphs 0011 to 0034 of JP-A-2013-54339, and the paragraph number 0013 to 0:58 of JP-A-2014-26228 can be used. Quinone compound. Further, a dye polymer can be used as another coloring agent. The dye polymer is preferably a dye used for dissolving in a solvent, but may also form particles. When the dye polymer is a particle, the dye polymer is dispersed in a solvent or the like and used. The pigment multimer in a particulate state can be obtained, for example, by emulsion polymerization. Specific examples thereof include a compound and a production method described in JP-A-2015-214682. In addition, the compound described in the above-mentioned Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei.

When the coloring composition of the present invention contains another coloring agent, the content of the other coloring agent is preferably 1.0 to 80% by mass, more preferably 2.0 to 70% by mass, based on the total mass of the pigment body and the other coloring agent. Further, the colored composition of the present invention may be substantially free of other coloring agents. For example, the content of the other coloring agent can be 0.1 parts by mass or less, or 0.05 parts by mass or less, or may not contain other coloring agents, for example, with respect to 100 parts by mass of the pigment body.

<<Resin>> The coloring composition of the present invention contains a resin. In the present invention, a resin having a resin (hereinafter also referred to as Resin A) having at least one selected from the group consisting of an acidic group and a basic group is used as the resin. Examples of the acidic group of the resin A include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. The basic group which the resin A has may be an amine group or the like. The colored composition of the present invention contains the above-mentioned resin A, whereby the dispersion stability of the above-described pigment body can be made good. Further, in the present invention, a resin (other resin) which does not have an acidic group and a basic group can be further used as the resin. Further, a resin mainly used to disperse a coloring agent such as a pigment is referred to as a dispersing agent. However, such use of the resin is only an example and can be used for purposes other than such use.

In the present invention, the weight average molecular weight (Mw) of the resin is preferably from 5,000 to 100,000.

In the colored composition of the present invention, the content of the resin is preferably from 20 to 99% by mass, more preferably from 30 to 98% by mass, based on the total solid content of the colored composition. Further, the content of the resin A is preferably from 20 to 99% by mass, more preferably from 30 to 98% by mass, based on the total solid content of the colored composition.

Further, in the colored composition of the present invention, the resin A is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, based on the total mass of the resin.

In the present invention, the resin A preferably contains an acidic resin or a basic resin. The resin A may contain two or more kinds of acidic resins. In this case, it is preferred that the basic resin is not substantially contained. Further, the resin A does not substantially contain a basic resin. For example, the ratio of the basic resin to the total mass of the resin A is preferably less than 1% by mass, more preferably less than 0.5% by mass, and further not included. good.

Further, the resin A may contain two or more kinds of basic resins. In this case, it is preferred that the acidic resin is not substantially contained. Further, the resin A does not substantially contain an acidic resin. For example, the ratio of the acidic resin to the total mass of the resin A is preferably less than 1% by mass, more preferably less than 0.5% by mass, and further preferably not contained.

Further, in the present invention, the acidic resin means a resin having a larger amount of acidic groups than the amount of the basic group. In the acidic resin, when the total amount of the acidic group and the amount of the basic group is 100 mol%, the amount of the acidic group is preferably 70 mol% or more, and is substantially only composed of an acidic group. The resin is better. Further, in the resin consisting essentially of an acidic group, for example, a resin having an acid group content of 95 mol% or more in the above ratio is preferable, and a resin having an acid group content of 99 mol% or more is more preferable. A resin containing a basic group is further preferred. An acidic group-based carboxyl group is preferred.

Further, the basic resin means a resin having a larger amount of a basic group than an acidic group. In the basic resin, when the total amount of the acidic group and the amount of the basic group is 100 mol%, the amount of the basic group is preferably 50 mol% or more. Further, in the resin which is substantially composed only of a basic group, for example, a resin having an amount of the basic group of 95 mol% or more is preferably used, and a resin having a basic group of 99 mol% or more is more preferable. Preferably, the resin which does not contain an acidic group is further preferable. A basic basic amine group is preferred.

The acid value of the acidic resin is preferably from 30 to 300 mgKOH/g. The lower limit is preferably 30 mgKOH/g or more, more preferably 40 mgKOH/g or more, and still more preferably 50 mgKOH/g or more. The upper limit is preferably 300 mgKOH/g or less, more preferably 200 mgKOH/g or less. Further, the alkali value of the acidic resin is preferably 100 mgKOH/g or less, more preferably 50 mgKOH/g or less, and still more preferably 10 mgKOH/g or less.

The basic value of the basic resin is preferably from 10 to 150 mgKOH/g. The lower limit is more preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, and still more preferably 30 mgKOH/g or more. The upper limit is preferably 150 mgKOH/g or less, and more preferably 100 mgKOH/g or less. Further, the acid value of the basic resin is preferably 150 mgKOH/g or less, more preferably 100 mgKOH/g or less, and still more preferably 50 mgKOH/g or less. Further, in the present invention, the acid value means the number of mg of potassium hydroxide required to neutralize the acidic component per 1 g of the solid component. Further, the base number means the number of mg of potassium hydroxide (KOH) per 1 g of the solid component and the equivalent amount of potassium hydroxide (KOH).

In the present invention, the above resin A preferably contains a graft copolymer. Further, in the present invention, the graft copolymer means a resin having a graft chain. Further, the graft chain means the end from the root of the main chain of the polymer to the group branched from the main chain. The graft copolymer can be preferably used, for example, as a dispersant.

As the graft copolymer, a resin having a graft chain having a number of atoms other than a hydrogen atom in the range of 40 to 10,000 is preferable. Further, the number of atoms other than the hydrogen atom per one of the graft chains is preferably from 40 to 10,000, more preferably from 50 to 2,000, still more preferably from 60 to 500.

Examples of the main chain structure of the graft copolymer include a (meth)acrylic resin, a polyester resin, a polyurethane resin, a polyurea resin, a polyamide resin, and a polyether resin. Among them, a (meth)acrylic resin is preferred. As a graft chain of the graft copolymer, in order to improve the interaction between the graft chain and the solvent, thereby improving the dispersibility, the graft chain having a poly(meth)acrylic acid structure, a polyester structure or a polyether structure is Preferably, the graft chain having a polyester structure or a polyether structure is more preferable.

In the present invention, the graft copolymer has a weight average molecular weight (Mw) of preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and still more preferably 10,000 to 30,000. The number average molecular weight (Mn) of the graft copolymer is preferably from 2,500 to 50,000, more preferably from 5,000 to 30,000, still more preferably from 5,000 to 15,000. Further, in the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the graft copolymer are polystyrene-equivalent values measured by gel permeation chromatography (GPC), and specifically, the following description is used. The values measured by the methods described in the examples.

As the macromonomer used in the production of the graft copolymer by radical polymerization, a known macromonomer can be used, and a macromonomer AA-6 (end group) manufactured by TOAGOSEI CO., LTD. Methyl methacrylate-based polymethyl methacrylate), AS-6 (polystyrene with terminal group of methacryl fluorenyl), AN-6S (styrene with terminal group of methacryl fluorenyl) Copolymer of acrylonitrile), AB-6 (polybutyl acrylate of methacryl fluorenyl group), PLACEL FM5 (2-hydroxyethyl methacrylate ε-hexyl) manufactured by Daicel Chemical Industries, Ltd. Lactone 5 molar equivalent plus finished product), FA10L (ε-caprolactone 2-hydroxyethyl acrylate 10-molar equivalent plus finished product), and polyester macromonomers described in JP-A-2-272009 .

Further, in the present invention, as the graft copolymer, an oligo imine-based graft copolymer containing at least one of a main chain and a side chain and containing a nitrogen atom can be used. The oligomerized imide graft copolymer has a repeating unit and a side chain of an oligomer chain having 40 to 10,000 atoms or a polymer chain Y and at least one of a main chain and a side chain having a basic nitrogen An atomic resin is preferred, and the repeating unit has a group X having a partial structure of a functional group having a pKa of 14 or less. Here, the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. The oligomeric imide graft copolymer preferably has a structure having a nitrogen atom having an alkali strength of pKb 14 or less, and more preferably has a structure having a nitrogen atom of pKb10 or less. In the present invention, the alkali strength pKb means pKb at a water temperature of 25 ° C, and is one of the indexes for quantitatively indicating the strength of the alkali, and has the same meaning as the basicity constant. The alkali strength pKb has a relationship of pKb=14-pKa with an acid strength pKa which will be described later.

The oligomeric imide graft copolymer is particularly preferably a repeating unit (i) and a side chain (ii) having an oligomer chain of 40 to 10,000 or a polymer chain Y, and the repeating unit (i) is Selected from a poly(lower alkylene imine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, a meta-xylenediamine-epichlorohydrin polycondensate repeating unit, and a poly A repeating unit having a basic nitrogen atom in at least one of the vinylamine-based repeating units, which is bonded to a basic nitrogen atom and has a group X having a partial structure of a functional group having a pKa of 14 or less.

The oligoimine-based graft copolymer is a resin containing a repeating unit represented by the following formula (I-1) and a repeating unit represented by the formula (I-2).

[Chemical Formula 1]

In the general formulae (I-1) and (I-2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group, and a each independently represents an integer of 1 to 5, and * represents a repeating unit. In the linking portion, X represents a group having a partial structure having a functional group of pKa 14 or less, and Y represents an oligomer chain or a polymer chain having 40 to 10,000 atoms.

The oligomeric imide graft copolymer is preferably further contained in the form of a repeating unit represented by the formula (I-3). In this way, the dispersion stability of the pigment body is further improved.

[Chemical Formula 2]

In the formula (I-3), R ¹ , R ² and a have the same meanings as in the formula (I-1), R ¹ , R ² and a. Y' represents an oligomer chain or a polymer chain having an anion group having an atomic number of 40 to 10,000. The repeating unit represented by the formula (I-3) can be added with an oligomer or a polymer having a group which forms a salt by reacting with an amine in a resin having a primary amine group or a secondary amine group in the main chain portion. And it is formed by reacting it.

In the formula (I-1), the formula (I-2) and the formula (I-3), R ¹ and R ² are preferably a hydrogen atom. From the viewpoint of availability of raw materials, a is preferably 2.

The oligomeric imide graft copolymer may contain a primary amine group or a third group in addition to the repeating unit represented by the general formula (I-1), the general formula (I-2) and the general formula (I-3). The lower alkyleneimine of the amine group is used as a repeating unit. Further, the nitrogen atom in the lower alkyleneimine repeating unit may be further bonded to a group represented by X, Y or Y' described in the general formulae (I-1) to (I-3).

The repeating unit represented by the formula (I-1) contains 1 to 80 mol%, preferably 3 to 50 mol%, of the total repeating unit contained in the oligoenimine-based graft copolymer. optimal. The repeating unit represented by the formula (I-2) contains 10 to 90 mol%, preferably 30 to 70 mol%, of the total repeating unit contained in the oligoenimine-based graft copolymer. optimal. The content ratio of the repeating unit represented by the formula (I-1) and the repeating unit represented by the formula (I-2) from the viewpoint of the dispersion stability and the balance between the hydrophilicity and the hydrophobicity [(I-1) : (I-2)] is preferably in the range of 10:1 to 1:100 in terms of molar ratio, and more preferably in the range of 1:1 to 1:10.

Further, the repeating unit represented by the formula (I-3) used in combination as needed contains an oligomer chain having an anionic group of 40 to 10,000 or a partial structure of the polymer chain Y' and a nitrogen of the main chain. The atomic ion bond is preferably from 0.5 to 20 mol%, preferably from 1 to 10 mol%, in the total repeating unit contained in the oligomeric imide graft copolymer from the viewpoint of the effect. . Further, the ionic bond of the polymer chain Y' can be confirmed by infrared spectroscopy or alkali titration.

Another preferred aspect of the oligomeric imide graft copolymer is a repeating unit represented by the following formula (II-1) as a repeating unit (i) and a repeating unit (ii) The aspect of the repeating unit represented by the formula (II-2).

[Chemical Formula 3]

In the general formulae (II-1) and (II-2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group. *, X and Y have the same meanings as *, X and Y in the general formulae (I-1) and (I-2).

In the oligomeric imide graft copolymer, it is preferred to further contain a repeating unit represented by the formula (II-3). In this way, the dispersion stability of the colorant or the like is further improved.

[Chemical Formula 4]

In the general formula ^(II-3), 3, the same as R ^4, R ^5, and ^{R 6 R 3, R 4,} R 5 and R meaning as the general formula R (II-1) ⁶ in. The meaning of Y' is the same as Y' in the formula (I-3).

In the general formulae (II-1), (II-2) and (II-3), the R ³ , R ⁴ , R ⁵ and R ⁶ -based hydrogen atoms are preferred from the viewpoint of availability of raw materials.

The repeating unit represented by the formula (II-1) contains 1 to 80 mol%, preferably 3 to 50 mol%, of the total repeating unit contained in the oligoenimine-based graft copolymer. optimal. The repeating unit represented by the formula (II-2) contains 10 to 90 mol%, preferably 30 to 70 mol%, of the total repeating unit contained in the oligomeric imide graft copolymer. optimal. The content ratio of the repeating unit represented by the general formula (II-1) and the repeating unit represented by the general formula (II-2) from the viewpoint of the dispersion stability and the balance between the hydrophilicity and the hydrophobicity [(II-1) ): (II-2)] is preferably in the range of 10:1 to 1:100 in terms of molar ratio, and more preferably in the range of 1:1 to 1:10. The repeating unit represented by the formula (II-3) used in combination as needed contains 0.5 to 20 mol%, preferably 1 to 10 mol%, based on the total repeating unit in the oligomeric imide graft copolymer. For the best.

From the viewpoint of dispersion stability, the oligomeric imide graft copolymer is particularly in a state containing both a repeating unit represented by the general formula (I-1) and a repeating unit represented by the general formula (I-2). For the best.

(The group X having a partial structure having a functional group of pKa14 or less) The group X has a functional group of pKa14 or less. The pKa of the functional group having a pKa of 14 or less in the group X is a value at a water temperature of 25 °C. Here, "pKa" means defined in the contents described in Chemical Handbook (II) (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, MARUZEN Co., Ltd.). The "functional group of pKa14 or less" is not particularly limited as long as the physical properties satisfy the above conditions, and the pKa of the known functional group satisfies the above range, but in particular, the pKa is 12 or less. A functional group is preferred, and a functional group having a pKa of 11 or less is preferred. Specific examples of the group X include a carboxylic acid group (pKa: about 3 to 5), a sulfonic acid group (pKa: about -3 to -2), and -COCH ₂ CO- (pKa: 8 to 10). Left and right), -COCH ₂ CN (pKa: about 8 to 11), -CONHCO-, phenolic hydroxyl group, -R _F CH ₂ OH or -(R _F ) ₂ CHOH (R _F represents perfluoroalkyl group. pKa: 9 ~11 or so), sulfonamide group (pKa: about 9 to 11), etc., especially carboxylic acid group (pKa: about 3 to 5), sulfonic acid group (pKa: about -3 to -2), -COCH ₂ CO - (pKa: about 8 to 10) is preferred.

It is preferred that the group X is directly bonded to a basic nitrogen atom in a repeating unit having a basic nitrogen atom. The nitrogen atom having a repeating unit of a basic nitrogen atom is not only covalently bonded to the partial structure X, but may also be linked by ion bonding to form a salt. The group X is particularly preferably a structure represented by the following formula (V-1), formula (V-2) or formula (V-3).

[Chemical Formula 5]

In the general formula (V-1) and the general formula (V-2), U represents a single bond or a divalent linking group. d and e each independently represent 0 or 1. In the formula (V-3), Q represents a mercapto group or an alkoxycarbonyl group.

Examples of the divalent linking group represented by U include an alkylene group, an arylene group, an alkyleneoxy group or the like which may have an oxygen atom, and particularly an alkylene group having 1 to 30 carbon atoms or a carbon number. An arylene group of 6 to 20 is preferred, and an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms is most preferred. Further, from the viewpoint of productivity, d is preferably 1 and e is preferably 0.

Q represents a mercapto or alkoxycarbonyl group. As the mercapto group in Q, a mercapto group having 1 to 30 carbon atoms is preferred, and an ethylidene group is preferred. As the alkoxycarbonyl group in Q, Q is preferable from the viewpoint of easy production of an oxime group and availability of a raw material (precursor of the group X).

(Oligomer chain or polymer chain Y having an atomic number of 40 to 10,000) The oligomer chain or polymer chain Y having an atomic number of 40 to 10,000 includes a main copolymer capable of grafting with an oligoimide-based copolymer. A known polymer chain such as a polyester, a polyamide, a polyimine or a poly(meth)acrylate to which a chain is bonded. It is preferred that the bonding site of Y with the oligomeric imide graft copolymer is Y. It is preferred that Y is bonded to the basic nitrogen atom of the above repeating unit (i). The basic nitrogen atom of the repeating unit (i) is bonded to Y by a covalent bond, an ionic bond, or a covalent bond and a mixed bond of an ionic bond. The ratio of the basic nitrogen atom of the repeating unit (i) to the bonding mode of Y is a covalent bond and: an ion bond and =100:0 to 0:100 is preferable, and 95:5 to 5:95 is more preferable. 90:10~10:90 is the best. Y is preferably bonded to the basic nitrogen atom of the repeating unit (i), or as a carboxylic acid and a basic nitrogen atom of the repeating unit (i).

From the viewpoint of dispersibility, dispersion stability, and developability, the number of atoms of the oligomer chain or polymer chain Y is preferably from 50 to 5,000, more preferably from 60 to 3,000. The number average molecular weight of Y can be measured by using the polystyrene equivalent value of the GPC method. The number average molecular weight of Y is preferably from 1,000 to 50,000, and from 1,000 to 30,000 is preferable from the viewpoint of dispersibility, dispersion stability, and developability. Y is preferably a side chain structure. With respect to the main chain structure, it is preferable that Y is connected to two or more molecules of the resin, and it is preferable to connect five or more. For the details of Y, the contents described in paragraphs 0086 to 0098 of JP-A-2013-064979 can be referred to, and the contents are incorporated in the present specification.

The oligoimide-based graft copolymer described above can be synthesized by the method described in paragraphs 0110 to 0117 of JP-A-2013-064979. Specific examples of the oligoenimine-based graft copolymer include the resins described in paragraphs 0099 to 0109 and 0119 to 0124 of JP-A-2013-064979, which is incorporated herein by reference. .

In the present invention, a copolymer containing a repeating unit represented by any one of the formula (A1) and the formula (A2) and a repeating unit having an acidic group can be used as the graft copolymer. [Chemical Formula 6]

In the general formulae (A1) and (A2), R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² each independently represent -CO-, -C(=O)O-. , -CONH-, -OC(=O)- or a phenyl group, and L ¹ and L ² each independently represent a single bond or a divalent organic linking group, and A ¹ and A ² each independently represent a monovalent organic group. The bases, m and n each independently represent an integer of 2 to 8, and p and q each independently represent an integer of 1 to 100.

R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferred. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. As R ¹ , R ² , R ⁴ and R ⁵ , a hydrogen atom is preferred, and as R ³ and R ⁶ , a hydrogen atom or a methyl group is also preferable from the viewpoint of the adsorption efficiency on the surface of the pigment.

X ¹ and X ² each independently represent -CO-, -C(=O)O-, -CONH-, -OC(=O)- or a phenyl group. Among them, from the viewpoint of the adsorption property to the pigment, -C(=O)O-, -CONH-, and phenyl are preferred, and -C(=O)O- is preferred.

L ¹ and L ² each independently represent a single bond or a divalent organic linking group. The divalent organic linking group, a substituted or unsubstituted alkylene group, and a divalent organic linking group composed of an alkylene group and a hetero atom or a partial structure containing a hetero atom are preferred. As the alkylene group, an alkylene group having 1 to 12 carbon atoms is preferred, an alkylene group having 1 to 8 carbon atoms is further preferred, and an alkylene group having 1 to 4 carbon atoms is particularly preferred. . Examples of the hetero atom in the partial structure containing a hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. Among them, an oxygen atom or a nitrogen atom is preferred. The divalent organic linking group has a terminal selected from the group consisting of -C(=O)-, -OC(=O)-, -NHC (=) from the viewpoint of adsorption to the pigment. It is preferred that the hetero atom or the partial structure containing a hetero atom in O)- is bonded to an adjacent oxygen atom via a hetero atom or a partial structure containing a hetero atom. Here, the adjacent oxygen atom means an oxygen atom bonded to L ¹ in the general formula (A1) and L ² in the general formula (A2) at the terminal side of the side chain.

A ¹ and A ² each independently represent a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferred. The substituents described in Paragraph No. 0028 of JP-A-2009-256572 are incorporated herein by reference.

A ¹ and A ^{2 are} a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, and 5 to 5 carbon atoms from the viewpoint of dispersion stability and developability. The cyclic alkyl group of 20 is preferably a linear alkyl group having 4 to 15 carbon atoms, a branched alkyl group having 4 to 15 carbon atoms, and a cyclic alkyl group having 6 to 10 carbon atoms. More preferably, a linear alkyl group having 6 to 10 carbon atoms and a branched alkyl group having 6 to 12 carbon atoms are further preferred.

m and n each independently represent an integer of 2-8. From the viewpoint of dispersion stability and developability, 4 to 6 is preferred, and 5 is most preferred.

p and q each independently represent an integer of 1 to 100. It is also possible to mix two or more types of P different and different q. From the viewpoint of dispersion stability and developability, p and q are preferably from 5 to 60, more preferably from 5 to 40, and further preferably from 5 to 20.

The details of the repeating unit represented by the formula (A1) and the repeating unit represented by the formula (A2) can be referred to in paragraphs 0034 to 0044 of JP-A-2009-256572, and the contents are incorporated. In this manual.

The repeating unit having an acidic group can be constituted by using a monomer having an acidic group. Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, a vinyl monomer having a phosphoric acid group, and the like. Examples of the vinyl monomer having a carboxyl group include (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid. Dimer and the like. Further, addition of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate to a cyclic anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride or cyclohexanedicarboxylic anhydride may be used. The reactant, ω-carboxy-polycaprolactone mono(meth)acrylate or the like. Further, as the precursor of the carboxyl group, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride can be used. Among them, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and maleic anhydride, phthalic anhydride, succinic anhydride, or cyclohexane dicarboxyl is considered from the viewpoint of development removability of the unexposed portion. An addition reactant of a cyclic anhydride such as an acid anhydride is preferred. Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid and the like. Examples of the vinyl monomer having a phosphoric acid group include mono(2-propenyloxyethyl) phosphate and mono(1-methyl-2-propenyloxyethyl phosphate). Further, as a repeating unit having an acidic group, the descriptions of paragraphs 0067 to 0069 of JP-A-2008-165059 can be referred to, and the contents thereof are included in the present specification.

The details of the graft copolymer described above can be referred to in paragraphs 0021 to 0,088 of JP-A-2009-256572, which is incorporated herein by reference.

The colored composition of the present invention may contain two or more kinds of resins. When two or more kinds of resins are contained, the difference between the solubility parameters of the resins (hereinafter also referred to as SP values) is 6 (J/cm ³ ) ^0.5 or less, preferably 0 to 4 (J/cm ³ ) ^0.5 is more preferable. . When the difference in SP value is within the above range, the dispersion stability of the pigment body can be improved. Further, in the present invention, the SP value is a value obtained by the Hoy method. As a document of the Hoy method, HL Hoy: J. Paint Tech., 42 (540), 76-118 (1970) and SP value basis, application and calculation method (Shanmoto, Information Agency, 2005) can be preferably cited.

<<<Dispersant>>> In the present invention, it is preferred to use at least one resin (resin A) selected from the group consisting of an acidic group and a basic group as a dispersing agent. That is, in the case where at least one resin selected from the group consisting of an acidic group and a basic group is present, the colored composition of the present invention is produced by a step of dispersing a pigment body having a metal oxide on at least a part of the surface of the organic pigment. Preferably. The dispersing agent may, for example, be a block copolymer, a random copolymer or a graft copolymer, and a graft copolymer is preferred. The graft copolymer is exemplified above. Examples of the dispersant include an acidic dispersant (acidic resin) and an alkaline dispersant (basic resin).

The dispersing agent may be used alone or in combination of two or more. From the viewpoint of dispersion stability, it is particularly preferable to use only one type of dispersant. The colored composition of the present invention is a composition containing two or more kinds of pigment bodies, and it is preferred that two or more kinds of pigment bodies are dispersed only in an acidic dispersant or dispersed together only in an alkaline dispersant. When two or more kinds of dispersants are used in combination, the difference in SP value between the dispersants is preferably 6 (J/cm ³ ) ^0.5 or less, and more preferably 0 to 4 (J/cm ³ ) ^0.5 . When the difference in SP value is within the above range, the dispersion stability of the pigment body can be improved. When two or more kinds of dispersing agents are used in combination, the dispersing agent is preferably composed of only an acidic resin or only an alkali resin. Further, the dispersant is substantially composed only of an acidic resin. For example, the ratio of the acidic resin to the total mass of the dispersant is preferably 99% by mass or more, more preferably 99.5% by mass or more, and only the acidic resin is used. Further preferred. Further, the dispersing agent is substantially composed only of a basic resin. For example, the ratio of the basic resin is preferably 99% by mass or more, more preferably 99.5% by mass or more, based on the total mass of the dispersing agent, and only alkaline. The resin composition is further preferable.

The dispersant can also be obtained as a commercial product. As a specific example, "DA-7301" manufactured by KUSUMOTO Chemicals, LTD.; "DISPERBYK-101 (polyamide-amine phosphate), 107 manufactured by BYK Chemie Co., Ltd.) (Carboxylic acid ester), 110 (acid group containing acid group), 111 (phosphate type dispersing agent), 130 (polyamide), 161, 162, 163, 164, 165, 166, 168, 170 (polymer copolymerization) ", 2164", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)" manufactured by BYK-Chemie Co., Ltd., "EFKA4047, 4050-4165 (polyurethane system), EFKA 4330 to 4340 (block copolymer) manufactured by EFKA Co., Ltd. ), 4400 ~ 4402 (modified polyacrylate), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo) "Phosphorus Derivatives""; "AJISPER PB821, PB822, PB880, PB881" manufactured by AJINOMOTO FINE-TECHNO Co., Inc.; "FLOWLEN TG-710 (urethane oligomer)", KYOEISHA CHEMICAL, manufactured by KYOEISHA CHEMICAL CO., LTD. CO., LTD. manufactures "POLYFLOW No. 50E, No. 300 (acrylic copolymer) Manufactured by KUSUMOTO Chemicals, Ltd. "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725 "KM Corporation manufactures "DEMOL RN, N (formalin naphthalenesulfonate polycondensate), MS, C, SN-B (aromatic sulfonate fumarate polycondensate)", manufactured by KAO Corporation "HOMOGENOL L-18 (polymer) Polycarboxylate)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)" manufactured by KAO Corporation, "ACETAMIN86 (stearylamine acetate)" manufactured by KAO Corporation; manufactured by LUBRIZOL JAPAN, LTD. "SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional portion at the end), 24000, 28000, 32000, 38500 (grafted polymer)"; manufactured by Nikko Chemicals Co., Ltd. "NIKKOR T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)" ; KAWAKEN FINE CHEMICALS CO., LTD. manufactures "HINOACT T-8000E", etc.; Shin-Etsu Chemi "Organic siloxane polymer KP341" manufactured by cal Co., Ltd.; MORISHITA & CO., LTD. Manufacture "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401" EFKA Polymer 450", "DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100" by SUN NOPCO LIMITED; "ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72" manufactured by ADEKA CORPORATION "IONET (trade name) S-20" and the like are manufactured by P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123", and SANYO CHEMICAL INDUSTRIES, LTD. Further, "Acryl base FFS-6752, Acryl base FFS-187, Akurikyua-RD-F8" can be produced using FUJIKURAKASEI CO., LTD.; "CYCLOMER P" can be manufactured by Daicel Corporation. Further, the resin described with the above dispersant can also be used in applications other than the dispersant. For example, it can be used as a binder.

<<<Alkali Soluble Resin>> In the present invention, a resin having a group having at least one group which promotes alkali solubility in a molecule (also referred to as an alkali-soluble resin) can be used as the resin. In addition, alkali-soluble resins can also be used as a dispersant and a binder.

The molecular weight of the alkali-soluble resin is not particularly limited, but the weight average molecular weight (Mw) is preferably from 5,000 to 100,000. Further, the number average molecular weight (Mn) is preferably from 1,000 to 20,000. The alkali-soluble resin may be a linear organic high molecular polymer, or may have at least one base which promotes alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). The alkaloid-soluble resin is appropriately selected.

As the alkali-soluble resin, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable from the viewpoint of heat resistance. From the viewpoint of developability, an acrylic resin, an acrylamide resin, and an acrylic/acrylamide copolymer resin are preferable. Examples of the group which promotes alkali solubility (hereinafter, also referred to as an acidic group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and are soluble in an organic solvent, and can be carried out by a weak alkali aqueous solution. A developer is preferred, and a particularly preferred one is (meth)acrylic acid. These acidic groups may be used alone or in combination of two or more.

In the case of producing an alkali-soluble resin, for example, a method based on a known radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical initiator, and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and the conditions can be experimentally set.

As the alkali-soluble resin, a polymer having a carboxylic acid in a side chain is preferred, and examples thereof include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial ester. An alkali-soluble phenol resin such as a maleic acid copolymer or a novolac type resin; an acid cellulose derivative having a carboxyl group in a side chain; and an acid anhydride added to a polymer having a hydroxyl group. In particular, a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith is preferred as the alkali-soluble resin. Examples of the other monomer copolymerizable with (meth)acrylic acid include an alkyl (meth)acrylate, an aryl (meth)acrylate, and a vinyl compound. Examples of the (meth)acrylic acid alkyl ester and the (meth)acrylic acid aryl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid Benzyl ester, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, and the like. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, and polymethyl methacrylate. Giant monomer and so on. N-phenylmaleimide, N-cyclohexylmaleimide, and the like are mentioned as the N-substituted maleimide monomer described in Japanese Laid-Open Patent Publication No. Hei 10-300922. Further, the other monomers copolymerizable with the (meth)acrylic acid may be used alone or in combination of two or more.

Moreover, in order to improve the crosslinking efficiency of the coloring composition in the present invention, an alkali-soluble resin having a polymerizable group can be used. Examples of the polymerizable group include a (meth)allyl group and a (meth)acryl fluorenyl group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin or the like containing a polymerizable group in a side chain is used. The alkali-soluble resin containing a polymerizable group is preferably a resin obtained by reacting an isocyanate group with a hydroxyl group and leaving one unreacted isocyanate group in advance, and containing a polymerizable group such as a (meth)acryl fluorenyl group. An alkali-soluble resin modified with a urethane obtained by reacting a compound with a carboxyl group-containing acrylic resin; obtained by a reaction of a carboxyl group-containing acrylic resin with a compound having an epoxy group and a polymerizable double bond in the molecule An alkali-soluble resin; an acid pendant acrylic epoxy resin; an alkali-soluble resin obtained by reacting a hydroxyl group-containing acrylic resin with a dibasic acid anhydride having a polymerizable double bond; and a hydroxyl group-containing acrylic resin and An alkali-soluble resin obtained by reacting a compound having an isocyanate group and a polymerizable group; and the following resin is obtained by alkaline treatment as described in JP-A-2002-229207 and JP-A-2003-335814 An alkali-soluble resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or the β-position in the side chain. Examples of the alkali-soluble resin containing a polymerizable group include DIANAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co., Ltd.), and VISCOAT R- 264, KS RESIST 106 (both manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (all manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD.), and Ebecryl 3800 (DAICEL UCB CO., LTD., manufactured by Akurikyua-RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.).

As the alkali-soluble resin, benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/(meth)acrylic acid-2-hydroxyethyl copolymer may be preferably used. a multicomponent copolymer composed of benzyl (meth)acrylate/(meth)acrylic acid/other monomer. Further, a copolymer of 2-hydroxyethyl (meth)acrylate may be preferably used, and 2-hydroxypropyl (meth)acrylate/polyphenyl group described in JP-A-7-140654 Ethylene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid Copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/A Benzyl acrylate / methacrylic acid copolymer and the like.

It is also preferred that the alkali-soluble resin contains a polymer (a) which contains a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (below) Further, the monomer components of these compounds are sometimes referred to as "ether dimers".

[Chemical Formula 7]

In the formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. [Chemical Formula 8] In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. Specific examples of the general formula (ED2) can be referred to the description of JP-A-2010-168539.

In the general formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include a methyl group, an ethyl group, and a n-propyl group. a linear or branched alkyl group such as isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl or 2-ethylhexyl; an aryl group such as phenyl; An alicyclic group such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl or 2-methyl-2-adamantyl; An alkyl group substituted with an alkoxy group such as a methoxyethyl group or a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a benzyl group or the like. Among them, from the viewpoint of heat resistance, a substituent such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group which is not easily desorbed from a primary or secondary carbon by acid or heat is preferred.

Specific examples of the ether dimer can be referred to, for example, in paragraph 0317 of JP-A-2013-29760, which is incorporated herein by reference. The ether dimer may be used alone or in combination of two or more. The structure of the compound represented by the free radical formula (ED) may also copolymerize other monomers.

The alkali-soluble resin may also contain a structural unit derived from a compound represented by the following formula (X). [Chemical Formula 9] In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or may have a benzene ring having 1 to 20 carbon atoms. alkyl. n represents an integer of 1 to 15.

In the above formula (X), the alkylene group of R ₂ has preferably 2 to 3 carbon atoms. Further, the alkyl group of R ₃ has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and the alkyl group of R ₃ may contain a benzene ring. The alkyl group having 1 to 20 carbon atoms and containing a benzene ring represented by R ₃ may, for example, be a benzyl group or a 2-phenyl(iso)propyl group.

The alkali-soluble resin can be referred to the following paragraphs of JP-A No. 2012-208494, paragraphs 0558 to 0571 (paragraphs 0685 to 0700 of the specification of the corresponding US Patent Application Publication No. 2012/0235099), and the contents are incorporated herein. In the manual. In addition, the copolymer (B) described in paragraphs 0029 to 0063 described in JP-A-2012-32767, and the alkali-soluble resin used in the examples, and the paragraph number of JP-A-2012-208474 can be used. The adhesive resin described in 0088 to 0098 and the adhesive resin used in the examples, the adhesive resin described in paragraphs 0022 to 0032 of JP-A-2012-137531, and the adhesive resin used in the examples, The adhesive resin described in paragraphs 0132 to 0143 of JP-A-2013-024934, and the adhesive resin used in the examples, and the adhesives described in paragraphs 0092 to 0098 of JP-A-2011-242752 The resin and the binder resin used in the examples, and the binder resin described in paragraphs 0030 to 0072 of JP-A-2012-032770. This is incorporated into the specification of the present application.

The acid value of the alkali-soluble resin is preferably from 30 to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more. The upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, particularly preferably 150 mgKOH/g or less, and even more preferably 120 mgKOH/g or less.

When the coloring composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 1 to 15% by mass based on the total solid content of the coloring composition, more preferably 2 to 12% by mass, and 3 to 10% by mass. It is further preferred. The colored composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. When two or more types of alkali-soluble resins are contained, the total amount thereof is preferably in the above range.

<<Solvent>> The coloring composition of the present invention preferably contains a solvent. The solvent is not particularly limited as long as it satisfies the coatability of the colored composition. The solvent can be appropriately selected depending on the use.

Examples of the solvent include water and an organic solvent. It is preferred that the water use deionized water, that is, ion-exchanged water, distilled water or the like. Further, neutral, alkaline, and acidic water can be used depending on the materials used. The organic solvent may, for example, be an ester, and examples thereof include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, and butyl propionate. , isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, oxyacetic acid) Butyl ester (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-oxypropionic acid Base esters (for example: methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethyl) Methyl oxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-oxopropionate (eg methyl 2-oxypropionate, ethyl 2-oxypropionate) , propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropionic acid Methyl ester, ethyl 2-ethoxypropionate), methyl 2-oxy-2-methylpropanoate and 2-oxy-2-methyl Ethyl propyl propionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetate methyl acetate, ethyl acetate ethyl acetate, methyl 2-butyrate acid, ethyl 2-butyrate acid, etc.; as the ether, for example, diethylene glycol dimethyl ether, Tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethyl Carbitol acetate (diethylene glycol monoethyl ether acetate), diethylene glycol monobutyl ether, butyl carbitol acetate (diethylene glycol monobutyl ether acetate), propylene glycol monomethyl Ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, etc.; examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, and 2-heptanone. 3-heptanone or the like; examples of the aromatic hydrocarbons include toluene and xylene.

From the viewpoint of improving the solubility of the resin or the like, the coating surface, and the like, it is also preferred to mix two or more of these solvents. For example, selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate , 3-methoxypropionic acid methyl ester, 2-heptanone, cyclopentanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether A mixed solution of two or more kinds of acid esters is preferred.

Further, in the present invention, the solvent can preferably be water or a mixture of water and a water-soluble organic solvent. In the present invention, the water-soluble organic solvent means that 1 g or more of the organic solvent is dissolved with respect to 100 g of water at 20 °C. Specific examples of the water-soluble organic solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, and cyclohexanol. Alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, hexanediol, pentanediol, glycerin, hexanetriol Polyols such as thiodiglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, Propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether Ethylene glycol derivatives, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethylethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, An amine such as triethylenetetramine, polyethyleneimine or tetramethylpropanediamine, formamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylene Sulfone, sulfolane, 2 Pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone, and the like.

The content of the peroxide in the solvent is preferably 0.8 mmol/L or less, and a solvent containing substantially no peroxide is preferably used. Further, as the solvent, an organic solvent having a small metal content is preferably used. For example, the metal content of the organic solvent is preferably 10 ppb or less. The metal content of the organic solvent may be used as the ppt level as needed, and the high purity solvent is supplied, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

When the coloring composition of the present invention contains two or more kinds of solvents, a solvent having a difference in SP value of 6 (J/cm ³ ) ^0.5 or less is preferably used in combination. The difference in SP value is 5 (J/cm ³ ) ^0.5 or less is more preferable, and 0 to 4 (J/cm ³ ) ^0.5 is further preferable. Further, the difference between the SP value of the resin contained in the colored composition and the SP value of the solvent is preferably 6 (J/cm ³ ) ^0.5 or less, more preferably 0 to 5 (J/cm ³ ) ^0.5 .

From the viewpoint of coating properties, the total solid content concentration of the colored composition in the solvent content is preferably from 5 to 80% by mass. The lower limit is, for example, 10% by mass or more, more preferably. The upper limit is, for example, 60% by mass or less, more preferably 50% by mass or less. The colored composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably in the above range.

<<Polymerizable Compound>> The colored composition of the present invention preferably contains a polymerizable compound. A known compound can be used as the polymerizable compound. For example, a compound containing a group having an ethylenically unsaturated bond, a cyclic ether (epoxy group, oxetane) group, or a methylol group can be given. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryl fluorenyl group. In the present invention, a polymerizable compound is preferably a photopolymerizable compound.

The polymerizable compound may be, for example, any one of a chemical form such as a monomer or a prepolymer (dimer, trimer, and oligomer or the mixture and the plurality of polymers). The polymerizable compound is preferably a monomer. The molecular weight of the polymerizable compound is preferably from 100 to 3,000, more preferably from 250 to 1,500. The polymerizable compound is preferably a 3- to 15-functional (meth) acrylate compound, and more preferably a 3- to 6-functional (meth) acrylate compound. Examples of the monomer and the prepolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters thereof, and decylamines thereof. The class and the above-mentioned polymer are preferably esters of an unsaturated carboxylic acid and an aliphatic polyol compound, amides of an unsaturated carboxylic acid and an aliphatic polyamine compound, and the like. Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, or an addition reaction product of a monofunctional or polyfunctional isocyanate or epoxy group, and A dehydration condensation reaction product of a monofunctional or polyfunctional carboxylic acid or the like. Further, a reaction product of an unsaturated carboxylic acid ester or a guanamine having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol is also preferable. A reaction product of an unsaturated carboxylic acid ester or a guanamine having a detachable substituent such as a halogen group or a tosyloxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol is also preferred. Further, in place of the above unsaturated carboxylic acid, a compound group substituted with a vinylbenzene derivative such as an unsaturated phosphonic acid or styrene, a vinyl ether or an allyl ether may be used. As the specific compound, the compound described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

In the present invention, a compound having one or more groups having an ethylenically unsaturated bond and having a boiling point of 100 ° C or higher at normal pressure is also preferable as the polymerizable compound. For example, the compound described in Paragraph No. 0227 of JP-A-2013-29760, and paragraphs 0254 to 0257 of JP-A-2008-292970 can be referred to, and the contents are incorporated in the present specification.

The polymerizable compound is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by NIPPON KAYAKU CO., LTD.) or dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; NIPPON KAYAKU CO.). , manufactured by LTD.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by NIPPON KAYAKU CO., LTD.), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD) DPHA; manufactured by NIPPON KAYAKU CO., LTD., manufactured by A-DPH-12E; manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., and the (meth)acryloyl group via ethylene glycol residue, propylene glycol residue The structure of the bond (for example, SR454, SR499, marketed by SARTOMER Company, Inc.). These types of oligomers can also be used. Further, NK ester A-TMMT (manufactured by Pentaerythritol tetraacrylate SHIN-NAKAMURA CHEMICAL CO., LTD.) KAYARAD RP-1040 (manufactured by NIPPON KAYAKU CO., LTD.) or the like can be used. Further, SR339A (2-phenoxyethyl acrylate), CD420 (3,3,5-trimethylcyclohexyl ester), SR395 (isobutyl acrylate) commercially available from SARTOMER Company, Inc., may also be used. NVC (N-vinyl caprolactam) commercially available from BASF Corporation. The aspect of the preferred polymerizable compound is shown below.

The polymerizable compound may have an acidic group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. As the polymerizable compound having an acidic group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and a non-aromatic carboxylic anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acidic group. More preferably, the compound is particularly preferred in the case where the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercial item, for example, ARONIX TO-2349, M-305, M-510, M-520, etc. are manufactured by TOAGOSEI CO., LTD.

The acid value of the polymerizable compound having an acidic group is preferably from 0.1 to 40 mgKOH/g, and particularly preferably from 5 to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development and dissolution characteristics are good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and handling. Further, the photopolymerizability is good and the curability is good.

A compound having a caprolactone structure among the polymerizable compounds is also preferred. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include ε-caprolactone-modified polyfunctional (meth) acrylate, which is ε-caprolactone. The modified polyfunctional (meth) acrylate can be obtained by using trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, three Polyols such as pentaerythritol, glycerin, diglycerin, and trimethylol melamine are obtained by esterification with (meth)acrylic acid and ε-caprolactone. Among them, a compound having a caprolactone structure represented by the following formula (Z-1) is preferred.

[Chemical Formula 10]

In the general formula (Z-1), all of the six R's are represented by the following formula (Z-2), or one to five of the six R are represented by the following formula (Z-2) The group represented by the formula is the group represented by the following formula (Z-3).

[Chemical Formula 11]

In the formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond.

[Chemical Formula 12]

In the formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond.

A polymerizable compound having a caprolactone structure is commercially available, for example, from NIPPON KAYAKU CO., LTD. as KAYARAD DPCA series, and DPCA-20 (in the above formulas (Z-1) to (Z-3), m= 1. The number of groups represented by the formula (Z-2) = 2, the compound in which all R ¹ are hydrogen atoms), DPCA-30 (in the above formula (Z-1) to (Z-3), m = 1. The number of groups represented by the formula (Z-2) = 3, the compound in which all R ¹ are a hydrogen atom), and DPCA-60 (in the above formula (Z-1) to (Z-3), m = 1. The number of groups represented by the formula (Z-2) = 6, the compound in which all of R ¹ is a hydrogen atom), DPCA-120 (in the above formula (Z-1) to (Z-3), m = 2. A compound represented by the formula (Z-2) = 6, a compound in which all R ¹ are a hydrogen atom).

As the polymerizable compound, a compound represented by the following formula (Z-4) or (Z-5) can be used.

[Chemical Formula 13]

In the general formulae (Z-4) and (Z-5), E independently represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, y each independently represents an integer of 0 to 10, and X each independently represents a (meth)acryloyl group, a hydrogen atom or a carboxyl group. In the general formula (Z-4), the total of (meth)acrylonyl groups is three or four, and m each independently represents an integer of from 0 to 10, and the total of each m is an integer of from 0 to 40. In the general formula (Z-5), the total of (meth)acrylonyl groups is 5 or 6, and n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

In the general formula (Z-4), m is preferably an integer of 0 to 6, and an integer of 0 to 4 is more preferably. Further, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable. In the general formula (Z-5), n is an integer of 0 to 6 and preferably an integer of 0 to 4 is more preferable. Further, the total of n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and an integer of 6 to 12 is particularly preferable. Further, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in the formula (Z-4) or the formula (Z-5) is preferred. It is a form in which the end of the oxygen atom side is bonded to X.

The compound represented by the formula (Z-4) or the formula (Z-5) may be used alone or in combination of two or more. In the general formula (Z-5), the form in which all six X are acrylonitrile groups is particularly preferable.

In addition, the total content of the polymerizable compound of the compound represented by the formula (Z-4) or the formula (Z-5) is preferably 20% by mass or more, more preferably 50% by mass or more.

The compound represented by the formula (Z-4) or the formula (Z-5) can be synthesized by a conventionally known procedure: a ring-opening skeleton of ethylene oxide or propylene oxide by a ring-opening addition reaction a step of bonding to pentaerythritol or dipentaerythritol; and, for example, a step of introducing (meth)acrylofluorene and a terminal hydroxyl group of the ring-opening skeleton to introduce a (meth)acrylonitrile group. Each step is a well-known step, and those skilled in the art can easily synthesize a compound represented by the formula (Z-4) or (Z-5).

Among the compounds represented by the formula (Z-4) or the formula (Z-5), a pentaerythritol derivative and/or a dipentaerythritol derivative are more preferable. Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to (f)"), wherein the compounds (a) and (b) are exemplified. ), (e), (f) are preferred.

[Chemical Formula 14]

[Chemical Formula 15]

The commercially available product of the polymerizable compound represented by the general formulae (Z-4) or (Z-5), for example, SR having a tetrafunctional acrylate having four ethyleneoxy chains manufactured by SARTOMER Company, Inc. -494, DPCA-60 of 6-functional acrylate having 6 pentadienyloxy chains, TPA-330 having 3 functional acrylates of isobutyleneoxy chain, and the like, manufactured by NIPPON KAYAKU CO., LTD.

The urethane acrylates described in Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. A urethane compound having an ethylene oxide-based skeleton described in Japanese Patent Publication No. Sho 62-49860, Japanese Patent Publication No. Sho 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 The class is also suitable. In addition, the addition of an amine-based structure and a sulfide structure in the molecule is described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. As a polymerizable compound, a coloring composition having a very good light-sensing speed can be obtained. The commercially available product is urethane oligomer UAS-10, UAB-140 (made by SANYO-KOKUSAKU PULP CO., LTD.), UA-7200 (made by SHIN-NAKAMURA CHEMICAL CO., LTD.), DPHA. -40H (manufactured by NIPPON KAYAKU CO., LTD.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by KYOEISHA CHEMICAL CO., LTD.).

In the colored composition of the present invention, the content of the curable compound relative to the total solid content of the colored composition is preferably from 0.1 to 40% by mass. The lower limit is, for example, 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is, for example, preferably 30% by mass or less, more preferably 20% by mass or less. The curable compound may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably in the above range.

<<Polyfunctional thiol compound>> The colored composition of the present invention may contain a polyfunctional thiol compound having two or more fluorenyl groups in the molecule for the purpose of promoting the reaction of the polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkanethiol, and a compound having a structure represented by the following formula (T1) is preferred. General formula (T1) [Chemical Formula 16] (In the formula (T1), n represents an integer of 2 to 4, and L represents a linking group of 2 to 4 valence.)

In the above formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, n is 2, and an L-alkyl group having 2 to 12 carbon atoms is particularly preferable. . Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulae (T2) to (T4), and compounds represented by the structural formula (T2) are particularly preferred. These polyfunctional thiols can be used singly or in combination of plural kinds.

[Chemical Formula 17]

When the coloring composition of the present invention contains a polyfunctional thiol, the content of the polyfunctional thiol compound is preferably from 0.3 to 8.9% by mass, more preferably from 0.8 to 6.4% by mass, based on the total solid content of the coloring composition. Further, the polyfunctional thiol may be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like.

<<Photopolymerization initiator>> The coloring composition of the invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferred that the ultraviolet region has a sensitivity to visible light. Further, it may be an active agent which generates a living radical by some action with a photo-stimulated sensitizer, or may be an initiator which initiates cationic polymerization depending on the kind of the monomer. Further, the photopolymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 moles in a range of from about 300 nm to 800 nm (more preferably from 330 nm to 500 nm).

Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton or a oxadiazole skeleton), a mercaptophosphine compound such as a mercaptophosphine oxide, a hexaarylbisimidazole, and an anthracene. An anthracene compound such as a derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, or a hydroxyacetophenone. Examples of the halogenated hydrocarbon compound having a triazine skeleton include the following compounds, such as those described in Bull. et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), and compounds described in British Patent No. 1,388,492. The compound described in JP-A-53-133428, the compound described in the specification of German Patent No. 3337024, and the compound described in J. Org. Chem.; 29, 1527 (1964) by FC Schaefer et al., JP-A-62-58241 The compound described in the Japanese Patent Publication No. Hei 5-281728, the compound described in JP-A-H05-34920, and the compound described in the specification of U.S. Patent No. 4,212,976.

Further, from the viewpoint of exposure sensitivity, it is selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a mercaptophosphine compound, a phosphine oxide compound, Metallocene compound, hydrazine compound, triallyl imidazole dimer, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivative thereof, cyclopentadiene-benzene-iron complex A compound of the group consisting of a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound is preferred.

a trihalomethyltriazine compound, an α-amino ketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, a benzophenone compound, and an acetophenone compound are Further preferably, at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an anthraquinone compound, a triallyl imidazole dimer, and a benzophenone compound is particularly preferred.

In particular, when the coloring composition of the present invention is used in the production of a color filter of a solid-state image sensor, since it is necessary to form a fine pattern in a tapered shape, it is important to develop the hardenability and the manner in which no residue is formed in the unexposed portion. . From such a viewpoint, it is particularly preferable to use a ruthenium compound as a photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state image sensor, exposure is performed by a stepper in exposure for curing. However, the exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator. In view of this, in the case of forming a fine pattern such as a solid-state image sensor, it is particularly preferable to use a ruthenium compound as a photopolymerization initiator. Further, the transferability can be better optimized by using a ruthenium compound. Specific examples of the photopolymerization initiator can be referred to, for example, in paragraphs 0265 to 0268 of JP-A-2013-29760, which is incorporated herein by reference.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be suitably used. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969 and a mercaptophosphine-based initiator described in Patent No. 4,258,899 can be used. As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade name: all manufactured by BASF Corporation) can be used. As the amino acetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF Corporation) which are commercially available can be used. The amine acetophenone-based initiator may also be a compound described in JP-A-2009-191179, which has an absorption wavelength matched with a long-wavelength light source such as 365 nm or 405 nm. As the mercaptophosphine-based initiator, commercially available products IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF Corporation) can be used.

As the photopolymerization initiator, a ruthenium compound can be more preferably mentioned. As a specific example of the ruthenium compound, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166 can be used. In the present invention, examples of the ruthenium compound which can be suitably used include 3-benzylideneoxyimidobutan-2-one and 3-ethyloxyiminobutan-2-one. 3-propenyloxyimidobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxyimino-1-phenylpropane-1- Ketone, 2-benzylideneoxyimido-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2one, and 2-ethoxycarbonyloxyl Iminoamino-1-phenylpropan-1-one and the like. Also, JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, and Japanese specials are also mentioned. The compound described in each of the publications such as JP-A-2000-80068, JP-A-2000-80068, and JP-A-2006-342166, and JP-A-2006-342166. In the commercial product, IRGACURE-OXE01 (manufactured by BASF Corporation) and IRGACURE-OXE02 (manufactured by BASF Corporation) can also be suitably used. Further, TR-PBG-304 (manufactured by Changzhou Strong Electronic New Material Co., Ltd.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used.

In addition, as the ruthenium compound other than the above, a compound described in Japanese Patent Laid-Open Publication No. 2009-519904, which is linked to the N-position of the carbazole, and No. 7626957 in which a hetero substituent is introduced at the benzophenone site may be used. The compound described in the specification, the compound described in the specification of the Japanese Patent Laid-Open Publication No. 2010-15025, and the ketone described in the specification of the Japanese Patent Laid-Open Publication No. 2009-292039, and the ketone described in the publication No. 2009-131189. The ruthenium compound, the compound described in the specification of U.S. Patent No. 7,569,910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has a maximum absorption at 405 nm, and has a good sensitivity to a g-line light source, and Japanese Laid-Open Patent Publication No. 2009-221114 The compound or the like described. For example, it is preferable to refer to paragraphs 0274 to 0725 of JP-A-2013-29760, which is incorporated herein by reference. Specifically, as the hydrazine compound, a compound represented by the following formula (OX-1) is preferred. Further, in the ruthenium compound, the N-O bond of ruthenium may be a ruthenium compound of the (E) form, and the N-O bond of ruthenium may be a ruthenium compound of the (Z) form, or may be a mixture of the (E) form and the (Z) form.

[Chemical Formula 18]

In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. In the formula (OX-1), as a monovalent substituent represented by R, a monovalent non-metal atomic group is preferred. The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the above substituent may be further substituted with another substituent. The substituent may, for example, be a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group or an aryl group. In the formula (OX-1), as the one-valent substituent represented by B, an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferred. These groups may have one or more substituents. The substituent may be exemplified as the substituent. In the formula (OX-1), as the divalent organic group represented by A, an alkylene group having a carbon number of 1 to 12, a cycloalkylene group or an alkynylene group is preferred. These groups may have one or more substituents. The substituent may be exemplified as the substituent.

The present invention can also use a ruthenium compound having a fluorine atom as a photopolymerization initiator. Specific examples of the ruthenium compound having a fluorine atom include the compounds described in JP-A-2010-262028, and the compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471 Compound (C-3) or the like described in the publication. This content is incorporated in this specification.

In the present invention, as the photopolymerization initiator, a ruthenium compound having a nitro group can be used. Specific examples of the ruthenium compound having a nitro group include those described in paragraphs 0031 to 0047 of JP-A-2013-114249 and paragraphs 0008 to 0102 and 0070 to 0079 of JP-A-2014-137466. Compound and ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

The present invention can also use a compound represented by the following formula (1) or (2) as a photopolymerization initiator. [Chemical Formula 19]

In the formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or An aralkyl group having 7 to 30 carbon atoms. When R ¹ and R ² are a phenyl group, the phenyl groups may be bonded to each other to form a fluorenyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or a carbon atom. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group. .

^{(2), R 1, 1, R 2} , R 3 , and R is the same formula R ^2, R ³ and R meanings formula R (1) ⁴ of ^4, R ⁵ represents -R ^6, -OR ^6, -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, halogen atom or Hydroxy group, R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms. X represents a direct bond or a carbonyl group, and a represents an integer of 0-4.

In the above formulas (1) and (2), R ¹ and R ² are each independently a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclohexyl group or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. It is preferred that X is a direct bond. Specific examples of the compound represented by the formula (1) and the formula (2) include, for example, the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated in this specification.

Specific examples of the ruthenium compound which is preferably used in the present invention are shown below, but the present invention is not limited thereto. [Chemical Formula 20]

The ruthenium compound is preferably one having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably having a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably having a higher absorbance at 365 nm and 405 nm. Among the ruthenium compounds, from the viewpoint of sensitivity, the molar absorption coefficient at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and particularly preferably from 5,000 to 200,000. The molar absorption coefficient of the compound can be measured by a known method, for example, using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Company), and using an ethyl acetate solvent, preferably measured at a concentration of 0.01 g/L. . The photopolymerization initiator to be used in the present invention may be used in combination of two or more kinds as needed.

The content of the photopolymerization initiator is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, even more preferably from 1 to 20% by mass, based on the total solid content of the coloring composition. Within this range, better sensitivity and pattern formation can be obtained. The colored composition of the present invention may contain only one kind of photopolymerization initiator, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

<<Pigment Derivative>> The coloring composition of the present invention preferably contains a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of the organic pigment is substituted by an acidic group, a basic group or a phthalimine methyl group. As the pigment derivative, a pigment derivative having an acidic group or a basic group is preferable from the viewpoint of dispersibility and dispersion stability. Pigment derivatives having a basic group are particularly preferred.

Examples of the organic pigment constituting the pigment derivative include a diketopyrrolopyrrole pigment, an azo pigment, a phthalocyanine pigment, an anthraquinone pigment, a quinacridone pigment, and a dioxazine pigment. A purple ring ketone pigment, an anthraquinone pigment, a thioindole pigment, an isoporphyrin pigment, an isoindolinone pigment, a quinophthalone pigment, a Shilin pigment, a metal complex pigment, and the like. Further, as the acidic group of the pigment derivative, a sulfonic acid group, a carboxylic acid group and a salt thereof are preferable, and a carboxylic acid group and a sulfonic acid group are further preferable, and a sulfonic acid group is particularly preferable. As the basic group of the pigment derivative, an amine group is preferred, and a tertiary amine group is particularly preferred.

The content of the pigment derivative in the colored composition of the present invention is preferably from 1 to 30% by mass based on the total mass of the pigment. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, and more preferably 19% by mass or less. The pigment derivative may be used alone or in combination of two or more.

<<Polymerization Inhibitor>> In the colored composition of the present invention, in order to prevent unnecessary thermal polymerization of the polymerizable compound during production or storage of the colored composition, it is desirable to add a small amount of a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4'-sulfur. Di-bis(3-methyl-6-tert-butylphenol), 2,2'-methyl bis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine first Salt and so on. In the case where the coloring composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably from about 0.01 to 5% by mass based on the total solid content of the coloring composition. The colored composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types of polymerization inhibitors are contained, the total amount thereof is preferably in the above range.

<<Interfacial Active Agent>> From the viewpoint of further improving the coatability, various surfactants may be added to the colored composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.

For example, when a coating liquid is prepared by containing a fluorine-based surfactant, liquid characteristics (especially fluidity) at the time of preparation of a coating liquid are further improved. In other words, when a film is formed using a coloring composition containing a fluorine-based surfactant, the wettability of the surface to be coated is reduced by reducing the interfacial tension between the surface to be coated and the coating liquid. It is improved and the coating property to the coated surface is improved. Therefore, even when a film having a thickness of about several μm is formed with a small amount of liquid, it is more effective to form a film having a small thickness unevenness and a uniform thickness.

The fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, and particularly preferably from 7 to 25% by mass. The fluorine-containing surfactant having a fluorine content in this range is effective in thickness uniformity and liquid-saving property of the coating film, and the solubility in the colored composition is also good.

Examples of the fluorine-based surfactant include MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F141, MEGAFAC F142, MEGAFAC F143, MEGAFAC F144, MEGAFAC R30, MEGAFAC F437, MEGAFAC F475, and MEGAFAC F479. , MEGAFAC F482, MEGAFAC F554, MEGAFAC F780, MEGAFAC F781, MEGAFAC F781 (above, manufactured by DIC Corporation); FLUORAD FC430, FLUORAD FC431, FLUORAD FC171 (above, manufactured by SUMITOMO 3M Limited); SURFLON S-382, SURFLON SC-101, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC1068, SURFLON SC-381, SURFLON SC-383, SURFLON S393, SURFLON KH-40 (above, manufactured by ASAHI GLASS CO., LTD.); PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), and the like. A block polymer can also be used as the fluorine-based surfactant. Specific examples thereof include a compound described in JP-A-2011-89090.

The fluorine-based surfactant can also preferably use a repeating unit derived from a (meth) acrylate compound having a fluorine atom and have two or more (more preferably 5 or more) alkoxy groups (vinyloxy group, propylene) The fluorine-containing polymer compound having a repeating unit derived from a (meth) acrylate compound, which is preferably an oxy group, is exemplified as the fluorine-based surfactant used in the present invention. [Chemical Formula 21] The weight average molecular weight of the above compound is preferably from 3,000 to 50,000, for example, 14,000. In the above compounds, the % of the ratio of each repeating unit is based on mass%. The fluorine-based surfactant can also use a fluorine-containing polymer having an ethylenically unsaturated group in a side chain as a fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A-2010-164965. For example, MEGAFAC RS-101, RS-102, RS-718K, and the like are manufactured by DIC Corporation.

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and the like, and ethoxylates (for example, propoxylated glycerol, ethoxylated). Glycerin, etc., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol Laurate, polyethylene glycol distearate, sorbitan fatty acid ester (PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2, TETRONIC 304, 701, 704, 901, 904 manufactured by BASF Corporation) 150R1), SOLSPERSE 20000 (LUBRIZOL JAPAN, LTD.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, PIONIN D-6112-W, D- 6315 (manufactured by TAKEMOTO OIL & FAT CO., LTD.), OLEFIN E1010, SURFYNOL 104, 400, 440 (manufactured by Nissin Chemical Industries, Ltd.), and the like.

Specific examples of the cation-based surfactant include an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and a (meth)acrylic (co)polymer POLYFLOW No. 75 and No. 90. , No. 95 (manufactured by KYOEISHA CHEMICAL CO., LTD.), W001 (manufactured by YUSHO CO., LTD.), and the like.

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by YUSHO CO., LTD.).

Examples of the anthrone-based surfactants include "TORAY SILICONE DC3PA", "TORAY SILICONE SH7PA", "TORAY SILICONE DC11PA", "TORAY SILICONE SH21PA", and "TORAY SILICONE SH28PA" manufactured by DOW CORNING TORAY CO., LTD. "TORAY SILICONE SH29PA", "TORAY SILICONE SH30PA", "TORAY SILICONE SH8400"; MOMENTIVE PERFORMANCE MATERIALS Inc. manufactures "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452"; "KP341", "KF6001", "KF6002" manufactured by Shin-Etsu Chemical Co., Ltd.; "BYK307", "BYK323", "BYK330" and the like manufactured by BYK Chemie CO., LTD.

In the case where the coloring composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the coloring composition. The colored composition of the present invention may contain only one type of surfactant, or may contain two or more types. In the case where two or more kinds of surfactants are contained, the total amount thereof is preferably in the above range.

<<Other Additives>> In the colored composition of the present invention, various additives can be blended as needed. Various additions can be appropriately selected depending on the use. For example, in the case of a colored composition for color filter formation, a filler, an antioxidant, an ultraviolet absorber, a coagulation inhibitor, or the like can be blended as another additive. Examples of such additives include the additives described in paragraphs 0155 to 0156 of JP-A-2004-295116, the contents of which are incorporated herein by reference. Further, when the colored composition of the present invention is used as an ink composition for inkjet or a composition for printing ink, it can be further blended with a lubricant, a filler, an antifoaming agent, a gelling agent, and thickening as other additives. Agent, specific resistance adjusting agent, film forming agent, ultraviolet absorber, antioxidant, anti-fading agent, anti-mold agent, rust inhibitor, and the like. As such additives, the additives described in paragraphs 0163 to 0170 of JP-A-2014-24980 can be mentioned, and the contents are incorporated in the present specification.

The content of the second group element (calcium, magnesium, etc.) in the coloring composition is 50 ppm or less, from the viewpoint of suppressing occurrence of defects or the like, depending on the raw material to be used. Preferably, it is preferred to control to 0.01 to 10 ppm. Further, the amount of the inorganic metal salt in the colored composition is preferably 100 ppm or less, and more preferably 0.5 to 50 ppm.

<Method for Preparing Colored Composition> The colored composition of the present invention can be produced by mixing the above components. In the production of the colored composition, the respective components may be blended in the entirety, or the components may be successively mixed after being dissolved and dispersed in a solvent. In the method for producing a colored composition of the present invention, when a resin (resin A) selected from at least one of an acidic group and a basic group is present, a step of dispersing the pigment body (dispersion step) is preferred. The above dispersion step can be carried out by further adding a solvent and/or a pigment derivative as needed. The dispersion step can be carried out using a dispersing device such as a bead mill.

Further, when two or more kinds of pigment bodies are contained, in the case where the resin A is present, the colored composition of the present invention can be produced by simultaneously dispersing a plurality of pigment bodies. In other words, it is possible to produce by mixing two or more kinds of pigment bodies with the resin A and simultaneously dispersing a plurality of pigment bodies. Since the pigment body used in the colored composition of the present invention has a metal oxide on at least a part of the surface of the organic pigment, the surface state of the organic pigment can be made almost the same regardless of the type of the organic pigment. Thereby, even if a plurality of pigment bodies are simultaneously dispersed, the difference in dispersion of the respective pigment bodies is less likely to occur, and a coloring composition excellent in dispersion stability can be obtained. Further, the dispersion step can be carried out in the form of a pigment, and a composition (dispersion) in which each pigment body is dispersed can be mixed and produced.

The resin A used in the dispersion step may be one type or two or more types. From the viewpoint of dispersion stability, only one type is preferable. When two or more types are used, the resin A is preferably composed of only an acidic resin or a basic resin alone. Further, the difference between the SP values of the resins A is preferably 6 (J/cm ³ ) ^0.5 or less, and more preferably 0 to 5 (J/cm ³ ) ^0.5 . When the difference between the SP values of the resins A is within the above range, the dispersion stability of the pigment body can be improved. Further, when a solvent is used in the dispersion step, the solvent may be used alone or in combination of two or more. When two or more kinds are used, the difference between the SP values of the solvents is preferably 6 (J/cm ³ ) ^0.5 or less, more preferably 0 to 5 (J/cm ³ ) ^0.5 . When the difference in SP value is within the above range, the dispersion stability of the pigment body can be improved. Further, the difference between the SP values of the resin A and the solvent is preferably 6 (J/cm ³ ) ^0.5 or less, and more preferably 0 to 5 (J/cm ³ ) ^0.5 .

The coloring composition of the present invention is obtained by adding a component such as a polymerizable compound or a photopolymerization initiator to the composition (dispersion liquid) after the dispersion step. The other components may be uniformly compounded, or may be successively blended after dissolving and dispersing the components in a solvent. Further, the order of input and the working conditions in the case of blending the respective components are not particularly limited. For example, the coloring composition may be prepared by dissolving and dispersing the total component in a solvent at the same time, and if necessary, each component may be appropriately used as a solution or a dispersion of two or more kinds, and when it is used (at the time of coating), the components may be used. Mix to prepare a colored composition.

In the method for producing a colored composition of the present invention, it is preferred to filter with a filter for the purpose of removing foreign matter and reducing defects. The filter can be used without any particular limitation as long as it is used by a user for filtration or the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon-6 or nylon-6,6, or a polyolefin resin such as polyethylene or polypropylene (PP) may be used (including high density and super High molecular weight) filter. Among these raw materials, polypropylene (containing high density polypropylene) is preferred. The pore diameter of the filter is preferably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. By setting this range, it is possible to reliably remove fine foreign matter which hinders preparation of a uniform and smooth coloring composition in the subsequent step.

When using a filter, it is also possible to combine different filters for use. At this time, the filtration by the first filter may be performed only once, or may be performed twice or more. Further, the first filter having a different pore diameter may be combined within the above range. The aperture here can be found in the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL LTD., ADVANTECH TOYO KAISHA, LTD., NIHON ENTEGRIS K.K. (formerly Mykrolis Corporation) or KITZ MICROFILTER CORPORATION. The second filter can be formed of the same material or the like as the first filter described above. For example, the filtration by the first filter can be performed only by the dispersion, and after the other components are mixed, the filtration by the second filter is performed.

The colored composition of the present invention is preferably used for forming a colored layer of a color filter because it can form a cured film having good light resistance, transfer property, and flatness. Further, the colored composition of the present invention can be preferably used for a solid-state imaging device such as a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS), and a color filter used in an image display device such as a liquid crystal display device. The coloring pattern of a light sheet or the like is used for forming. When the coloring composition of the present invention is used as a color filter forming application, it is preferred to further contain a polymerizable compound and a photopolymerization initiator.

Further, the coloring composition of the present invention can also be preferably used as an ink composition for inkjet. Here, the inkjet means that an ink composition pressurized by a pump or a piezoelectric element is sprayed onto a substrate object from a nozzle hole to form an image.

Preferred physical properties of the ink composition for ink jet are as follows. A surface tension of 20 to 60 mN/m is preferred. More preferably, it is 20 to 45 mN/m, and further preferably 25 to 35 mN/m. The surface tension was measured using a Wilhelmy type surface tension meter at 23 ° C and a relative humidity of 55%. The viscosity is preferably 1.2 to 8.0 mPa·s, more preferably 1.5 to 6.0 mPa·s, and still more preferably 1.8 to 4.5 mPa·s. Further, the measurement of the above viscosity was carried out at 23 ° C. The solid content concentration is preferably 5 to 60% by mass, more preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass.

The inkjet ink composition may also be an active energy ray-curable composition. The components used in the ink composition for inkjet, the inkjet device, and the image forming method using the inkjet ink composition can be described in JP-A-2015-151430 and JP-A-2012-177026. The content is incorporated into this specification.

Further, the coloring composition of the present invention can be preferably used as a printing ink composition. The printing method which can be applied is not particularly limited, and examples thereof include lithography, gravure printing, screen printing, and the like.

<Color Filter, Pattern Forming Method, and Method of Manufacturing Color Filter> Next, the color filter, the pattern forming method, and the method of producing the color filter of the present invention will be described in detail. Further, a method of manufacturing a color filter using the pattern forming method of the present invention will also be described.

The color filter of the present invention is formed by using the colored composition of the present invention. In the pattern forming method, it is preferred to form the colored composition layer on the support by using the colored composition of the present invention, and to remove the unnecessary portion to form a colored pattern. The pattern forming method can be preferably applied to the colored pattern forming the color filter. The pattern forming method may be patterned by a so-called photolithography method or may be patterned by a dry etching method. That is, a first preferred aspect of the method for producing a color filter of the present invention comprises the steps of forming a colored composition layer on a support using the colored composition of the present invention; and exposing the colored composition layer to a pattern And a step of developing the colored pattern by developing and removing the unexposed portion. A step of baking the colored composition layer (prebaking step) and a step of baking the developed color pattern (post baking step) may also be provided as needed. Further, a second preferred aspect of the method for producing a color filter of the present invention comprises the steps of forming a colored composition layer on a support and forming a colored layer by using the colored composition of the present invention; a step of forming a photoresist layer on the colored layer; a step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and using the resist pattern as an etch mask to dry-etch the colored layer to form a colored pattern The steps. The color filter of the present invention can be suitably obtained by the above production method. Hereinafter, the details will be described.

<<Step of Forming Colored Composition Layer>> In the step of forming the colored composition layer, a colored composition layer is formed on the support using the colored composition of the present invention.

As the support, for example, a substrate for a solid-state imaging device in which a solid-state imaging device (light-receiving element) such as a CCD or a CMOS is provided on a substrate (for example, a germanium substrate) can be used. The colored pattern in the present invention may be formed on the solid-state imaging device forming surface side (surface) of the solid-state imaging device substrate, or may be formed on the solid-state imaging device non-forming surface side (back surface). In order to improve the adhesion to the upper layer, prevent the diffusion of the substance, or achieve planarization of the surface of the substrate, an undercoat layer may be provided on the support as needed.

As a method of applying the coloring composition of the present invention to a support, various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be used.

The drying (prebaking) of the colored composition layer applied to the support can be carried out using a hot plate, an oven or the like at 50 to 140 ° C for 10 to 300 seconds.

<<Exposure Step>> Next, the colored composition layer formed on the support is exposed to a pattern (exposure step). For example, the colored composition layer formed on the support can be exposed to a pattern by exposure using a mask having a predetermined mask pattern by using an exposure device such as a stepping machine. Thereby, the exposed portion can be hardened. As the radiation (light) which can be used for exposure, it is preferable to use ultraviolet rays such as g-line or i-line (i-line is particularly preferable). The irradiation amount (exposure amount) is preferably, for example, 30 to 1,500 mJ/cm ² , more preferably 50 to 1000 mJ/cm ^{2 , and most} preferably 80 to 500 mJ/cm ² .

The film thickness of the cured film is preferably 2.0 μm or less, more preferably 1.0 μm or less, and further preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, and can be 0.2 μm or more. By setting the film thickness to 2.0 μm or less, it is easy to obtain high resolution and high adhesion.

<<<Pattern Forming Step>> Next, the unexposed portion is developed and removed to form a colored pattern (pattern forming step). The development removal for the unexposed portion can be performed using a developer. Thereby, the colored composition layer of the unexposed part in the exposure step is eluted in the developing solution, and only the portion where the light is hardened remains. As the developer, an organic alkaline developer which does not damage the solid image sensor and the circuit of the substrate is preferable. The temperature of the developer is preferably, for example, 20 to 30 °C. The development time is preferably from 20 to 180 seconds. Further, in order to improve the residue removal property, the developer may be repeatedly oscillated every 60 seconds for a plurality of times to supply a new developer.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, diethylene glycol amine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5,4 , 0]-7-undecene and other organic basic compounds. The alkaline aqueous solution obtained by diluting the alkaline agents with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developing solution. Further, an inorganic base may be used in the developer. As the inorganic base, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate or the like is preferable. Further, a surfactant may be used in the developer. Examples of the surfactant include a surfactant described in the above colored composition, and a nonionic surfactant is preferred. Further, in the case of using a developer composed of such an alkaline aqueous solution, it is generally washed (rinsed) with pure water after development.

After the development, it is preferred to carry out heat treatment (post-baking) after performing the drying. In order to form a multicolor coloring pattern, it is possible to repeat the steps for each color to produce a cured film. Thereby, a color filter can be obtained. The post-baking is heat treatment after development for complete hardening, and the heating temperature is preferably 100 to 240 ° C, more preferably 200 to 240 ° C. The Young's modulus of the film of the film after post-baking is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa. The film after development can be post-baked in a continuous or batch manner using a heating means such as a hot plate or a convection oven (hot air circulation dryer) or a high-frequency heater.

The color filter of the present invention can be preferably applied to a solid-state imaging device such as a CCD or a CMOS, and is particularly preferably used in a high-resolution CCD, CMOS or the like exceeding 1 million pixels. The color filter of the present invention can be used, for example, as a color filter disposed between a light receiving portion constituting each pixel of a CCD or CMOS and a microlens for collecting light.

The coloring pattern (colored pixel) of the color filter of the present invention has a film thickness of preferably 2.0 μm or less, more preferably 1.0 μm or less, and further preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 0.2 μm or more. Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 0.2 μm or more.

In the case of forming a pattern by dry etching, the contents described in JP-A-2013-64993 can be referred to, and the contents are incorporated in the present specification.

<Solid-State Imaging Device> The solid-state imaging device includes the above-described color filter of the present invention. The configuration of the solid-state imaging device is not particularly limited as long as it is a configuration in which the color filter of the present invention is provided as a solid-state imaging device, and the following configuration is exemplified.

A plurality of photodiodes constituting a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode made of a polycrystalline silicon or the like are provided on the support, and the photoelectric The polarizer and the transfer electrode have a light-shielding film made of tungsten or the like which opens only the light-receiving portion of the photodiode, and the light-shielding film is formed to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. A device protective film made of tantalum nitride or the like has the color filter of the present invention on the device protective film.

Further, it may be configured to have a light collecting means (for example, a microlens or the like, the same below) on the protective layer of the device and on the lower side of the color filter (the side close to the support), or may have a color filter. The composition of the concentrating mechanism, and the like.

Further, the color filter may have a configuration in which a cured film forming a pixel of each color is embedded in a space partitioned into a square shape via a spacer, for example. In this case, the pixel spacer with respect to each color is preferably a low refractive index. An example of the image pickup apparatus having such a configuration is the apparatus described in Japanese Laid-Open Patent Publication No. 2012-227478, and the Japanese Patent Publication No. JP-A-2014-179577.

<Image display device>

The color filter of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device. In particular, the use for a liquid crystal display device is preferred. The liquid crystal display device including the color filter of the present invention can display a high-definition image in which the color of the displayed image is good and the display characteristics are excellent.

The definition of the image display device and the details of each image display device are described, for example, in "Electronic display device (Kogyo Chosakai Publishing Co., Ltd., issued in 1990)", "Display device (Ibukishun) Zhang, Sangyo Tosho Co., Ltd., released in the first year of Heisei) and so on. Further, the liquid crystal display device is described, for example, in "Next-Generation Liquid Crystal Display Technology (Edited by Kogyo Chosakai Publishing Co., Ltd., 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next-generation liquid crystal display technology".

The color filter of the present invention can also be used in a liquid crystal display device of a color TFT (Thin Film Transistor) type. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (KYORITSU SHUPPAN CO., LTD., issued in 1996)". In addition, the present invention is also applicable to a liquid crystal display device in which a viewing angle such as a horizontal electric field driving method such as IPS (In Plane Switching) or a pixel division method such as MVA (Multi-domain Vertical Alignment) is expanded, or STN (Super-Twist Nematic). ), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Optically Compensated Bend). Moreover, the color filter of the present invention can also be provided in a bright and high-resolution COA (Color-filter On Array) method. In the COA liquid crystal display device, in addition to the usual required characteristics as described above, the required characteristics of the color filter layer may be required for the interlayer insulating film, that is, the low dielectric constant and the peeling liquid resistance. . Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA liquid crystal display device having high resolution and long-term durability. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin coating may be provided on the color filter layer. These image display methods are described, for example, on page 43 of "EL, PDP, LCD Display - Technology and Market Trends - (Toray Research Center, Inc. Survey and Research Department, issued in 2001)".

The liquid crystal display device including the color filter of the present invention comprises, in addition to the color filter of the present invention, an electrode substrate, a polarizing film, a retardation film, a backlight device, a spacer, and a viewing angle compensation film. . The color filter of the present invention can be applied to a liquid crystal display device composed of such known members. These components are described, for example, in "94 Markets for Liquid Crystal Display Peripherals and Chemical Products (issued by Kanda Co., Ltd., CMC CO., LTD.)", "2003 Current Status and Future Prospects of Liquid Crystal Related Markets (Vol. 2)" "FUJI CHIMERA RESEARCH INSTITUTE, INC., issued in 2003)". The backlight is described in SID meeting Digest 1380 (2005) (A. Konno et. al), monthly publication December 2005, pages 18 to 24 (Island Kang Yu), monthly publication, December 2005 issue, 25 to 30 pages. (Yamamu Longming) and so on.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a conventional three-wavelength tube of a cold cathode tube, and red, green, and blue diodes can be used. As a backlight, the (LED) light source can provide a liquid crystal display device having high brightness and high color reproducibility. [Examples]

Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the invention is not limited to the specific examples shown below. In addition, unless otherwise indicated, "part" and "%" are mass standards. Further, the dispersion liquid containing the pigment body and the dispersion liquid containing the pigment are collectively referred to as a pigment dispersion liquid hereinafter.

<Measurement of Weight Average Molecular Weight> The weight average molecular weight was measured by the following method. Column type: Column TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000 and TOSOH TSKgel Super HZ2000 Development solvent: Tetrahydrofuran Column temperature: 40 °C Flow rate (sample injection amount): 1.0 μL (sample concentration: 0.1 mass) %) Device name: HLC-8220GPC manufactured by TOSOH Corporation Detector: RI (refractive index) detector calibration curve Base resin: polystyrene

<Viscosity measurement> The viscosity of the sample was measured by adjusting the sample temperature to 23 ° C using an E-type viscometer "TV-20 type viscometer / cone type TVE-20L" (manufactured by TOKI SANGYO CO., LTD.).

<Production of Pigment Body P1 to P10> A mixture of 100 parts by mass of the organic pigment shown in Table 1 and 10 parts by mass of ethyl decanoate and 90 parts by mass of methanol was stirred at 0 ° C for 10 hours, and then stirred at 20 ° C for 20 hours. hour. The solid component was collected by filtration, dried at 25 ° C for 24 hours, dried at 100 ° C for 10 hours, and dried at 200 ° C for 1 hour, and then pulverized to obtain a pigment body in which an organic pigment was coated with SiO ₂ .

【Table 1】 The symbols in the table are as follows. PR254 : CI Pigment Red 254 PR177 : CI Pigment Red 177 PY150 : CI Pigment Yellow 150 PY139 : CI Pigment Yellow 139 PY185 : CI Pigment Yellow 185 PG36 : CI Pigment Green 36 PG7 : CI Pigment Green 7 PG58 : CI Pigment Green 58 PB15: 6: CI Pigment Blue 15:6 PV23: CI Pigment Violet 23

<Test Example 1> A zirconia bead having a diameter of 0.3 mm was used, and a bead mill (further using a high-pressure disperser NANO-3000-10 (manufactured by NIHON BEECO., LTD.) with a pressure-reducing mechanism) was used. The mixed liquid of the composition was mixed for 1 to 10 hours to prepare a pigment dispersion liquid using the pigment coated with SiO ₂ described in Tables 2 to 4 and a pigment dispersion liquid using the pigment not coated with SiO ₂ described in Table 5; . In addition, the viscosity is measured every one hour from the start of mixing by the bead mill. The numerical values in the table indicate parts by mass. Further, the values of P1 to P10 and the resins 1, 2, 4, and 5 are values in terms of solid content.

【Table 2】 【table 3】 【Table 4】 【table 5】

The materials shown in the table are as follows. P1 to P10: the above-mentioned pigment bodies P1 to P10 resin 1: the following structure (graft copolymer, weight average molecular weight 22900, SP value 23.8 (J/cm ³ ) ^0.5 , propylene glycol methyl ether acetate 20 mass% solution) [Chemical Formula 22] Resin 2: the following structure (graft copolymer, weight average molecular weight 10400, SP value 18.6 (J/cm ³ ) ^0.5 ) [Chemical Formula 23] Resin 4: manufactured by BYK Chemie CO., LTD. DISPERBYK-2164 (resin having a main skeleton of polyurethane and having a polyester or polyether chain in the side chain, SP value of 19.9 (J/cm ³ ) ^0.5 ) Resin 5: the following structure (poly Caprolactone resin, weight molecular weight 20900, SP value 19.6 (J/cm ³ ) ^0.5 ) [Chemical Formula 24] PGMEA: propylene glycol methyl ether acetate (SP value = 17.9 (J/cm ³ ) ^0.5 )

<Dispersion Appropriate Time> Using a zirconia bead having a diameter of 0.3 mm, the mixed liquid having the composition shown in Tables 2 to 5 was mixed in a bead mill for 1 to 10 hours. Further, the viscosity was measured at a constant interval from the start of mixing by the bead mill. The range from the minimum value of the viscosity at the time of dispersion of the mixed liquid to the Δ viscosity value of 10% or less was defined as the dispersion appropriate time, and the appropriate dispersion time was evaluated on the following basis. Δ viscosity value (%) = (viscosity measurement value of the mixed solution / viscosity minimum value at the time of dispersion of the mixed liquid) × 100 4: 3 hours or more 3: 1 hour or more and less than 3 hours 2: 20 minutes or more and less than 1 hour 1: less than 20 minutes

<Dispersion stability> Using a zirconia beads having a diameter of 0.3 mm, the mixed liquid having the composition shown in Tables 2 to 5 is dispersed in a time when the viscosity at the time of dispersion is minimized to produce a pigment dispersion liquid or Pigment dispersion. The obtained pigment body dispersion or pigment dispersion liquid was stored under the conditions of 23 ° C and a humidity of 45% for 1 month. Next, the viscosity change rate of the pigment dispersion liquid was measured, and the dispersion stability was evaluated on the following basis. Viscosity change rate = (viscosity after storage for 1 month / viscosity immediately after manufacture) × 100 4: viscosity change rate is 5% or less 3: viscosity change rate is more than 5% and less than 10% 2: viscosity change rate is greater than 10% and less than 15% 1: viscosity change rate is greater than 15%

<Heat resistance> A ZnO dispersion having a diameter of 0.3 mm was used, and the mixed liquid having the composition described in Tables 2 to 5 was dispersed in a time when the viscosity at the time of dispersion was minimized to produce a pigment dispersion liquid. The obtained pigment dispersion liquid was applied onto a glass substrate (1737 glass substrate, thickness: 0.7 mm, manufactured by Corning Incorporated), using a spin coater (manufactured by MIKASA CO., LTD), and the film thickness after drying was 0.6 μm. Using a hot plate, prebaking at 100 ° C for 2 minutes, and heating at 200 ° C for 5 minutes to produce a film (film before heat treatment). The obtained film was heated and treated at 260 ° C for 10 minutes using a hot plate (film after heat treatment). The spectral characteristics of the film before and after the heat treatment were measured using a MCPD3000 (manufactured by Otsuka Electronics Co., Ltd.) as a spectrometer, and the heat resistance was evaluated on the following basis. Further, the maximum spectral characteristic change rate is the largest among the spectral characteristic change rates in a certain wavelength region. Rate of change of spectral characteristics = (| (transmittance of film after heat treatment - transmittance of film before heat treatment) | / transmittance of film before heat treatment) × 100 Maximum wavelength in a wavelength range of 4:400 to 700 nm The characteristic change rate is 0.5% or less. In the wavelength range of 3:400 to 700 nm, the maximum spectral characteristic change rate is more than 0.5% and 0.8% or less. In the wavelength range of 2:400 to 700 nm, the maximum spectral characteristic change rate is greater than 0.8% and 1.5%. In the following 1:400 to 700 nm wavelength region, the maximum spectral characteristic change rate is greater than 1.5%

<Light resistance> Using a zirconia beads having a diameter of 0.3 mm, the mixed liquid composed of the compositions described in Tables 2 to 5 was dispersed in a time when the viscosity at the time of dispersion was minimized to produce a pigment dispersion liquid. The obtained pigment dispersion liquid was applied onto a glass substrate (1737 glass substrate, thickness: 0.7 mm, manufactured by Corning Incorporated), using a spin coater (manufactured by MIKASA CO., LTD), and the film thickness after drying was 0.6 μm. Using a hot plate, prebaking at 100 ° C for 2 minutes, and heating at 200 ° C for 5 minutes to produce a film (film before light irradiation treatment). The obtained film was irradiated with 10,000 lux of light by a xenon lamp through an ultraviolet cut filter for 100 hours (film after light irradiation treatment). The spectral characteristics before and after the light irradiation treatment were measured using a MCPD3000 (manufactured by Otsuka Electronics Co., Ltd.) as a spectrometer, and the light resistance was evaluated on the following basis. Further, the maximum spectral characteristic change rate is the largest among the spectral characteristic change rates in a certain wavelength region. Rate of change of spectral characteristics = (| (transmittance of film after light irradiation treatment - transmittance of film before light irradiation treatment) | / transmittance of film before light irradiation treatment) × 100 4: 400 to 700 nm in a wavelength region The maximum spectral characteristic change rate is 0.5% or less. In the wavelength range of 3:400 to 700 nm, the maximum spectral characteristic change rate is more than 0.5% and 0.8% or less. In the wavelength range of 2:400 to 700 nm, the maximum spectral characteristic change rate is greater than 0.8%. And the maximum spectral characteristic change rate is greater than 1.5% in the wavelength range of 1:400 to 700 nm below 1.5%.

As shown in the above table, the pigment body in the examples was excellent in dispersion stability and did not depend on the kind of the pigment. Further, the dispersion suitable time can be made longer. Further, a film excellent in heat resistance and light resistance can be formed.

On the other hand, in the comparative examples, the dispersion stability was different depending on the type of the pigment, and the dispersion stability was excellent in Comparative Examples R1-1, R1-2, and R1-4, but in Comparative Example R1-3 and Comparative Example R1-5, In Comparative Example R1-6, the dispersion stability was poor, and after 1 hour from the start of dispersion, it became a gel, and heat resistance and light resistance were not evaluated.

Further, in Comparative Examples R1-1, R1-2, and R1-4, at least one of heat resistance and light resistance was inferior.

The coloring composition obtained by adding a polymerizable compound, a photopolymerization initiator, and an alkali-soluble resin to the pigment dispersion liquid of Examples 1-1 to 1-10 is preferably used as a color filter. Further, the ink composition for inkjet and the ink composition for printing can be prepared by using the pigment dispersion liquids of Examples 1-1 to 1-10.

<Test Example 2>

Each of the pigment dispersion liquids was prepared by mixing a mixture of the compositions described in the following Table using zirconia beads having a diameter of 0.3 mm for 3 hours in a bead mill. The numerical values in the table indicate parts by mass. Further, the values of P1 to P10 and the resins 1 to 3 are values converted in terms of solid content.

[Table 10]

The materials shown in the table are as follows. P1 to P10: the above-mentioned pigment bodies P1 to P10 Resin 1, 2: Resin 1, 2 Resin 3: the following structure (graft copolymer, weight average molecular weight 11400, SP value 19.6 (J/cm ³ ) ^0.5 , propylene glycol A Ethyl ether acetate 20% solution) [Chemical Formula 25] PGMEA: propylene glycol methyl ether acetate (SP value = 17.9 (J/cm ³ ) ^0.5 ) cyclohexanone (SP value = 20.9 (J/cm ³ ) ^0.5 ) EEP: 3-ethoxypropionate ethyl ester ( SP value = 18.2 (J/cm ³ ) ^0.5 )

Each of the pigment dispersion liquids was mixed at a ratio shown in the following table, and the mixture was stirred in a stirrer at 60 rpm for 60 minutes to prepare a mixed liquid.

With respect to the obtained mixed liquid, the dispersion stability was evaluated in the same manner as in Example 1.

As shown in the above table, the dispersion stability was excellent in the examples.

<Test Example 3> Manufacturing of color filter

(Preparation of coloring composition A1)

The coloring composition A1 (the pigment body concentration was 38.58% by mass of the total solid content of the coloring composition) was prepared by stirring the ingredients shown below at 200 rpm for 30 minutes using a stirrer. The coloring composition A1 is not good in foreign matter.

Pigment dispersion liquid produced in Example 1-1 (solid content concentration: 25.0% by mass, pigment body concentration: 12.5% by mass): 64.9 g

Photopolymerization initiator (IRGACURE OXE01 by BASF): 0.49g

Polymerizable Compound 1 (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.): 1.74 g

Polymerizable Compound 2 (KAYARAD RP1040, manufactured by Nippon Kayaku Co., Ltd.): 0.68 g

Alkali-soluble resin (made by Daicel Corporation. CYCLOMER P) Body composition concentration 50% by mass): 3.42g

Surfactant (nonionic surfactant PIONIN D-6315 (TAKE MOTO OIL & FAT CO., LTD.): 0.18g

Solvent (propylene glycol monomethyl ether acetate (PGMEA)): 28.6g

(Preparation of coloring composition A2~A10)

In the preparation of the coloring composition A1, a method of preparing the coloring composition A1 is used in addition to the pigment dispersion liquids produced in Examples 1-2 to 1-10 instead of the pigment dispersion liquid produced in Example 1-1. The colored compositions A2 to A10 were prepared in the same manner. These colored compositions are not good for foreign matter.

(manufacture of color filters)

A base coating agent (CT-4000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied onto the ruthenium substrate, and heated at 220 ° C for 5 minutes to form a transparent underlayer having a thickness of 0.1 μm.

On the transparent underlayer, the colored composition layers A1 to A10 prepared above were used to form a colored composition layer, and prebaked at 100 ° C for 120 seconds to form a colored composition layer having a thickness of 0.6 μm. The colored composition layer was irradiated with an exposure amount of 350 mJ/cm ² by an i-line stepper exposure apparatus (FPA3000i5+, manufactured by Canon Inc.) and via an Island pattern mask. Next, a developing solution C D-2060 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was sprayed onto the ruthenium substrate using a straight nozzle, and a spin-on immersion development was performed for 60 seconds. Next, rinsing, spin drying, and post-baking treatment at 200 ° C for 5 minutes were performed to form an island pattern of 1.4 μm pattern tetragonal.

Regarding the pattern to be manufactured, the pattern outline and the development residue were confirmed. Even with any of the coloring compositions, the pattern is formed to be sharper and has good performance as a color filter. In addition, a pattern scanning electron microscope S9260 (manufactured by Hitachi High-Technologies Corporation) was used and pattern inspection was performed at a magnification of 20,000 times.

<Test Example 4> Inkjet ejection test A mixture of the following components was stirred for 10 minutes at 2,500 rotations/min using a stirrer (L4R manufactured by Silverson Co., Ltd.). Next, a bead mill disperser DISPERMAT LS (manufactured by VMA Corporation) was placed, and YZ balls (manufactured by Nikkato Corporation) having a diameter of 0.65 mm were used, and dispersion was performed at 2,500 rotations/min for 6 hours. Thus, a yellow mill base YM1 was prepared. Pigment body P4 29.7 parts SOLSPERSE 22000 (manufactured by LUBRIZOL JAPAN LTD.) 1.6 parts DISPERBYK-168 (solid content 30%, manufactured by BYK Chemie CO., LTD.) 28.0 parts SR339A (polymerizable compound, 2-phenoxyethyl acrylate) , manufactured by SARTOMER Company, Inc.) 39.7 parts of p-methoxyphenol (polymerization inhibitor) 1.0 part

The following ingredients were stirred for 15 minutes at 2,500 rotations/min using a stirrer (L4R manufactured by Silverson Co., Ltd.). Next, filtration was carried out using a cartridge filter manufactured by NIHON PALL LTD. (product name: profile II AB01A01014J). The yellow ink composition Y1 was thus obtained. Yellow mill base YM1 8 parts IRGACURE-184 (photopolymerization initiator, 1-hydroxycyclohexyl phenyl ketone, manufactured by BASF) 3 parts IRGACURE-TPO (photopolymerization initiator, 2,4,6-trimethyl Benzobenzyldiphenylphosphine oxide, manufactured by BASF Corporation, 9.5 parts CD420 (3,3,5-trimethylcyclohexyl ester, manufactured by SARTOMER Company, Inc.) 37.5 parts of NVC (polymerizable compound, N-ethylene) Base hexamethyleneamine, manufactured by BASF Corporation, 13.8 parts of SR395 (polymerizable compound, isoamyl acrylate, manufactured by SARTOMER Company, Inc.) 24.6 parts FIRSTCURE ITX (Zengmin Pigment, Isopropylthioxanthone, ChemFirst Inc.) Manufactured) 3.2 parts of p-methoxyphenol (polymerization inhibitor) 0.4 parts

An ink set composed of a yellow ink composition Y1, a magenta ink, a cyan ink, and a black ink (a magenta ink, a cyan ink, and a black ink are respectively UVijet KI ink series KI867, KI215, KI004 (manufactured by Fuji Film Speciality Ink Sytems)) 1 Filled in LuxelJet UV350GTW, a UV inkjet printer manufactured by Fujifilm Corporation, and printed a test image. After hardening, a dot pattern having no cracks, bleeding, or the like in the pattern is obtained.

Claims (19)

A coloring composition comprising: a pigment body having two or more kinds of metal oxides different from each other on at least a part of the surface of the organic pigment; and a resin having at least one selected from the group consisting of an acidic group and a basic group. The colored composition according to claim 1, wherein the metal oxide is an oxide of an element selected from the group consisting of Si, Al, Zr, and In. The colored composition according to claim 1, wherein the metal oxide is an oxide of Si. The coloring composition according to any one of claims 1 to 3, wherein the resin contains a graft copolymer. The colored composition according to any one of the first to third aspects of the invention, wherein the pigment body has 1 to 25 parts by mass of the metal oxide based on 100 parts by mass of the organic pigment. The coloring composition according to any one of the first to third aspects of the present invention includes two or more kinds of the pigment bodies different from each other, and two or more kinds of the pigment bodies different from each other contain organic pigments different from each other. The colored composition according to any one of the first to third aspects of the present invention includes two or more kinds of the pigment bodies different from each other, and each of the pigment bodies contains an oxide of Si. The colored composition according to any one of the first to third aspects of the present invention, wherein the resin contains two or more kinds of acidic resins or two or more kinds of basic resins. The colored composition according to any one of claims 1 to 3, wherein the resin contains a resin having a difference of two or more solubility parameters of 6 (J/cm ³ ) ^0.5 or less. The colored composition according to any one of claims 1 to 3, further comprising a polymerizable compound. The colored composition according to claim 10, further comprising a photopolymerization initiator. The colored composition according to any one of claims 1 to 3, further comprising a solvent. The coloring composition according to any one of the first to third aspects of the invention, wherein the two or more kinds of the pigment bodies are different from each other, and the two or more kinds of the pigment bodies are different from each other. At least a part of the surface of the organic pigment has the aforementioned metal oxide, and each of the metal oxides contains an oxide of Si. The colored composition according to any one of claims 1 to 3, which is used for a color filter. A method for producing a colored composition comprising the steps of dispersing two or more pigment bodies different from each other in the presence of a resin, wherein the resin has an acid selected from the group consisting of At least one of the group of the base and the basic group, at least a portion of the surface of the organic pigment of the pigment body is coated with a metal oxide. In the method for producing a colored composition according to claim 15, the two or more kinds of the pigment bodies are different from each other, and the two or more kinds of the pigment bodies are different from each other on the surface of the organic pigment. At least a part of the aforementioned metal oxides each contain an oxide of Si. A color filter using the coloring composition according to any one of items 1 to 14. A coloring composition according to any one of items 1 to 14, wherein the coloring composition according to any one of the items 1 to 14. A printing ink composition using the coloring composition according to any one of items 1 to 14.