JP2008088272A - Curable coloring composition, color filter, and liquid crystal display device using color filter - Google Patents

Abstract

【選択図】なしEven when a colorant is contained in a high concentration, the colorant has excellent dispersibility, suitability for slit coating, ink jet clogging, and good leveling of ink coating liquid. A curable coloring composition capable of forming a colored pixel portion having excellent flatness is provided.
A curable coloring composition containing a colorant, a dispersion resin, a polymerization initiator, a polymerizable compound, and a solvent, the solvent having (A) a boiling point at normal pressure. A solvent having a solubility parameter of 8.5 to 10.5 and a boiling point of 130 to 170 ° C. at normal pressure, the dispersion resin having the following general formula: A curable coloring composition comprising a polymer compound represented by (1) [R ¹ : (m + n) -valent organic linking group, R ² : single bond, divalent organic linking group, A ¹ : monovalent organic group having an organic dye structure or the like, m = 1 to 8, n = 2 to 9 (m + n = 3 to 10), P ¹ : polymer skeleton].

[Selection figure] None

Description

  The present invention relates to a curable coloring composition suitable for producing a color filter by a slit coating method and an ink jet method, a color filter produced using the curable coloring composition, and a production using the color filter. The present invention relates to a liquid crystal display device.

In recent years, with the increase in screen size of TVs and other devices, the size of pixels has increased, and production efficiency has advantages compared to the photolithographic method. Expected as a law, many methods are disclosed.
Further, color filters for TV use are required to have advanced color characteristics such as contrast, and finer organic pigments as colorants have been used.

As the above method, a resin composition for an ink jet color filter containing a solvent having a boiling point of 250 ° C. or higher, a binder resin, and a colorant is disclosed (for example, see Patent Document 1).
However, since the boiling point of the solvent to be used is too high, flatness in the drying process can be ensured, but since the binder resin has a high molecular weight, the viscosity is high and a stable discharge performance of the resin composition cannot be obtained.

Also, an aqueous color filter ink containing 60% by weight or more of a solvent having a boiling point of 150 to 250 ° C. and one or more of glycerin, diethylene glycol, and ethylene glycol is disclosed (see, for example, Patent Document 2). .
However, although the boiling point of the solvent is 150 ° C. to 250 ° C., those actually exemplified are PGMEA (boiling point 146 ° C.), EEP (boiling point 170 ° C.), and hydrophilic glycerin as a wetting agent. And the flatness of the colored layer was inferior.

Further, there is a method in which a thermosetting ink composition for a color filter containing a binder and an epoxy group-containing monomer is used as a first aspect, and a composition that defines wettability and specifies a solvent type is a second aspect. (For example, refer to Patent Document 3).
However, since it is an ink composition containing an ether bond, a solvent having an OH group or the like to ensure wettability to the substrate, or a solvent containing a diethylene glycol-based ether bond, the reliability as a color filter, for example, the pigment The dispersion stability was deteriorated.
Furthermore, an ink set for a color filter that is an active energy ray-curable ink containing a pigment containing R, G, and B, and a monofunctional and polyfunctional monomer is disclosed (for example, see Patent Document 4).
However, the dispersibility of the pigment as the colorant is not sufficient, and the performance (for example, contrast, etc.) when the color filter obtained using the ink set is made into a panel is inferior. In addition, there is a problem that clogging of the ink jet nozzle is likely to occur.

Even when such fine particles are used as the colorant, the nozzle tip of the inkjet is not clogged, and when the droplets adhere to the substrate, the leveling property of the ink coating liquid is good and the flatness is excellent. In addition, a method capable of forming a color filter pixel has been desired.
JP 2000-310706 A JP-A-11-202114 JP 2001-350012 A JP 2002-371216 A

The object of the present invention, which has been made in consideration of the problems in the prior art, is excellent in dispersibility of the colorant even when it contains a high concentration of the colorant, and is suitable for slit coating. An object of the present invention is to provide a curable coloring composition that is free from clogging, has good leveling properties of ink and coating liquid, and can form a colored pixel portion having excellent flatness.
Another object of the present invention is to provide a high-contrast color filter by a slit coating method or an inkjet method, and a liquid crystal display device using the same.

<1> A curable coloring composition containing a colorant, a dispersion resin, a polymerization initiator, a polymerizable compound, and a solvent, wherein the solvent has a boiling point of 180 at normal pressure (A). A solvent having a solubility parameter of 8.5 to 10.5 and a boiling point of 130 to 170 ° C. at normal pressure, and the dispersion resin is represented by the following general formula ( 1) a polymer containing a copolymer unit derived from a monomer represented by the following general formula (I), and a polymer containing a structural unit represented by the following general formula (a) A curable coloring composition comprising at least one selected from coalescence.

In general formula (1), R ¹ represents an (m + n) -valent organic linking group, and R ² represents a single bond or a divalent organic linking group. A ¹ is a monovalent organic group containing an organic dye structure or a heterocyclic ring, or an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms Represents a monovalent organic group having a group selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ¹ may be the same or different. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer skeleton.

In general formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (═O ) Represents one selected from S-, -OC (= O)-, -OCONH-, and -NHCO-. Y represents any one selected from NR ⁰³ , O, and S, and R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group. In the formula, N and Y are connected to each other to form a cyclic structure. m and n are each independently 0 or 1.

In general formula (a), R ^1a represents hydrogen or a methyl group, R ^2a represents an alkylene group, and Z ¹ represents a nitrogen-containing heterocyclic structure.
<2> The solvent (A) having a boiling point at normal pressure of 180 ° C. or higher and 280 ° C. or lower is selected from the compounds represented by the following general formula (i), general formula (ii), and general formula (iii) The curable coloring composition as described in <1>, wherein the curable coloring composition comprises 5% by mass to 80% by mass with respect to the total mass of the solvent contained in the curable coloring composition.
R ¹ —O— (C ₂ H ₄ O) _n —R ² general formula (i)
R ¹ —O— (C ₃ H ₆ O) _n —R ² general formula (ii)
R ¹ —O— (C ₄ H ₈ O) _n —R ² general formula (iii)

In general formula (i), general formula (ii), and general formula (iii), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an aralkyl group, Represents a carbonyl group. R ¹ and R ² do not represent a hydrogen atom at the same time. n represents an integer of 1 to 4.

<3> One or more selected from (meth) acrylic acid, maleic acid, maleic anhydride, and crotonic acid, and one selected from butyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene One or more types of alkali-soluble resins selected from the above-mentioned copolymers are 5% by mass to 50% by mass with respect to the total mass of the resin components including the dispersion resin. The curable coloring composition as described in 1> or <2>.
<4> The polymerization initiator contained in the curable coloring composition is a photopolymerization initiator, and the total solid content of the curable coloring composition is 10 with respect to the total amount of the curable coloring composition. The curable coloring composition according to any one of <1> to <3>, wherein the curable coloring composition is applied by a slit coating method.
<5> The polymerization initiator contained in the curable coloring composition is a thermal polymerization initiator, and the total solid content of the curable coloring composition is 25 with respect to the total amount of the curable coloring composition. The curable coloring composition according to any one of <1> to <3>, which is mass% to 60 mass% and is applied by an inkjet method.
<6> A color filter comprising a colored layer produced using the curable coloring composition according to any one of <1> to <5>.
<7> A liquid crystal display device comprising the color filter according to <6>.

Although the operation of the present invention is not clear, it is estimated as follows.
The curable coloring composition of the present invention has a boiling point in a predetermined range, and the dispersion resin in the present invention is used in combination with the solvent (A) and the solvent (B) having specific physical properties. In the curable coloring composition, the molecular chain spreads in the curable coloring composition, the adsorptivity to the pigment particles increases, and the molecular chains of the dispersed resin adsorbed on the pigment particles expand. Since the protective colloidal properties are improved and the dispersion stability of the pigment is improved, it is considered that a colored pixel portion having excellent storage stability and leveling property of the coating liquid and excellent flatness can be formed.

According to the present invention, even when the colorant is contained in a high concentration, the colorant is excellent in dispersibility, suitable for slit coating, no clogging of the inkjet nozzle, and ink and coating liquid. Therefore, it is possible to provide a curable coloring composition capable of forming a colored pixel portion having excellent leveling properties and excellent flatness.
In addition, according to the present invention, a high-contrast color filter by a slit coating method or an inkjet method, and a liquid crystal display device using the same can be provided.

Hereinafter, the curable coloring composition of the present invention, a color filter produced using the curable coloring composition, and a liquid crystal display device produced using the color filter will be described in detail.
[Curable coloring composition]
The curable coloring composition of the present invention is a curable coloring composition containing a colorant, a dispersion resin, a polymerization initiator, a polymerizable compound, and a solvent, wherein the solvent is (A) A solvent whose boiling point at normal pressure is 180 ° C. or higher and 280 ° C. or lower, and (B) a solvent whose solubility parameter is 8.5 to 10.5 and whose boiling point at normal pressure is 130 to 170 ° C., The dispersion resin is represented by a polymer compound represented by the following general formula (1), a polymer containing a copolymer unit derived from a monomer represented by the following general formula (I), and the following general formula (a). It contains at least one selected from polymers containing structural units.

In general formula (1), R ¹ represents an (m + n) -valent organic linking group, and R ² represents a single bond or a divalent organic linking group. A ¹ is a monovalent organic group containing an organic dye structure or a heterocyclic ring, or an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms Represents a monovalent organic group having a group selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ¹ may be the same or different. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer skeleton.

In general formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (═O ) Represents one selected from S-, -OC (= O)-, -OCONH-, and -NHCO-. Y represents any one selected from NR ⁰³ , O, and S, and R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group. In the formula, N and Y are connected to each other to form a cyclic structure. m and n are each independently 0 or 1.

In general formula (a), R ^1a represents hydrogen or a methyl group, R ^2a represents an alkylene group, and Z ¹ represents a nitrogen-containing heterocyclic structure.

  Hereinafter, the solvent, the dispersion resin, the colorant, the polymerizable compound, and the polymerization initiator, which are essential components of the curable coloring composition of the present invention, will be described.

<Solvent>
The solvent contained in the curable coloring composition of the present invention includes (A) a solvent having a boiling point of 180 ° C. or higher and 280 ° C. or lower at normal pressure, and (B) a solubility parameter of 8.5 to 10.5. And a solvent having a boiling point of 130 to 170 ° C. under pressure.
Below, each solvent is demonstrated.

((A) Solvent having a boiling point of 180 ° C. or higher and 280 ° C. or lower at normal pressure)
The curable coloring composition of the present invention contains (A) a solvent having a boiling point of 180 ° C. or higher and 280 ° C. or lower at normal pressure (hereinafter, appropriately referred to as “high boiling point solvent”).

  The high boiling point compound in the present invention must have a boiling point of 180 ° C. or higher and 280 ° C. or lower, preferably 190 ° C. or higher and 270 ° C. or lower, and most preferably 210 ° C. or higher and 250 ° C. or lower. . By containing the high boiling point solvent, it is possible to prevent the slit from being dried at the time of slit coating, to exhibit leveling properties after coating, and to prevent coating unevenness, coating stripes, and the like. Further, in the ink jet system, it is possible to prevent the nozzle from being dried and promote the flattening of the liquid after droplet ejection.

  Examples of the solvent having a boiling point of 180 ° C. or higher and 280 ° C. or lower at normal pressure include ester-based, ether-based, and ketone-based solvents, but it is not dispersed to have strong polar groups such as carboxylic acid residues. It is preferable from the viewpoint of stability.

  Among these, as the high boiling point solvent in the present invention, at least one selected from compounds represented by the following general formula (i), general formula (ii), and general formula (iii) is used as the curable coloring agent. It is preferable that 5 mass%-80 mass% is included with respect to the total mass of the solvent contained in a composition.

R ¹ —O— (C ₂ H ₄ O) _n —R ² general formula (i)
_{^{R 1 -O- (C 3 H 6}} O) n -R 2 Formula (i)
R ¹ —O— (C ₄ H ₈ O) _n —R ² general formula (iii)

In general formula (i), general formula (ii), and general formula (iii), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an aralkyl group, Represents an aryl group or a carbonyl group. R ¹ and R ² do not represent a hydrogen atom at the same time. n represents an integer of 1 to 4.

In the general formula (i) to general formula (iii), when R ¹ and R ² are represented by a linear or branched alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, n-propyl, i -Propyl, propenyl, n-butyl, sec-butyl, tert-butyl, other linear, branched saturated, unsaturated pentyl, hexyl, heptyl, octyl, pentenyl, hexenyl, octenyl groups, etc. Preferably, methyl, ethyl, i-propyl, n-butyl and the like can be mentioned.
In the general formula (i) to general formula (iii), when R ¹ and R ² are represented by an aralkyl group, for example, benzyl, o-methylbenzyl, m-methylbenzyl, p-methylbenzyl, phenethyl, etc. And preferably include phenyl and benzyl.
In the general formula (i) to general formula (iii), when R ¹ and R ² are each represented by an aryl group, examples thereof include phenyl, o-tolyl, m-tolyl, and p-tolyl.
In the general formula (i) to general formula (iii), when R ¹ and R ² are represented by a carbonyl group, examples thereof include acetyl, propionyl, propylcarbonyl, and the like.

Among these, when neither R ¹ nor R ² is a hydrogen atom, preferred examples include a methyl group, an ethyl group, a propyl group, a phenyl group and an acetyl group, or an acetyl group. When either R ¹ or R ² is a hydrogen atom, the substituent represented by the other that is not a hydrogen atom is preferably a methyl group, ethyl, propyl, phenyl or acetyl group.

Specific examples of the high boiling point solvent in the present invention are represented by the following (1) to (15).
(1) Diethylene glycol diethyl ether (boiling point 188 ° C)
(2) Diethylene glycol monoethyl ether acetate (boiling point 217 ° C.)
(3) Diethylene glycol monobutyl ether (boiling point 231 ° C.)
(4) Diethylene glycol monobutyl ether acetate (boiling point 247 ° C.)
(5) Propylene glycol n-propyl ether acetate (boiling point 187 ° C.)
(6) Propylene glycol diacetate (boiling point 190 ° C)
(7) Propylene glycol n-butyl ether acetate (boiling point 211 ° C.)
(8) Propylene glycol phenyl ether (boiling point 243 ° C.)
(9) Propylene glycol phenyl ether acetate (boiling point 258 ° C)
(10) Dipropylene glycol monomethyl ether acetate (boiling point 209 ° C.)
(11) Dipropylene glycol n-propyl ether acetate (boiling point 232 ° C.)
(12) Dipropylene glycol n-butyl ether acetate (boiling point 250 ° C.)
(13) Tripropylene glycol mono n-butyl ether (boiling point 274 ° C.)
(14) Tripropylene glycol methyl ether acetate (boiling point 263 ° C.)
(15) 1,3-butylene glycol diacetate (boiling point 232 ° C.)

  Among the (1) to (15), the (6), (7), (10), (11), (12), and (15) are particularly preferable.

In the case of the slit coating method, the content of the high boiling point solvent in the present invention is preferably 5% by mass to 80% by mass with respect to the total mass of the solvent in the curable coloring composition of the present invention. The content is more preferably from 60% by mass to 60% by mass, and particularly preferably from 5% by mass to 30% by mass. Moreover, in the case of an inkjet system, it is preferable to contain 5 mass%-80 mass%, and it is especially preferable that 20 mass%-80 mass% are contained. When the content of the high boiling point solvent is 5% by mass or more, the effect of suppressing clogging of nozzles and the like is exhibited. When the content of the high boiling point solvent is 80% by mass or less, the drying property of the coating film formed on the substrate is good, and the tact time in the coating process can be shortened.
The high boiling point solvents in the present invention may be used alone or in combination of two or more.

((B) Solvent having a solubility parameter of 8.5 to 10.5 and a boiling point of 130 to 170 ° C. at normal pressure)
The curable coloring composition of the present invention comprises (B) a solvent having a solubility parameter of 8.5 to 10.5 and a boiling point at normal pressure of 130 to 170 ° C. (hereinafter, appropriately referred to as “dispersed resin dissolving solvent”). Containing).

The solubility parameter is a solubility parameter calculated by the Fedors method (hereinafter referred to as “SP value” as appropriate), and the SP value of the solvent for dissolving the dispersed resin in the present invention is 8.5 to 10.5. Is more preferable, and 9.0-10.0 are more preferable.
The SP value in the present invention can be expressed by the following equation.
SP value (δ) = (ΔH / V) 1/2
In the formula, ΔH represents the heat of vaporization (cal), and V represents the molar volume (cm ³ ). ΔH and V are the total heat of molar evaporation (Δei) of the atomic group described in “POLYMER ENGINEERING AND SCIENCE, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (151-153)” The sum (V) of (ΔH) and molar volume (Δvi) can be used.

  In addition, the solvent for dissolving a dispersed resin in the present invention needs to have a boiling point of 130 ° C. to 170 ° C. at normal pressure in addition to the SP value having the above range. The boiling point at normal pressure is more preferably 140 ° C to 160 ° C. When the SP value of the solvent for dissolving the dispersed resin and the boiling point at normal pressure are in these ranges, head clogging is suppressed, dispersion stability is good, and storage stability is excellent.

  Examples of the solvent for dissolving the dispersion resin in the present invention include ester-based, ketone-based, and ether-based solvents. A compound having a structure in which one end of glycols such as ethylene glycol and propylene glycol has an ether bond and the other has an ester bond. Most preferred.

  Specific examples of the solvent for dissolving the dispersed resin in the present invention are shown in the following (1) to (12).

(1) Ethyl lactate (SP value 10.0, boiling point 154 ° C.)
(2) Ethyl 3-methoxypropionate (SP value 10.1, boiling point 158 ° C.)
(3) Ethyl 3-ethoxypropionate (SP value 8.8, boiling point 169 ° C.)
(4) Methyl 3-ethoxypropionate (SP value 9.3, boiling point 165 ° C.)
(5) Methyl 3-methoxypropionate (SP value 9.5, boiling point 145 ° C.)
(6) Methyl 2-ethoxypropionate (SP value 9.2, boiling point 162 ° C.)
(7) Ethyl cellosolve acetate (SP value 9.4, boiling point 156 ° C.)
(8) Isoamyl propionate (SP value 8.5, boiling point 160 ° C.)
(9) 2-Heptanone (SP value 8.8, boiling point 152 ° C.)
(10) Cyclohexanone (SP value 9.9, boiling point 156 ° C.)
(11) Propylene glycol monomethyl ether acetate (SP value 9.2, boiling point 146 ° C.)
(12) Propylene glycol ethyl ether acetate (SP value 9.1, boiling point 156 ° C.)

  Among the (1) to (12), the (1), (2), (3), (7), (10), (11), and (12) are more preferable, and the (1), (2), (3), (10), (11) and (12) are particularly preferred.

As a preferred combination of the (A) high boiling point solvent and the (B) solvent for dissolving the dispersed resin in the present invention, (A) the high boiling point solvent is propylene glycol diacetate, propylene glycol n-butyl ether acetate, dipropylene glycol monomethyl ether acetate. Dipropylene glycol n-propyl ether acetate, dipropylene glycol n-butyl ether acetate, and 1,3-butylene glycol diacetate. (B) Dispersing resin dissolving solvent is ethyl lactate, ethyl 3-methoxypropionate, 3- Ethyl ethoxypropionate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate.
As a particularly preferred combination, (A) the high boiling point solvent is at least one selected from the group of propylene glycol n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, and 1,3-butylene glycol diacetate, and (B) The solvent for dissolving the dispersion resin is a combination of ethyl lactate and propylene glycol monomethyl ether acetate.

In the case of the slit coating method, the content of the solvent for dissolving the dispersed resin in the present invention is preferably 5% by mass to 80% by mass with respect to the total mass of the solvent in the curable coloring composition of the present invention. The content is more preferably 5% by mass to 60% by mass, and particularly preferably 5% by mass to 30% by mass. Moreover, in the case of an inkjet system, it is preferable to contain 5 mass%-80 mass%, and it is especially preferable that 20 mass%-80 mass% are contained. When the content of the high boiling point solvent is 5% by mass or more, the effect of suppressing clogging of nozzles and the like is exhibited. When the content of the high boiling point solvent is 80% by mass or less, the drying property of the coating film formed on the substrate is good, and the tact time in the coating process can be shortened.
The high boiling point solvents in the present invention may be used alone or in combination of two or more.

In the present invention, the mass ratio of the (A) high boiling point solvent and the (B) solvent for dissolving the dispersed resin, and the solid content of the curable coloring composition of the present invention are preferable in the slit coating method and the inkjet method, respectively. Have a range.
In the case of the slit coating method, if the mass ratio of (A) the high boiling point solvent and (B) the solvent for dissolving the dispersed resin is (A) / (B) = 5/100 or more, drying of the slit nozzle, coating stripes, Generation of foreign matter can be suppressed. When the mass ratio of (A) high boiling point solvent and (B) solvent for dissolving dispersed resin is (A) / (B) = 40/100 or less, the coated substrate can be dried in a short time, and the coated substrate When the substrate is conveyed, the substrate is not bent, thickness unevenness due to the flow of the coating liquid is suppressed, and the uniformity of the film thickness is maintained. Moreover, 10 mass%-16 mass% are preferable with respect to the mass of the curable coloring composition of this invention, and content of the solid content contained in the curable coloring composition of this invention is 12 mass%-16 mass%. % Is more preferable. When the solid content is 10% by mass or more, dripping of the curable coloring composition from the slit opening can be prevented, and the drying load can be reduced. When the solid content is 16% by mass or less, the viscosity of the curable coloring composition of the present invention can be suppressed, the coating speed can be improved, and the tact time can be increased. Moreover, when forming a colored layer by a slit coating system, a photoinitiator is used suitably as a polymerization initiator contained in the curable coloring composition of this invention. This will be described in detail later.
In the case of the inkjet method, the leveling property after droplet ejection is good when the mass ratio of (A) high boiling point solvent and (B) solvent for dissolving dispersed resin is (A) / (B) = 50/100 or more. The film thickness difference within the pixel can be suppressed, and nozzle drying and nozzle clogging can be prevented. When the mass ratio of the (A) high boiling point solvent and the (B) solvent for dissolving the dispersion resin is (A) / (B) = 300/100 or less, the solubility of the dispersion resin, the dispersant and the like is good. , Dispersibility can be maintained. Further, the solid content in the curable coloring composition of the present invention is preferably 25% by mass to 60% by mass, and preferably 30% by mass to 50% by mass with respect to the mass of the curable coloring composition of the present invention. % Is more preferable. When the solid content is 25% by mass or more, it is possible to prevent color mixing caused by overflow of the curable coloring composition from the partition walls of the black matrix (BM). A pigment is fully disperse | distributed as content of the said solid content is 60 mass% or less, and clogging with an inkjet nozzle or the piping of an ink can be suppressed. Moreover, when forming a colored layer by an inkjet system, a thermal polymerization initiator is used suitably as a polymerization initiator contained in the curable coloring composition of this invention. This will be described in detail later.

The curable coloring composition of the present invention is used in combination with a solvent other than (A) the high-boiling solvent having the specific structure and (B) the solvent for dissolving the dispersed resin, as long as the effects of the present invention are not impaired. can do.
Such high-boiling solvents include diethylene glycol monoethyl ether, 3,5,5-trimethyl-2-cyclohexen-1-one, butyl lactate, 2-ethylhexyl acetate, 3-methoxy-3-methylbutyl acetate, and γ-butyrolactone. Is mentioned.

  Further, as the medium and low boiling point solvents, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters , Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-oxy 3-oxypropionic acid alkyl esters such as ethyl propionate; methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 −Me Propyl xylpropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2 -Ethyl methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, propylene glycol monomethyl ether Tate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; and aromatic hydrocarbons such as toluene, Kishireshi and the like.

<Dispersed resin>
In the curable coloring composition of the present invention, from the viewpoint of dispersion stability and storage stability, the dispersion resin is represented by a polymer compound represented by the following general formula (1), and represented by the following general formula (I). 1 or more types chosen from the polymer containing the copolymer unit derived from a monomer, and the polymer containing the structural unit represented by the following general formula (a) are contained.

In general formula (1), R ¹ represents an (m + n) -valent organic linking group, and R ² represents a single bond or a divalent organic linking group. A ¹ is a monovalent organic group containing an organic dye structure or a heterocyclic ring, or an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms Represents a monovalent organic group having a group selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ¹ may be the same or different. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer skeleton.

In the formula, R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (═O ) Represents one selected from S-, -OC (= O)-, -OCONH-, and -NHCO-. Y represents any one selected from NR ⁰³ , O, and S, and R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group. In the formula, N and Y are connected to each other to form a cyclic structure. m and n are each independently 0 or 1.

In the formula, R ^1a represents hydrogen or a methyl group, R ^2a represents an alkylene group, and Z ¹ represents a nitrogen-containing heterocyclic structure.

  Hereinafter, (B-1) a polymer compound represented by the general formula (1) and (B-2) a copolymer derived from the monomer represented by the general formula (I), which are suitable as the dispersion resin in the present invention. The polymer containing a polymer unit and the polymer containing the structural unit represented by (B-3) general formula (a) are demonstrated.

[(B-1) Polymer Compound Represented by General Formula (1): (B-1) Specific Dispersion Resin]
First, a polymer compound represented by the following general formula (1) (hereinafter, appropriately referred to as “(B-1) specific dispersion resin”) will be described.

In the general formula (1), A ¹ represents a monovalent organic group containing an organic dye structure or a heterocyclic ring, or an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, or a coordinating oxygen. A monovalent organic group having a group selected from an atom-containing group, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ¹ may be the same or different.

  More specifically, the “monovalent organic group having an organic dye structure” includes, for example, phthalocyanine-based, insoluble azo-based, azo lake-based, anthraquinone-based, quinacridone-based, dioxazine-based, diketo, and the like. Preferred examples include monovalent organic groups having a pyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, flavanthrone, perinone, perylene, thioindigo dye structure, and the like. Monovalent organic groups having an azo lake, anthraquinone, dioxazine, or diketopyrrolopyrrole dye structure are more preferred, and a monovalent organic group having a phthalocyanine, anthraquinone, or diketopyrrolopyrrole dye structure is more preferable. Is particularly preferred.

  Examples of the “monovalent organic group having a heterocyclic ring” include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, and triazole. , Thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, Preferred examples include monovalent organic groups having carbazole, acridine, acridone, anthraquinone, etc., and pyrroline, pyrrolidine, pyrazole, Zolin, pyrazolidine, imidazole, triazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, carbazole, acridine, acridone And monovalent organic groups having anthraquinone and the like are more preferable.

  The organic dye structure or heterocyclic ring may have a substituent, and examples of the substituent include alkyl groups having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. C1-C6 acyloxy groups such as aryl groups having 6 to 16 carbon atoms, such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, and acetoxy groups, methoxy groups, and ethoxy groups Alkoxy groups having 1 to 20 carbon atoms such as halogen atoms such as chlorine and bromine, methoxycarbonyl groups, ethoxycarbonyl groups, cyclohexyloxycarbonyl groups, etc., alkoxycarbonyl groups having 2 to 7 carbon atoms, cyano groups, t- And carbonic acid ester groups such as butyl carbonate. Here, these substituents may be bonded to the organic dye structure or the heterocyclic ring through the following structural unit or a linking group constituted by combining the structural units.

  Examples of the “monovalent organic group having an acidic group” include a monovalent organic group having a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphate group, a monophosphate group, a borate group, and the like. Preferred examples include monovalent organic groups having a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, and the like, and a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. A monovalent organic group having the above and the like is particularly preferable.

Examples of the “monovalent organic group having a group having a basic nitrogen atom” include, for example, a monovalent organic group having an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R). ¹⁰ ) having a monovalent organic group (wherein R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or 7 or more carbon atoms). Preferred examples include a monovalent organic group having a guanidyl group represented by the following formula (a1), a monovalent organic group having an amidinyl group represented by the following formula (a2), and the like. It is done.

In formula (a1), R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
In formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among these, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ each independently has 1 to 10 carbon atoms. An alkyl group, a phenyl group, and a benzyl group.), A guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms. Represents a phenyl group or a benzyl group. ] An amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. ] Is more preferable.
In particular, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms. , A phenyl group and a benzyl group.), A guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 5 carbon atoms, phenyl Represents a benzyl group. ] An amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group. Etc. are preferably used.

Examples of the “urea group” include —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a carbon number, Preferred examples include aryl groups having 6 or more and aralkyl groups having 7 or more carbon atoms, and —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom or 1 carbon atom). More preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.) —NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom or 1 to 10 carbon atoms) An alkyl group, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are particularly preferable.

Examples of the “urethane group” include —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , —OCONR ²² R ²³ (where R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like. -NHCOOR ¹⁸ , -OCONHR ²¹ (here And R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like, more preferably —NHCOOR ¹⁸ , -OCONHR ^{21 (wherein,} R ^{18, R 21} each independently represents an alkyl group having from 1 to 10 carbon atoms, having 6 or more ant carbon Group, represents a number of 7 or more aralkyl group having a carbon.), Etc. are particularly preferred.

  Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether.

  Preferred examples of the “hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. More preferred are an alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 4 to 15 carbon atoms (for example, an octyl group, a dodecyl group, etc.), and an aryl having 6 to 15 carbon atoms. A group (for example, phenyl group, naphthyl group, etc.), an aralkyl group having 7 to 15 carbon atoms (for example, benzyl group, etc.) and the like are particularly preferable.

  Examples of the “alkoxysilyl group” include a trimethoxysilyl group and a triethoxysilyl group.

The organic linking group bonded to the adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200. An organic linking group consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms is preferred, and this organic linking group may be unsubstituted or may further have a substituent.
Specific examples of the organic linking group include the following structural units or groups formed by combining the structural units.

  When the organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. C1-C6 alkoxy such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide group, acetoxy group, etc., C1-C6 acyloxy group, methoxy group, ethoxy group, etc. Group, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, etc. Can be mentioned.

In the above, as A ¹ , at least one site selected from an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms is used. It is preferable that it is a monovalent organic group to contain.

The A ¹ is more preferably a monovalent organic group represented by the following general formula (4).

In the general formula (4), B ¹ represents the adsorption site (that is, an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, or a group having a coordinating oxygen atom). , A moiety selected from a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group), and R ²⁴ represents a single bond or an (a + 1) -valent organic linking group. a represents an integer of 1 to 10, and a number of B ¹ may be the same or different.

Examples of the adsorption site represented by B ¹ include the same adsorption sites that constitute A ¹ in the general formula (1), and preferred examples are also the same.
Among these, a site selected from an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms is preferable.

R ²⁴ represents a single bond or an (a + 1) -valent organic linking group, and a represents 1 to 10. Preferably, a is 1-7, more preferably, a is 1-5, and particularly preferably, a is 1-3.
(A + 1) valent organic linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, And groups consisting of 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.

  Specific examples of the (a + 1) -valent organic linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure).

R ²⁴ may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and An (a + 1) valent organic linking group consisting of 0 to 10 sulfur atoms is preferred, a single bond or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 More preferred are (a + 1) valent organic linking groups consisting of up to 1 oxygen atom, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond, or 1 to 10 (A + 1) valence consisting of 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms The organic linking group is particularly preferred.

  Among the above, when the (a + 1) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, and the like. Such as an aryloxy group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl carbonate And the like, and the like.

In the general formula (1), R ² represents a single bond or a divalent organic linking group. n R ² may be the same or different.
The divalent organic linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 Groups comprising from 20 to 20 sulfur atoms are included and may be unsubstituted or further substituted.

  Specific examples of the divalent organic linking group include the following structural units or groups formed by combining the structural units.

R ² may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and Divalent organic linking groups consisting of 0 to 10 sulfur atoms are preferred, single bond or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 And more preferably a divalent organic linking group consisting of 1 to 50 hydrogen atoms and 0 to 7 sulfur atoms, a single bond or 1 to 10 carbon atoms, A divalent organic linking group consisting of 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms, in particular preferable.

  Among the above, when the divalent organic linking group has a substituent, examples of the substituent include carbon having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a carbon such as a phenyl group and a naphthyl group. Carbon number such as acyloxy group having 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc., methoxy group, ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. And carbonate ester groups.

In the general formula (1), R ¹ represents an (m + n) -valent organic linking group. m + n satisfies 3-10.
The (m + n) -valent organic linking group represented by R ¹ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups consisting of up to 200 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.

  Specific examples of the (m + n) -valent organic linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure).

  (M + n) -valent organic linking group includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, And preferably a group consisting of 0 to 10 sulfur atoms, preferably 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 More preferred are groups consisting of up to 5 hydrogen atoms and 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms. Particularly preferred are groups consisting of 1 to 80 hydrogen atoms and 0 to 5 sulfur atoms.

  Among the above, when the (m + n) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Such as an aryloxy group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl carbonate And the like, and the like.

Specific examples (specific examples (1) to (17)) of the (m + n) -valent organic linking group represented by R ¹ are shown below. However, the present invention is not limited to these.

  Among the above specific examples, the most preferable (m + n) -valent organic linking group is the following group from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents.

In said general formula (1), m represents 1-8. As m, 1-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable.
Moreover, in said general formula (1), n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In the general formula (1), P ¹ represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. The m P ¹ may be the same or different.
Among polymers, in order to constitute a polymer skeleton, a vinyl monomer polymer or copolymer, ester polymer, ether polymer, urethane polymer, amide polymer, epoxy polymer, silicone polymer, and these Modified product or copolymer [eg, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer, etc. (any of random copolymer, block copolymer, graft copolymer) May be included). At least one selected from the group consisting of: a vinyl monomer polymer or copolymer, an ester polymer, an ether polymer, a urethane polymer, and a modified product or copolymer thereof. At least one kind is more preferred, and a polymer or copolymer of vinyl monomers is particularly preferred.
Furthermore, the polymer is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, for example, when used as a pigment dispersant, the affinity with the dispersion medium is weakened, and it may not be possible to secure a sufficient adsorption layer for stabilizing the dispersion.

Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides Styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having an acidic group, and the like are preferable.
Hereinafter, preferable examples of these vinyl monomers will be described.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, (meth) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid acetoxyethyl, (meth) acrylic acid phenyl, (meth) 2-hydroxyethyl acrylate, (meth) acrylic acid-2-hydroxypropyl, (meth ) Acrylic acid-3-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl, (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid 2- (2- Methoxyethoxy) ethyl, 3-methoxy-2-hydroxypropyl (meth) acrylate, 2-chloroethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexylmethyl, (Meth) vinyl acrylate, (meth) acrylic acid-2-phenylvinyl, (meth) acrylic acid-1-propenyl, (meth) acrylic acid allyl, (meth) acrylic acid-2-allyloxyethyl, (meth) Propargyl acrylate, benzyl (meth) acrylate, diethylene glycol (meth) acrylate Methyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic Polyethylene glycol monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth ) Trifluoroethyl acrylate, octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Meth) acrylic acid tribromophenyl, (meth) tribromophenyl oxyethyl acrylate, and (meth) acrylic acid -γ- butyrolactone.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.

  (Meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (for example, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, etc. are also used. it can.

  In addition to the above compounds, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

Examples of the vinyl monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and the like.

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

  Furthermore, a vinyl monomer containing a phenolic hydroxyl group or a vinyl monomer containing a sulfonamide group can be used as the vinyl monomer having an acidic group.

  Among the polymer compounds represented by the general formula (1), the polymer compound represented by the following general formula (2) is preferable.

In the general formula (2), A ² represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms. Represents a monovalent organic group containing at least one portion selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ² may be the same or different.
Incidentally, A ² has the same meaning as the A ¹ in the general formula (1), a preferable embodiment thereof is also the same.

In the general formula (2), R ⁴ and R ⁵ each independently represents a single bond or a divalent organic linking group. The n R ^{4 s} may be the same or different. The m R ^{5 s} may be the same or different.
As the divalent organic linking group represented by R ⁴ and R ⁵ , the same ones as those mentioned as the divalent organic linking group represented by R ² in the general formula (1) are used, The preferred embodiment is also the same.

In the general formula (2), R ³ represents an (m + n) -valent organic linking group. m + n satisfies 3-10.
Examples of the (m + n) -valent organic linking group represented by R ³ include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups consisting of up to 100 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.
Specifically, the (m + n) -valent organic linking group represented by R ³ is the same as the (m + n) -valent organic linking group represented by R ¹ in the general formula (1). The preferred embodiments are the same.

In said general formula (2), m represents 1-8. As m, 1-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable.
Moreover, in said general formula (2), n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

Further, P ² in the general formula (2) represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. the m P ² can be the same or different. The preferred embodiment of the polymer is the same as P ¹ in Formula (1).

Among the polymer compounds represented by the general formula (2), those satisfying all of R ³ , R ⁴ , R ⁵ , P ² , m, and n shown below are most preferable.
R ³ : Specific examples (1), (2), (10), (11), (16), or (17)
R ⁴ : a single bond or the following structural unit or a combination of the structural units: “1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms” A divalent organic linking group comprising an atom, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms (which may have a substituent, for example, C1-C20 alkyl group such as methyl group and ethyl group, aryl group having 6 to 16 carbon atoms such as phenyl group and naphthyl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide Group, acyloxy group having 1 to 6 carbon atoms such as acetoxy group, alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group, halogen atom such as chlorine and bromine, methoxycarbonyl group An ethoxycarbonyl group, an alkoxycarbonyl group having from 2 to 7 carbon atoms such as cyclohexyl oxycarbonyl group, a cyano group, carbonate group, such as t- butyl carbonate, and the like.)

R ⁵ : single bond, ethylene group, propylene group, the following group (a), or the following group (b)
In the following groups, R ²⁵ represents a hydrogen atom or a methyl group, and l represents 1 or 2.

P ² : Polymer or copolymer of vinyl monomer, ester polymer, ether polymer, urethane polymer and modified products thereof m: 1 to 3
n: 3-6

  The acid value of the (B-1) specific dispersion resin in the present invention is preferably 200 (mgKOH / g) or less, more preferably 160 (mgKOH / g) or less, and particularly preferably 120 (mgKOH / g) or less. When the acid value exceeds 200 (mgKOH / g), the dispersibility and dispersion stability of the pigment may be deteriorated.

  As molecular weight of (B-1) specific dispersion resin in this invention, 3000-100000 are preferable at a weight average molecular weight, 5000-80000 are more preferable, 7000-60000 are especially preferable. When the weight average molecular weight is within the above range, good dispersibility and dispersion stability can be achieved.

(Synthesis method)
The polymer compound represented by the general formula (1) (including those represented by the general formula (2)) is not particularly limited, but can be synthesized by the following method.
1. A polymer in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group or the like is introduced at the terminal, an acid halide having a plurality of the adsorption sites, an alkyl halide having a plurality of the adsorption sites, or a plurality of the adsorption sites. A method of polymerizing the isocyanate and the like.
2. A method in which a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having a plurality of the adsorption sites are subjected to a Michael addition reaction.
3. A method of reacting a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having the adsorption site in the presence of a radical generator.
4). A method in which a polymer having a plurality of mercaptans introduced at its terminal is reacted with a compound having a carbon-carbon double bond and the adsorption site in the presence of a radical generator.
5. A method of radical polymerizing a vinyl monomer in the presence of a mercaptan compound having a plurality of the adsorption sites.

  Among the above, the polymer compound of the present invention is preferably a synthesis method of 2, 3, 4, 5 and more preferably a synthesis method of 3, 4, 5 because of ease of synthesis. In particular, when the polymer compound of the present invention has a structure represented by the general formula (2), it is most preferable to synthesize by the synthesis method 5 because of ease of synthesis.

  More specifically, the synthesis method 5 is preferably a method in which a vinyl monomer is radically polymerized in the presence of a compound represented by the following general formula (3).

In the general formula (3), R ⁶ , R ⁷ , A ³ , m, and n have the same meanings as R ³ , R ⁴ , A ² , m, and n in the general formula (2), respectively. The preferred embodiment is also the same.

The compound represented by the general formula (3) can be synthesized by the following method or the like, but the following method 7 is more preferable because of ease of synthesis.
6). A method of converting a halide compound having a plurality of adsorption sites into a mercaptan compound (a method of reacting with thiourea and hydrolyzing, a method of reacting directly with NaSH, a method of reacting with CH ₃ COSNa and hydrolyzing, etc.) )
7). Method of addition reaction of a compound having 3 to 10 mercapto groups in one molecule and a compound having the adsorption site and having a functional group capable of reacting with a mercapto group

Preferable examples of the “functional group capable of reacting with a mercapto group” in the synthesis method 7 include acid halides, alkyl halides, isocyanates, and carbon-carbon double bonds.
It is particularly preferable that the “functional group capable of reacting with a mercapto group” is a carbon-carbon double bond, and the addition reaction is a radical addition reaction. The carbon-carbon double bond is more preferably a mono- or di-substituted vinyl group in terms of reactivity with the mercapto group.

  Specific examples of the compound having 3 to 10 mercapto groups in one molecule [specific examples (18) to (34)] include the following compounds.

  Among the above, the following compounds are particularly preferable from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents.

  A compound having the adsorption site and having a carbon-carbon double bond (specifically, an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a coordination group) A group having a coordinated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group; and a carbon-carbon double bond Although it does not restrict | limit especially as a compound which has, The following are mentioned.

  The radical addition reaction product of the “compound having 3 to 10 mercapto groups in one molecule” and the “compound having the adsorption site and having a carbon-carbon double bond” is, for example, The above “compound having 3 to 10 mercapto groups in one molecule” and “compound having the adsorption site and having a carbon-carbon double bond” are dissolved in an appropriate solvent, It is obtained using a method (thiol-ene reaction method) in which a radical generator is added and added at about 50 ° C. to 100 ° C.

Examples of suitable solvents used in the thiol-ene reaction method include “compound having 3 to 10 mercapto groups in one molecule”, “having the adsorption site, and carbon-carbon double. It can be arbitrarily selected according to the solubility of the “compound having a bond” and the “radical addition reaction product to be produced”.
For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  In addition, as radical generators, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate An azo compound such as benzoyl peroxide, a peroxide such as benzoyl peroxide, and a persulfate such as potassium persulfate and ammonium persulfate can be used.

The vinyl monomer used in the synthesis method of 5 is not particularly limited, for example, those similar to the vinyl monomers used in obtaining the polymer skeleton represented by P ¹ of the general formula (1) is used It is done.

The above vinyl monomers may be polymerized alone or in combination of two or more.
In addition, when applied to a curable coloring composition that requires alkali development processing, the polymer compound of the present invention includes a vinyl monomer having one or more acidic groups and a vinyl monomer having no one or more acidic groups. And are more preferably copolymerized.

As the polymer compound of the present invention, those obtained by polymerizing these vinyl monomers and the compound represented by the general formula (3) by a known method according to a conventional method are preferable. In addition, the compound represented by the general formula (3) in the present invention functions as a chain transfer agent, and may be simply referred to as “chain transfer agent” hereinafter.
For example, a method in which these vinyl monomers and the chain transfer agent are dissolved in a suitable solvent, a radical polymerization initiator is added thereto and polymerized in a solution at about 50 ° C. to 220 ° C. (solution polymerization method) ) To obtain.

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  Examples of radical polymerization initiators include 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), and 2,2′-azobisisobutyric acid. An azo compound such as dimethyl, a peroxide such as benzoyl peroxide, and a persulfate such as potassium persulfate and ammonium persulfate can be used.

[(B-2) Polymer containing copolymer units derived from the monomer represented by formula (I): (B-2) Specific dispersion resin]
Next, a polymer containing a copolymer unit derived from a monomer represented by the following general formula (I) (hereinafter, referred to as “(B-2) specific dispersion resin”) will be described.

In the polymer containing copolymer units derived from the monomer represented by formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-. Y represents —NR ⁰³ —, —O—, —S—, or —N═, and is linked to an N atom via an adjacent atomic group to form a cyclic structure. R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group. m and n each independently represents 0 or 1.

  Hereinafter, the monomer represented by formula (I), which is an essential copolymer unit of the specific dispersion resin (B-2) in the present invention, will be described in detail.

In the general formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
The alkyl group represented by R ⁰¹ 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.
When the alkyl group represented by R ⁰¹ is a substituted alkyl group, examples of the substituent that can be introduced include a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, and a halogen group.
Specifically, preferred examples of the alkyl group represented by R ⁰¹ include methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2-hydroxy group. Examples thereof include an ethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group.

R ⁰² represents an alkylene group.
The alkylene group represented by R ⁰² is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms.
The alkylene group represented by R ⁰² may have a substituent when it can be introduced, and examples of the substituent include a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, and the like. It is done.
Specific examples of the preferable alkylene group represented by R ⁰² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.

  W represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and is —C (═O) O— or —CONH—. Is preferred.

Y represents —NR ⁰³ —, —O—, —S—, or —N═, and is linked to an N atom via an adjacent atomic group to form a cyclic structure.
R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably a hydrogen atom or a methyl group.
Y is particularly preferably -S-, -NH-, or -N =.

  Examples of the cyclic structure formed by linking Y with an N atom through an atomic group adjacent thereto include imidazole ring, pyrimidine ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, and the like, and , A condensed ring structure such as a benzimidazole ring, a benzthiazole ring, a benzoxazole ring, a purine ring, a quinazoline ring, and a perimidine ring, and a condensed ring structure is preferable from the viewpoint of affinity with a pigment. Of the condensed ring structures, a benzimidazole ring, a benzthiazole ring, and a benzoxazole ring are particularly preferred.

X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-.
X is particularly preferably —O—, —S—, —CONH—, —NHCONH—, and —NHC (═O) S—.

  m and n each independently represents 0 or 1, and it is particularly preferred that both m and n are 1.

  Preferred specific examples (monomer M-1 to monomer M-18) of the monomer represented by formula (I) are listed below, but the present invention is not limited thereto.

  The specific dispersion resin (B-2) in the present invention is further ethylenically terminated with a copolymer unit derived from the monomer represented by the general formula (I) from the viewpoint of imparting dispersion stability of the pigment. A graft copolymer containing a copolymer unit derived from a polymerizable oligomer having an unsaturated bond is particularly preferred.

  Such a polymerizable oligomer having an ethylenically unsaturated bond at the terminal is also called a macromonomer because it is a compound having a predetermined molecular weight. In the following description, the “polymerizable oligomer having an ethylenically unsaturated bond at the terminal” in the present invention may be appropriately referred to as “polymerizable oligomer” or “macromonomer”.

  The polymerizable oligomer optionally used in the present invention comprises a polymer chain part and a part of a polymerizable functional group having an ethylenically unsaturated double bond at its terminal. It is preferable from the viewpoint of obtaining a desired graft polymer that such a group having an ethylenically unsaturated double bond is present only at one end of the polymer chain. As the group having an ethylenically unsaturated double bond, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable.

Moreover, it is preferable that this macromonomer has the number average molecular weight (Mn) of polystyrene conversion in the range of 1000-10000, and the range of 2000-9000 is especially preferable.
The polymer chain portion is a homopolymer or copolymer formed from at least one monomer selected from the group consisting of alkyl (meth) acrylate, styrene and derivatives thereof, acrylonitrile, vinyl acetate and butadiene, or polyethylene oxide. Polypropylene oxide and polycaprolactone are generally used.

  The polymerizable oligomer is preferably an oligomer represented by the following general formula (II).

In general formula (II), R ¹¹ and R ¹³ each independently represent a hydrogen atom or a methyl group.
R ¹² represents a linking group containing an alkylene group having 1 to ¹² carbon atoms, and the linking group may be an alkylene group having 1 to 12 carbon atoms, or a plurality of the alkylene groups may be ester bonds or ethers. It may be linked via a bond, an amide bond or the like. R ¹² is preferably a group in which an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms is linked by breaking an ester bond. The alkylene group represented by R ¹² may further have a substituent (for example, a hydroxyl group).
Y ¹¹ represents a phenyl group having no substituent, a phenyl group having one alkyl group having 1 to 4 carbon atoms, or —COOR ¹⁴ . Here, R ¹⁴ represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms. Y is preferably a phenyl group or —COOR ¹⁴ where R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms.
q represents an integer of 20 to 200.

  Preferred examples of the polymerizable oligomer (macromonomer) that can be used in the synthesis of the (B-2) specific dispersion resin in the present invention include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and poly-i-. A polymer in which a (meth) acryloyl group is bonded to one molecular end of butyl (meth) acrylate or polystyrene can be exemplified. As such polymerizable oligomers available on the market, one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, manufactured by Toagosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer ( Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-terminal methacryloylated poly-n-butyl acrylate oligomer (Mn = 6000, trade name: AB-6, Toa Gosei Chemical Co., Ltd.) ) Made).

In order to obtain a specific acid value, the (B-2) specific dispersion resin according to the present invention preferably further includes a copolymer unit derived from a monomer having an acid group.
Monomers having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) mono [2- (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monoacrylate Mono (meth) acrylates such as both terminal carboxy polymers methacrylate and the like.

The (B-2) specific dispersion resin according to the present invention may further contain a copolymerizable vinyl monomer as a copolymer component as long as the effect is not impaired.
Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds.

That is, examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid n. -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxy (meth) acrylate Ethyl, 2-methoxyethyl (meth) acrylate, 2-ethoxy (meth) acrylate Chill, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) Acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether , Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dimethacrylate Cyclopentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromo (meth) acrylate Examples thereof include phenyl and tribromophenyloxyethyl (meth) acrylate.
In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl. Examples thereof include styrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.
Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  As a preferred embodiment of the (B-2) specific dispersion resin according to the present invention, it contains 2 to 50% by mass of a copolymer unit derived from the monomer represented by the general formula (I), and further at the end. 10 to 90% by mass of copolymer units derived from a polymerizable oligomer having an ethylenically unsaturated bond, 1 to 30% by mass of copolymer units derived from a monomer having an acid group, and copolymerization derived from a vinyl monomer The copolymer containing 0-20 mass% of a unit can be mentioned preferably.

  Specific examples of [B-2) specific dispersion resin [Exemplary Compound 1 to Exemplified Compound 16] that can be suitably used in the curable coloring composition of the present invention are listed below together with their weight average molecular weights. It is not limited.

Exemplary compound (1): monomer M-2 / terminal methacryloylated polymethyl methacrylate copolymer (10/90 mass%, weight average molecular weight 50000)
Exemplary compound (2): monomer M-2 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 25000)
Exemplary Compound (3): Monomer M-3 / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (5/10/85% by mass, weight average molecular weight 40000)
Exemplary compound (4): monomer M-3 / methacrylic acid / benzyl methacrylate copolymer / terminal methacryloylated polymethyl methacrylate copolymer (15/5/10/65 mass%, weight average molecular weight 60000)
Exemplary compound (5): monomer M-4 / terminal methacryloylated polymethyl methacrylate copolymer (10/90 mass%, weight average molecular weight 80,000)

Exemplary compound (6): monomer M-4 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 30000)
Exemplary Compound (7): Monomer M-5 / Acrylic acid / Terminal methacryloylated polymethyl methacrylate copolymer (25/15/60 mass%, weight average molecular weight 60000)
Exemplary Compound (8): Monomer M-5 / Terminal Methacryloylated Polybutyl Acrylate Copolymer (15/85% by Mass, Weight Average Molecular Weight 40000)
Exemplary compound (9): Monomer M-6 / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (15/10/75% by mass, weight average molecular weight 80000)
Exemplary Compound (10): Monomer M-6 / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (12/88% by Mass, Weight Average Molecular Weight 50000)

Exemplary compound (11): monomer M-7 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 25000)
Illustrative compound (12): monomer M-7 / methacrylic acid / benzyl methacrylate / methoxypolyethylene glycol methacrylate copolymer (10/10/50/30 mass%, weight average molecular weight 40000)
Exemplary compound (13): Monomer M-10 / 2-hydroxyethyl methacrylate / terminal methacryloylated polystyrene copolymer (5/10/85 mass%, weight average molecular weight 20000)
Illustrative compound (14): monomer M-10 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 25000)
Illustrative compound (15): monomer M-10 / methoxypolyethylene glycol methacrylate copolymer (15:85 mass%, weight average molecular weight 15000)
Exemplary Compound (16): Monomer M-13 / Methacrylic acid / Terminal methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 20000)

  The copolymer as described above, which is (B-2) the specific dispersion resin in the present invention, includes the monomer represented by the general formula (I), a polymerizable oligomer and other monomers used in combination as desired. It can be obtained by radical polymerization in a solvent. As the radical polymerization initiator, a known compound is used, and an azo initiator (for example, dimethyl-2,2′-azobis (2-methylpropionate), azobisisobutyronitrile, 2,2′- Azobis (2-amidinopropane) dihydrochloride, etc.) and peroxides (benzoyl peroxide, potassium persulfate, etc.) are preferably used. In addition to the initiator, a chain transfer agent (for example, 2-mercaptoethanol, 3-mercaptopropionic acid, 2-mercaptoacetic acid, dodecyl mercaptan) may be added and synthesized.

  (B-2) As for content of specific dispersion resin, 0.5-100 mass% is preferable with respect to the mass of the coloring agent mentioned later, and 3-70 mass% is more preferable. (B-2) When the content of the specific dispersion resin is within this range, a sufficient pigment dispersion effect can be obtained. Even if the pigment dispersant is added in an amount of more than 100% by mass, further improvement in the effect of the pigment dispersant may not be expected.

[(B-3) Polymer containing structural unit represented by general formula (a): (B-3) specific dispersion resin]
Subsequently, a polymer containing a structural unit represented by the following general formula (a) (hereinafter, appropriately referred to as “(B-3) specific dispersion resin”) will be described.

In the general formula (a), R ^1a represents hydrogen or a methyl group, R ^2a represents an alkylene group, and Z ¹ represents a nitrogen-containing heterocyclic structure.
^Examples of the alkylene group represented by R ^2a include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a 2-hydroxypropylene group, a methyleneoxy group, an ethyleneoxy group, a methyleneoxycarbonyl group, a methylenethio group, Among them, a methylene group, a methyleneoxy group, a methyleneoxycarbonyl group, and a methylenethio group are preferable.

In the general formula (a), Z ¹ represents a nitrogen-containing heterocyclic structure, specifically, for example, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, Examples thereof include quinoline ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea structure, and cyclic imide structure.
Among these, the nitrogen-containing heterocyclic structure represented by Z ¹ is preferably a structure represented by the following general formula (b) or general formula (c).

In the general formula (b), X ¹ represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), —O—, —S—, —NR—, and , -C (= O)-. Here, R represents a hydrogen atom or an alkyl group, and examples of the alkyl group when R represents an alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. , T-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among these, X ¹ is preferably a single bond, a methylene group, —O— or —C (═O) —, and particularly preferably —C (═O) —.

  In the general formula (b) and the general formula (c), the ring A, the ring B, and the ring C each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone A ring is preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

  Preferred specific examples of the structural unit represented by the general formula (a) [Exemplary monomers (M-1) to (M-7)] are listed below, but the present invention is not limited thereto.

The structural unit represented by the general formula (a) is preferably contained in an amount of 2% by mass to 50% by mass, and more preferably 4% by mass to 30% by mass, in the specific dispersion resin (B-3). It is especially preferable that 5 mass%-20 mass% is contained.
The (B-3) specific dispersion resin in the present invention is a graft containing, in addition to the structural unit represented by the general formula (a), a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal as a copolymer unit. A copolymer is particularly preferred.
Examples of the polymerizable oligomer having an ethylenically unsaturated double bond at the terminal include those similar to the polymerizable oligomer used as a copolymerization component in the above-mentioned (B-2) specific dispersion resin, and preferred embodiments thereof. The same applies to (oligomer represented by formula (II)) and preferred examples (specific examples).

In order to obtain a specific acid value, the (B-3) specific dispersion resin in the present invention preferably further contains a monomer having an acid group (structural unit) as a copolymerization component.
Examples of the monomer having an acid group include (meth) acrylic acid, p-vinylbenzoic acid, maleic acid, fumaric acid, itaconic acid, succinic anhydride adduct of 2-hydroxyethyl (meth) acrylate, (meth) And phthalic anhydride adduct of 2-hydroxyethyl acrylate.

The (B-3) specific dispersion resin in the present invention may further contain a copolymerizable vinyl monomer as a copolymer component as long as the effect is not impaired.
Examples of the vinyl monomer that can be used here include the same vinyl monomers used as the copolymerization component in the above-mentioned (B-2) specific dispersion resin, and preferred examples thereof are also the same.

  In addition, as a preferable aspect of the (B-3) specific dispersion resin in the present invention, the structural unit represented by the general formula (a) is included in an amount of 2% by mass to 50% by mass, and the terminal is ethylenically unsaturated. Preferred is a copolymer containing 10% by mass to 90% by mass of a polymerizable oligomer having a double bond, 1% by mass to 30% by mass of a structural unit having an acid group, and 0% by mass to 20% by mass of a vinyl monomer. Can do.

  Specific examples (B-3) of specific dispersed resins [Exemplary compounds (I) to (XV)] that can be suitably used for the curable coloring composition of the present invention are listed below together with their weight average molecular weights. It is not limited to these.

Exemplary Compound (I): Exemplary Monomer (M-1) / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (Copolymerization Ratio = 10/90% by Mass, Weight Average Molecular Weight 50000)
Illustrative compound (II): Illustrative monomer (M-1) / methacrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 25000)
Illustrative compound (III): Illustrative monomer (M-1) / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (5/10/85 mass%, weight average molecular weight 40000)
Illustrative compound (IV): Illustrative monomer (M-1) / methacrylic acid / benzyl methacrylate copolymer / terminal methacryloylated polymethyl methacrylate copolymer (15/5/10/65 mass%, weight average molecular weight 60000)
Exemplary compound (V): the exemplary monomer (M-5) / terminal methacryloylated polymethyl methacrylate copolymer (20/80 mass%, weight average molecular weight 80000)

Exemplified compound (VI): Exemplified monomer (M-5) / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75% by mass, weight average molecular weight 30000)
Exemplified compound (VII): Exemplified monomer (M-5) / acrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (25/15/60% by mass, weight average molecular weight 60000)
Exemplified compound (VIII): Exemplified monomer (M-5) / Terminal methacryloylated polybutyl acrylate copolymer (15/85% by mass, weight average molecular weight 40000)
Exemplified compound (IX): Exemplified monomer (M-5) / 2-hydroxyethyl methacrylate / terminated methacryloylated polymethyl methacrylate copolymer (15/10/75% by mass, weight average molecular weight 80000)
Exemplary compound (X): the above exemplary monomer (M-6) / terminal methacryloylated polymethyl methacrylate copolymer (12/88 mass%, weight average molecular weight 50000)

Exemplary Compound (XI): Exemplary Monomer (M-6) / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (10/15/75% by Mass, Weight Average Molecular Weight 25000)
Exemplified compound (XII): Exemplified monomer (M-6) / methacrylic acid / benzyl methacrylate / methoxypolyethylene glycol methacrylate copolymer (10/10/50/30% by mass, weight average molecular weight 40000)
Exemplified compound (XIII): Exemplified monomer (M-6) / 2-hydroxyethyl methacrylate / terminal methacryloylated polystyrene copolymer (5/10/85% by mass, weight average molecular weight 20000)
Exemplified compound (XIV): Exemplified monomer (M-6) / Methacrylic acid / Methyl methacrylate / Terminal methacryloylated polymethyl methacrylate copolymer (8/12/10/70 mass%, weight average molecular weight 60000)
Exemplary compound (XV): the above exemplary monomer (M-6) / methoxypolyethyleneglycol methacrylate copolymer (15: 85% by mass, weight average molecular weight 15000)

  The copolymer as described above, which is (B-3) the specific dispersion resin in the present invention, is a monomer that can be a structural unit represented by the general formula (a), a polymerizable oligomer used in combination as desired, Other monomers can be obtained by radical polymerization in a solvent. In this radical polymerization, the same radical polymerization initiator and chain transfer agent as those used when (B-2) the specific dispersion resin is synthesized are used.

  (B-3) As for content of specific dispersion resin, 0.5-100 mass% is preferable with respect to the mass of the coloring agent mentioned later, and 3-70 mass% is more preferable. (B-2) When the content of the specific dispersion resin is within this range, a sufficient pigment dispersion effect can be obtained. Even if the pigment dispersant is added in an amount of more than 100% by mass, further improvement in the effect of the pigment dispersant may not be expected.

  In order to disperse the colorant described later with the (B-1) specific dispersion resin and the dispersion resin, the dispersion resin and the solvent are added to the colorant to form a mill base, which is then subjected to a flashing treatment, a kneader, a ball mill, a sand mill, The dispersion treatment can be performed by a method such as a bead mill, a two or three roll mill, an extruder, a paint shaker, an ultrasonic disperser, or a homogenizer. Two or more of these processing methods can be combined. In order to uniformly disperse the carbon black, a dispersant described later can be used as necessary.

  The dispersion of the colorant can be performed using only the dispersion resin, but the following dispersant can also be used in combination. Examples of the dispersant that can be used in combination include a dispersant as described below. The dispersants can be used alone or in combination. As a result of the dispersion treatment, the resin is adsorbed on the surface of the colorant and carbon black, and at the same time, the aggregation of the colorant and carbon black particles is destroyed and the particle size is reduced.

Examples of the dispersant include a hydrophilic group such as a carboxyl group, an OH group, a sulfonic acid group, a phosphoric acid group, an amino group, a carbonyl group, and a polyoxyalkylene unit, a phenyl group (including a naphthalene ring), an alicyclic ring, and an alkyl group. In addition, compounds having a lipophilic part such as a substituted group, compounds having a pigment-like structure and a hydrophilic part and / or a lipophilic part are generally used, but the compounds exemplified below can be used. is there. However, it is not limited to these compounds.
EFKA-1101, 1120, 1125, 4008, 4009, 4046, 4047, 4520, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 5070, 5207 (manufactured by EFKA ADDITIVES), Anti-Terra-U, Anti-Terra-U100, Anti-Terra-204, Anti-Terra-205 Anti-Terra-P, Disperbyk-101, 102, 103, 106, 108, 109, 110, 111, 112, 151, P-104, P-104S, P105, 220S, 20 , 204, 205, 9075, 9076, 9077 (manufactured by BYK), Disparlon 7301, 325, 374, 234, 1220, 2100, 2200, KS260, KS273N, 1210, 2150, KS860, KS873N, 7004, 1813, 1860, 1401 , 1200, 550, EDAPLAN 470, 472, 480, 482, K-SPERSE 131, 152, 152MS (manufactured by Enomoto Kasei Co., Ltd.), Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000 (AVECIA), Carribbon B, L-400, Eleminol MBN-1, Sunspearl PS-2, PS-8, Ionette S-20 (manufactured by Sanyo Kasei) ) Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco) can be used. These may be used alone or in combination of two or more. Content of a dispersing agent is 1 mass%-25 mass% with respect to the total mass of a coloring agent, Preferably they are 2 mass%-20 mass%.

In addition, increasing the pigment concentration to create high color purity generally increases the thixotropy of the coating solution, which tends to cause film thickness unevenness after coating. It is important to ring to form a uniform thickness coating. For this reason, it is preferable to contain an appropriate surfactant in the curable coloring composition.
Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.

Nonionic surfactants, fluorine-based surfactants, silicon-based surfactants, and the like are added as surfactants for improving coating properties. Nonionic surfactants include, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers. Nonionic surfactants such as polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters are preferred. Specifically, polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; polyoxy Polyoxyethylene aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene polystyrylated ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene-propylene polystyrylated ether, polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate , Polyoxyalkylene dialkyl esters such as polyoxyethylene distearate, sorbitan fatty acid ester There are nonionic surfactants such as stealth and polyoxyalkylene sorbitan fatty acid esters. Specific examples of these include, for example, the Adeka Pluronic series, Adecanol series i, Tetronic series (above made by ADEKA), Emulgen series, Rheodor series (above made by Kao Corporation), Eleminol series, Nonipole series, Octopole Series, Dodecapol Series, New Pole Series (Sanyo Kasei Co., Ltd.), Pionein Series (Takemoto Yushi Co., Ltd.), Nissan Nonion Series (Nippon Yushi Co., Ltd.). These commercially available products can be used as appropriate. A preferable HLB value is 8 to 20, more preferably 10 to 17.
As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used. Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08 (Dainippon Ink Co., Ltd.), Florard FC -135, FC-170C, FC-430, FC-431 (Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145 S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801 and 802 (manufactured by JEMCO).
Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, and SF-8428. DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above GE Toshiba Silicone Co., Ltd.).
These surfactants are preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the resist solution. When the amount of the surfactant exceeds 5 parts by weight, surface roughness is likely to occur during coating and drying, and the smoothness tends to deteriorate.

Furthermore, the curable coloring composition of the present invention can contain an alkali-soluble resin as necessary.
The alkali-soluble resin that can be contained in the curable coloring composition of the present invention is a linear organic high molecular polymer, and a molecule (preferably, an acrylic copolymer or a styrene copolymer is a main chain. And an alkali-soluble resin having at least one group that promotes alkali solubility (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, etc.).

As a more preferable embodiment as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, As described in JP-A-59-53836 and JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, Acrylic copolymers such as maleic acid copolymers, partially esterified maleic acid copolymers, etc., acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having a hydroxyl group with an acid anhydride added Is mentioned.
The acid value of the polymer that the alkali-soluble resin has in the side chain is preferably 20 to 200 mgKOH / g, preferably 30 to 180 mgKOH / g, and more preferably 50 to 150 mgKOH / g.

As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Examples of the alkyl (meth) acrylates and aryl (meth) ^{_{acrylate, CH 2 = C (R 1}} ) (COOR 3) [wherein, ^{R 1} represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, ^{R 2} Represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) ) Acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl is an alkyl group having 1 to 8 carbon atoms) ), Hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate and the like.
Moreover, resin which has a polyalkylene oxide chain in a molecular side chain is also mentioned as a preferable aspect. The polyalkylene oxide chain may be a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof, and the terminal is a hydrogen atom or a linear or branched alkyl group.
1-20 are preferable and, as for the repeating unit of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable. Acrylic copolymers having a polyalkylene oxide chain in these side chains include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, and the like. A compound in which these terminal OH groups are alkyl-blocked, such as methoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol-propylene glycol) mono (meth) acrylate, etc. is used as a copolymerization component. Acrylic copolymer.

Moreover, as said vinyl compound, the compound represented by a following formula is mentioned.
CH ₂ = CR ¹ R ²

Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R ³ represents an alkyl group or carbon having 1 to 8 carbon atoms. Represents an aralkyl group of formula 6-12.

Specific examples include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.
Other monomers that can be copolymerized can be used singly or in combination of two or more. Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.

As already described, the acrylic resin has an acid value in the range of 20 to 200 mgKOH / g. When the acid value exceeds 200, the acrylic resin becomes too soluble in alkali and the appropriate development range (development latitude) becomes narrow. On the other hand, if it is too small, such as less than 20, the solubility in alkali is so small that it takes too much time for development, which is not preferable.
Also, the mass average molecular weight Mw (polystyrene conversion value measured by GPC method) of the acrylic resin is used to realize a viscosity range that is easy to use in the process of applying a color resist, etc., and to secure film strength. , Preferably from 2,000 to 100,000, more preferably from 3,000 to 50,000.
In order to make the acid value of acrylic resin into the range specified above, it can be easily performed by appropriately adjusting the copolymerization ratio of each monomer. Further, the range of the mass average molecular weight can be easily set by using an appropriate amount of a chain transfer agent according to the polymerization method when the monomers are copolymerized.

  The acrylic resin can be produced, for example, by a known radical polymerization method. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an acrylic resin by radical polymerization can be easily set by those skilled in the art. Is possible.

In order to improve the crosslinking efficiency of the curable coloring composition of the present invention, a resin having a polymerizable group in an alkali-soluble resin may be used alone or in combination with an alkali-soluble resin having no polymerizable group. A polymer containing a group, a (meth) acryl group, an aryloxyalkyl group or the like in the side chain is useful. The alkali-soluble resin having a polymerizable double bond can be developed with an alkali developer, and is further provided with photocurability and thermosetting. Examples of polymers containing these polymerizable groups ((1) to (4)) are shown below. If an alkali-soluble group such as a COOH group and an OH group and a carbon-carbon unsaturated bond are contained, It is not limited to.
(1) Urethane modification obtained by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting at least one (meth) acryloyl group with an acrylic resin containing a carboxyl group A polymerizable double bond-containing acrylic resin,
(2) An unsaturated group-containing acrylic resin obtained by a reaction between an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule.
(3) Acid pendant type epoxy acrylate resin.
(4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.
Of the above, the resins (1) and (2) are particularly preferable.

  As a specific example, a copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these, an OH group A compound obtained by reacting an epoxy ring having reactivity with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, a compound having an acid anhydride, an isocyanate group, or an acryloyl group in addition to the epoxy ring can be used. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used. Examples of the compound having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dynal NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group-containing Polyurethane acrylic oligomer, Diamond Shamrock Co., Ltd.). Ltd .; Biscort R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel) And UCB Co., Ltd.).

  As content of an acryl-type copolymer, the range of 0 mass%-50 mass% is preferable with respect to the total mass of the resin component containing the said dispersion resin contained in the curable coloring composition in this invention. . When the content of the acrylic copolymer is within the above range, even when the concentration of the colorant is increased, high sensitivity can be maintained, and the development speed can be optimized to obtain good development performance. Time can be shortened.

<Colorant>
The curable coloring composition of the present invention contains at least one colorant. By containing the colorant, a visible image having a desired color can be formed.
As the colorant, it is possible to use any of chromatic colorants such as R, G, and B that form color pixels of a color filter, and a black colorant that is generally used for forming a black matrix. it can.
In the curable coloring composition of the present invention, particularly when the curable coloring composition is constituted using a black colorant, the effect of the present invention, that is, high photosensitivity is obtained, and the development margin and the development latitude are increased. An effect excellent in good developability is exhibited to a higher degree. Therefore, as the colorant, a black colorant is suitable, and it is also suitable for RGB having a high color purity.

Examples of the black colorant include, but are not limited to, carbon black, titanium black, graphite, iron oxide, titanium oxide, and other pigments / dyes described later. Among these, carbon black, titanium black, and graphite are preferable, and carbon black is more preferable. These may be used in combination of two or more in addition to being used alone.
The mass ratio (mass of carbon black: mass of colorant used in combination) when two or more are used in combination is preferably in the range of 95: 5 to 60:40, more preferably 95: 5 to 70:30, 90 : 10 to 80:20 is more preferable. When there are a plurality of black colorants, the total mass is a plurality. When the mass ratio is within the above range, there is no aggregation of the dispersion and a stable coating film without unevenness can be formed.

Examples of the carbon black include carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, #M manufactured by Mitsubishi Chemical Corporation. 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N33 , Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LP; Carbon Black Thermax N990, N991, N907, N908, N990, N991, N908 manufactured by Curve Corporation; carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, manufactured by Asahi Carbon Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal; Carbon black Color Black Fw200, Color B ack Fw2, Color Black Fw2V, Color Black Fw1, Color Black Fw18, Color Black S170, Color Black S160, Special Black6, Special Black5, Special Black4, Special Black4A, Printex U, be mentioned PrintexV, Printex 140U, Printex 140V, etc. Can do.
Carbon black preferably has insulating properties. Insulating carbon black refers to carbon black that exhibits insulating properties when the volume resistance as a powder is measured by the following method. For example, an organic substance is adsorbed, coated or chemically bonded to the surface of carbon black particles ( It has an organic compound on the surface of carbon black particles, such as grafted).

As carbon blacks other than the above, for example, JP-A-11-60988, JP-A-11-60989, JP-A-10-330634, JP-A-11-80583, JP-A-11-80584, Resin-coated carbon black described in Kaihei 9-124969 and JP-A-9-95625 can be used. In addition, carbon black may be dispersed with the dispersion resin.
In the present invention, examples of the form of the pigment and carbon black dispersedly coated with the resin and the like include powder, paste, pellet, paste, and sheet.
A preferable average particle size of the pigment and carbon black dispersedly coated with the dispersion resin or the like is in the range of 0.003 μm to 0.2 μm, more preferably in the range of 0.005 μm to 0.15 μm, and still more preferably 0. 0.01 μm to 0.10 μm. As a result, various effects of the present invention, particularly developability and development reproducibility are further improved.

As a pigment used as a colorant such as RGB, an inorganic pigment or an organic pigment can be used. In addition, it is preferable to use a pigment having a small particle size as small as possible considering the fact that the pigment is preferably high transmittance regardless of inorganic or organic, but from the viewpoint of handling properties, Preferably, the pigment has an average particle size of 0.010 to 0.100 μm, and more preferably 0.010 to 0.050 μm.
Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And metal complex oxides.

As the organic pigment,
C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
C. I. Pigment Orange 36, 38, 43, 71;
C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;
C. I. Pigment Violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment Green 7, 36, 37;
C. I. Pigment Brown 25, 28;
C. I. Pigment Black 1, 7;
Etc.

In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the curable coloring composition of the present invention. Although the cause is not fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an effect.
Among the pigments, more preferable pigments include the following. However, it is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66, C.I. I. Pigment Green 7, 36, 37;
C. I. Pigment Black 1, 7

The organic pigment can be used in various combinations in order to increase color purity, in addition to being used alone. Specific examples are shown below.
Examples of red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them, and disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments or perylene red pigments. Mixing or the like is used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 is C.I. as a perylene pigment. I. Pigment red 155, C.I. I. Pigment Red 224 is C.I. as a diketopyrrolopyrrole pigment. I. Pigment Red 254, and C.I. I. Pigment yellow 83 or C.I. I. Mixing with Pigment Yellow 139 was good. The mass ratio of the red pigment to the yellow pigment was preferably 100: 5 to 100: 50. If it is less than 100: 5, the light transmittance of 400 to 500 nm cannot be suppressed, and the color purity may not be improved. On the other hand, if the ratio exceeds 100: 50, the dominant wavelength becomes shorter and the deviation from the NTSC target hue increases. In particular, the range of 100: 10 to 100: 30 is optimal. In the case of a combination of red pigments, it is adjusted according to the chromaticity.

  Examples of the green pigment include a halogenated phthalocyanine pigment alone or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment. I. Pigment Green 7, 36, or 37; I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, or C.I. I. Good mixing with Pigment Yellow 185. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. If it is less than 100: 5, the light transmittance of 400 to 450 nm cannot be suppressed, and the color purity cannot be increased. On the other hand, when the ratio exceeds 100: 150, the dominant wavelength becomes longer and the deviation from the NTSC target hue increases. A more preferable mass ratio is in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment alone or a mixture thereof with a dioxazine purple pigment is used. I. Pigment blue 15: 6 and C.I. I. Mixing with Pigment Violet 23 is good. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

When a dye is used as the colorant, a curable coloring composition that is uniformly dissolved is obtained.
There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

When the colorant is black (BM), the content of the colorant is preferably 40% by mass or more, more preferably 45% by mass or more, and 50% by mass with respect to the total solid content in the curable coloring composition. % To 75% by mass is more preferable.
In the case of red (R), 25 mass% or more is preferable, 30 mass% or more is more preferable, and 35 mass% or more and 50 mass% or less is still more preferable.
In the case of green (G), 35 mass% or more is preferable, 40 mass% or more is more preferable, and 45 mass% or more and 60 mass% or less is still more preferable.
In the case of blue (B), 25 mass% or more is preferable, 28 mass% or more is more preferable, and 30 mass% or more and 50 mass% or less is still more preferable.
When the content of the colorant is within the above range, ultraviolet rays (particularly 365 nm) used as exposure light do not reach the bottom of the exposed layer due to absorption of the colorant and the like, and the curable coloring composition is not sufficiently cured. For this reason, the lowermost part of the layer to be exposed is not sufficiently cured by exposure, and it is difficult to obtain a description in development. As a result, the development margin is small or the development latitude is small. Further, the absorbance of exposure light (and thus the degree of cure at the bottom of the colored layer) varies depending on the type of colorant (RGB and BM). The curable coloring composition of the present invention is effective when the content of the colorant is large. The curable coloring composition of the present invention can provide a colored layer with high color purity and good light-shielding properties, and the coating film has high sensitivity, and development property with better development margin and development latitude. Is obtained.

<Polymerization initiator>
The curable coloring composition of this invention contains a photoinitiator and a thermal polymerization initiator according to the coating method of a colored layer. Details are described below.
-Photopolymerization initiator-
The curable coloring composition of the present invention contains at least one photopolymerization initiator when a colored layer is applied on a substrate by a slit coating method. By using a photopolymerizable initiator, a higher degree of curing can be obtained, and the curability can be controlled as desired.
Examples of the photopolymerization initiator include active halogen compounds such as halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl substituted coumarin compounds, and at least one lophine dimer.

Among the active halogen compounds, examples of the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxax represented by the general formula IV described in JP-B-57-6096. And diazole compounds.
Specific examples of the 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole and 2-trichloromethyl-5. -(P-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole and the like.
Examples of the halomethyl-s-triazine compound include a vinyl-halomethyl-s-triazine compound represented by the general formula V described in JP-B-59-1281, and JP-A-53-133428. 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by general formula VI and 4- (p-aminophenyl) -2,6 represented by general formula VII -Di-halomethyl-s-triazine compounds and the like.
Specific examples of the vinyl-halomethyl-s-triazine compound include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like.

  Specific examples of the 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound include 2- (naphth-1-yl) -4,6-bis-trichloromethyl- s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis -Trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1 -Yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2 -[4- (2-Butoxye ) -Naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-Methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis -Trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy- Naphth-1-yl) 4,6-bis - trichloromethyl -s- triazine.

  Specific examples of the 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound include 4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2. , 6-Di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl ] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN- Etoki Carbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6- Di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo- pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N- (Ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [ o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonyl) Methyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [ o-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) amino Phenyl] -2,6-di (trichloromethyl) -s-triazine,

  4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di ( Chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s- Triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) ) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Til) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-) Ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s- Triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-tri 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6- [3-bromo-4- [N, N-bis (ethoxycarbonylmethyl) amino] phenyl] -1 , 3,5-triazine and the like.

  Particularly preferred among the 3-aryl substituted coumarin compounds are {(s-triazin-2-yl) amino} -3-arylcoumarin compounds.

The lophine dimer refers to a 2,4,5-triphenylimidazolyl dimer composed of two lophine residues.
Specific examples include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl). ) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, Examples include 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, and the like.

In addition to the above photopolymerization initiator, other known initiators can also be used.
For example, a vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660 and an α-carbonyl compound described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon-substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, a triallylimidazole dimer / p-aminophenylketone combination described in US Pat. No. 3,549,367, And benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516.
Moreover, Adeka optomer SP-150, 151, 170, 171, N-1717, N1414, etc. (above manufactured by Asahi Denka Co., Ltd.), OXE-01, OXE-02, CGI113, IR369, IR907, IR184, IR819 (manufactured by Ciba Specialties Chemicals Co. Ltd.) can also be used as a photopolymerization initiator.

  As for content of a photoinitiator, 0.5 mass%-20.0 mass% are preferable with respect to the total solid of a curable coloring composition, More preferably, 1.0 mass%-15.0 mass% It is. When the content of the photopolymerization initiator is in the above range, the polymerization and curing can be performed satisfactorily and a high film strength can be obtained.

The following sensitizers can be used in combination with the photopolymerization initiator as required.
Specific examples include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (dimethylamino) phenyl styryl ketone, p- (dimethylamino) phenyl-p-methylstyryl ketone, benzophenone, p- (dimethylamino) benzophenone (Or Michler's ketone), p (Diethylamino) benzophenone, benzoanthrone, 7- {L-4-chloro-6- (diethylamino) -S-triazinyl (2), 1-amino} -3-phenylcoumarin, and the like, and Japanese Patent Publication No. 51-48516 And the described benzothiazole compounds.

-Thermal polymerization initiator-
The curable coloring composition of this invention contains at least 1 type of a thermal-polymerization polymerization initiator, when apply | coating a colored layer on a board | substrate with an inkjet system. By using a photopolymerizable initiator, a higher degree of curing can be obtained, and the curability can be controlled as desired.

Here, there is a photopolymerization initiator that can be used as a thermal polymerization initiator.
For example, among the above thermal polymerization initiators, examples of the halomethyl oxadiazole include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, specifically 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl- 5- (p-methoxystyryl) -1,3,4-oxadiazole and the like can be mentioned.
Further, 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound, 4- (p-aminophenyl) -2,6-di described in JP-A-53-133428. -Halomethyl-s-triazine compounds, specifically 2- (naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1- Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy- Naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s- Triazine, 2- (2-me Xy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s -Triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis- Trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl)- 4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 4- [p-N, N -Di (ethoxycarboni Methyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2, 6-di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (Phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloro (Romethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN , N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m- Bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2 6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- ( m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo- p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) 2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [o- Bromo-pN, N-di (ethoxycarbonyl) aminophenyl] 2,6-di (trichloromethyl) -S-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine Etc.
Among these, 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] 2,6-di can be suitably used as the curable coloring composition of the present invention. (Trichloromethyl) -S-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine.

In addition to the above thermal polymerization initiator, other thermal polymerization initiators can be added to the curable coloring composition of the present invention as necessary.
Other thermal polymerization initiators include generally known organic peroxide compounds, azo compounds, active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine, and preferably have a decomposition temperature. It is a compound that is somewhat high and stable at room temperature, decomposes when heated, generates radicals, and becomes a polymerization initiator.

An organic peroxide compound refers to an organic compound having a —O—O— bond in the molecule.
When classified by chemical structure, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates and the like are listed.
Specifically, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, benzoyl peroxide, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, t-butyl peroxybenzoate, di-t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, t-butyl Peroxyacetate, t-hexyl peroxybenzoate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2 -Ethylhexyl monocarbonate, 2,5-dimethyl-2, -Bis (m-toluylperoxy) hexane, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisobutyrate, 1,1, 3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexinoyl peroxy) hexane, t-butyl peroxy-2-ethylhexanoate, t- Butyl peroxy maleic acid, cyclohexanone peroxide, methyl acetoacetate peroxide, methyl hexanone peroxide, acetyl acetone peroxide, 1,1-bis (t-hexyl proxy) -3,3,5-trimethylcyclohexane, 1,1 -Screw (t (Hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3.5 trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (T-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t -Butyl hydroperoxide and the like, and peroxyketal compounds such as 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane; diacyl peroxide compounds such as benzoyl peroxide; t-butylperoxybenzoate Peroxy Estes such as System compounds are preferred.

  Examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyronitrile), and the like. Is mentioned.

  Examples of the triazine compound include a vinyl-halomethyl-s-triazine compound described in JP-B-59-1281, and 2- (naphth-1-yl) -4,6-bis- described in JP-A-53-133428. Examples include halomethyl-s-triazine compounds and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compounds, specifically 2,4-bis (trichloromethyl) -6-p. -Methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6 -P-methoxystyryl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-to Azine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-todiazine, 4- [o-methyl-pN, N-di (ethoxy) Carbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-todiazine, 4- (pN-chloroethylcarbonylaminophenyleno) -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminopheny ] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s -Triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-, 6-di (trichloromethyl) -s-todiazine, 4- [o-fluoro-pN, N -Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (todichloromethyl) -s-todiazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di ( Todichloromethyl) -s-triazine, and the like.

  In this invention, it is not limited to the above thermal polymerization initiator, Other well-known things can also be used.

  When the content of the thermal polymerization initiator is 1% by mass or more with respect to the total solid content of the curable coloring composition of the present invention, the colored layer is sufficiently cured, and the curable coloring composition of the present invention. When the total solid content is 30% by mass or less, the viscosity of the composition is kept constant, and the stability over time is excellent. In addition, when a material having a relatively high half-life temperature (preferably 50 ° C. or higher, more preferably 80 ° C. or higher) is used, the composition can be suitably configured without changing with time. These initiators can be used alone or in combination of two or more.

<Polymerizable compound>
The curable coloring composition of this invention contains a photopolymerizable compound and a thermopolymerizable compound according to the coating method of a colored layer. Details are described below.
-Photopolymerizable compound-
The curable coloring composition of the present invention contains at least one photopolymerizable compound. By using it together with the photopolymerizable initiator, a higher degree of curing can be obtained, and the curability can be controlled as desired.
The photopolymerizable compound undergoes polymerization and curing under the action of the active species from the above-described photopolymerization initiator to form an image.
As the photopolymerizable compound, a compound having at least one ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is preferable, and a tetrafunctional or higher acrylate compound is more preferable.

Examples of the compound having at least one ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. Monofunctional acrylates and methacrylates; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (a (Liloyloxyethyl) Isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and then added (meth) acrylate after addition of ethylene oxide or propylene oxide, or poly (meth) acrylate of pentaerythritol or dipentaerythritol Urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Examples thereof include polyfunctional acrylates and methacrylates such as polyester acrylates described in Japanese Patent Publication No. 52-30490, and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

Further, compounds which are described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof and (meth) acrylated after addition of ethylene oxide or propylene oxide to the polyfunctional alcohol are also included. Can be used.
Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are via ethylene glycol or propylene glycol residues are preferable. These oligomer types are also used.

A photopolymerizable compound can be used individually by 1 type or in combination of 2 or more types.
As content of a photopolymerizable compound, Preferably it is 20 mass parts-200 mass parts with respect to 100 mass parts for the total solid of the curable coloring composition of this invention, More preferably, it is 50 mass parts-120. Part by mass. When the content is within the above range, curing can be performed satisfactorily.

-Thermally polymerizable compound-
The curable coloring composition of this invention contains at least 1 type of a thermopolymerizable compound. By using it together with the heat-polymerizable initiator, a higher degree of curing can be obtained, and the curability can be controlled as desired.

Here, the photopolymerizable compound can also be used as a thermally polymerizable compound.
Among them, preferred compounds are compounds having two or more ethylenically unsaturated groups, and those having a molecular weight of 1000 or less are preferred because of good smoothness after droplet ejection. Specifically, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, etc. Can be mentioned.

The curable coloring composition of the present invention may contain an epoxy compound as necessary.
The epoxy compound has at least two epoxy rings in one molecule. When the number of epoxy rings in one molecule is less than 2, the degree of curing becomes insufficient, and high solvent resistance and voltage holding ratio cannot be ensured.
The number of epoxy rings in one molecule is preferably 2 to 10, more preferably 2 to 5.

  As an epoxy compound (epoxy compound according to the present invention) having at least two epoxy rings in one molecule and having a calculated epoxy equivalent (molecular weight / epoxy ring number) of 100 to 500, bisphenol A type, cresol novolak Type, biphenyl type, alicyclic epoxy compound and the like. For example, as the bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( As mentioned above, manufactured by Toto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103 and the like (manufactured by Nagase Kasei Co., Ltd.), Plaxel GL-61, GL-62, G101, G102 (manufactured by Daicel Chemical Industries). Bisphenol F type and bisphenol S type similar to these can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel Cytec Co., Ltd.) can also be used. Further, as the cresol novolak type, Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Tohto Kasei Co., Ltd.), Denacol EM-125, etc. ) Is 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl or the like as the biphenyl type, and the alicyclic epoxy compound is Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100, etc. As mentioned above, Toto Kasei Co., Ltd.) can be mentioned. Furthermore, 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid Examples thereof include diglycidyl esters, other amine type epoxy resins such as Epototo YH-434 and YH-434L, and glycidyl esters obtained by modifying dimer acid in the skeleton of bisphenol A type epoxy resin.

  In the ink jet system, the epoxy compound can be added in a range not exceeding 50% by mass with respect to the total solid content excluding the pigment of the curable coloring composition. When the resin content is within the above range, the effect of suppressing volume shrinkage during curing is high, and when a cured film is formed by applying droplets to a partitioned area as in the ink jet method, a uniform thickness is obtained. A surface is obtained and the film has excellent solvent resistance. In the case of the slit coating method, the addition of 10% by mass or less greatly improves the solvent resistance and scratch resistance of the film.

<Other ingredients>
In addition to the above components, the curable coloring composition of the present invention includes various additives as necessary, for example, fillers, polymer compounds other than the alkali-soluble resins, surfactants other than the above, adhesion promoters, oxidation An inhibitor, an ultraviolet absorber, an aggregation inhibitor and the like can be blended.
Specific examples of various additives include fillers such as glass and alumina; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyl Dimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, (meth) acryloylpropyltrimethoxysilane, (meth) acryloylpropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacrylo Adhesion promoters such as cyclopropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol) and 2,6-di-tert-butylphenol And ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

Further, in order to promote the alkali solubility of the uncured part and further improve the developability of the curable coloring composition, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is added. be able to.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Others such as phenoxyacetic acid, methoxyphenoxyacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, umberic acid Carboxylic acid is mentioned.

  In addition to the above, it is preferable to add a thermal polymerization inhibitor to the curable coloring composition of the present invention. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl- 6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

<Color filter and liquid display element>
The color filter of the present invention is generally configured by providing a plurality of colored pixels having different hues and a black matrix separating the colored pixels. For these (particularly black matrix), the curable coloring composition of the present invention described above is applied onto a substrate to form a colored layer, dried (prebaked), exposed to a desired pattern, and then subjected to development processing. Can be produced.
The color filter of the present invention is constituted by using the curable coloring composition of the present invention described above. For example, the curable coloring composition prepared in a liquid state is coated on a desired substrate to be sensitized. It can be formed by forming a photoconductive layer, exposing the formed photocurable layer in a pattern, developing, and the like. Moreover, since the black matrix is configured using the curable coloring composition described above, the black matrix has a high optical density of black and is configured in a good sharp pattern with a rectangular cross section.
Below, an example of the manufacturing method of the color filter of this invention is shown.

-Preparation of curable coloring composition-
The curable coloring composition of the present invention contains a colorant, an acrylic copolymer (alkali-soluble resin) according to the present invention, a polymerizable compound, a photopolymerization initiator, and other components as necessary (preferably It can be prepared by mixing with a solvent and mixing and dispersing using various mixers and dispersers.
The step of mixing and dispersing (mixing and dispersing step) is preferably composed of kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted. In addition, it is preferable that the pigment type used in the kneading and dispersing steps is previously refined in particle size by a salt milling method or the like. A method of salt milling is known from Japanese Patent No. 3130217, Japanese translations of PCT publication No. 2003-504480 and the like. Also, fine pigments formed by the build-up method can be used.
In the kneading and dispersing step, the surface of the colorant particles of the raw material is promoted to be wetted with the constituent components mainly composed of the resin component of the vehicle, and the colorant particles and the solids of the vehicle solution / Convert to solution interface. In the fine dispersion step, the colorant particles are dispersed to a fine state close to primary particles by mixing and stirring together with a dispersion medium for fine particles of glass, zirconia or ceramic. Therefore, in the kneading and dispersing step, it is necessary to convert the interface formed by the colorant particle surface from air to a solution. Therefore, a strong shearing force and compressive force are required. On the other hand, in the fine dispersion step, it is necessary to uniformly and evenly distribute the particles to a fine state, and a disperser that applies impact force and shear force to the aggregated colorant particles, Preferably has a relatively low viscosity.

The kneading and dispersing step for producing a color filter using the curable coloring composition of the present invention includes first a colorant such as an organic pigment or carbon black, a part of the dispersion resin in the present invention, and a dispersant or The surface treatment agent is kneaded together with a part of the solvent. Examples of the machine used for kneading include two rolls, three rolls, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single screw or a twin screw extruder, and the like. Next, the remaining solvent and the dispersion resin in the present invention (the remainder not used for the kneading) are added, and a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc. are used, and 0.01-1 mm Disperse with beads made of glass, zirconia, etc. It is possible to omit the kneading step. In that case, a colorant such as a pigment, the dispersion resin in the present invention and, if necessary, a dispersant or a surface treatment agent are dispersed in beads together with a solvent. In this case, it is preferable to add the dispersion resin in the present invention for use in kneading during the dispersion.
For details on kneading and dispersing, see T.W. C. Also described in “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964).

-Application of curable coloring composition-
A curable coloring composition is applied on a substrate directly or via another layer by a coating method such as spin coating, slit coating method, casting coating method, roll coating method, ink jet method, etc. to form a photocurable coloring layer. Although formed, the curable coloring composition of the present invention exhibits the effect of the present invention particularly when applied by a slit coating method or an inkjet method.

(Slit application method)
Conventionally used spin (spin) coating, slit & spin methods require the rotation of the substrate, and the film thickness of the curable coloring composition dropped on the substrate is made uniform by the rotation of the substrate. A large load is applied to the rotation of the glass substrate due to an increase in size, and it has become difficult to rotate the large substrate. For this reason, a curable coloring composition is uniformly discharged onto a glass substrate using a slit-shaped nozzle having a width necessary for slit coating, and the slit nozzle or the glass substrate is moved at a uniform speed for coating (slit coating). ) Has been developed.
The moving speed of the slit nozzle is usually 50 to 200 mm / sec. Slit coating is not continuous, but is a single-wafer coating in which substrates are coated one by one. In the meantime, a curable coloring composition is required so that no foreign matter is generated by aggregation of the colorant or drying of the nozzle. The curable coloring composition is required to have liquid properties that prevent liquid from being discharged from the nozzle in a state where discharge is not necessary, but at the application end portion. Moreover, the curable coloring composition needs to have high fluidity (leveling property) so that the uniformity of a coating film can be ensured between drying and solidification.
For sheet-fed coating, equipment for cleaning the slit nozzle every time coating is devised. There are a method of wiping the nozzle each time, a method of preliminarily applying a small amount of coating liquid prior to coating, and cleaning the nozzle. The present invention is effective for both, but a method for discharging in advance is particularly desirable.

-Pattern formation-
The colored layer formed as described above is subjected to pattern exposure through a predetermined photomask, only the exposed portion is cured, and the operation of developing and removing the unexposed portion with a developer is repeated for the desired number of hues. A color filter provided with a colored image (including pixels and a black matrix) having a desired hue (for example, three colors or four colors such as R, G, B, and black) can be manufactured.
At this time, the light source used for exposure is preferably a high-pressure mercury lamp. In particular, ultraviolet rays such as g-line, h-line, i-line, and j-line are preferable, and ultraviolet rays including i-line and h-line as main components and including j-line are preferable. The exposure machine can be a proximity type exposure machine, a mirror projection system or a stepper system.

The thickness (after drying) of the colored layer formed using the curable coloring composition is generally preferably from 0.3 to 5.0 μm, more preferably from 0.5 to 3.5 μm, particularly preferably from 1.0 to 2.5 μm.
The colored layer can be dried (prebaked) by heating in a temperature range of 50 to 140 ° C. for 10 to 300 seconds with a hot plate, an oven, or the like. Especially, it is preferable to heat for 60 to 180 seconds in a 70-130 degreeC temperature range, and it is more preferable to heat for 90 to 120 seconds in a 90-120 degreeC temperature range. Drying can be complemented by vacuum drying after pre-baking.

-Development processing-
The development treatment is preferably an alkali development treatment, and an uncured portion is eluted in an alkaline aqueous solution by exposure to leave only a photocured cured portion.
Any developer can be used as long as it dissolves the uncured portion and does not dissolve the cured portion forming the filter portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used, and an alkaline developer is particularly preferable.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentrations of alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene are 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass is preferably used.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is preferably in the range of 20 to 90 seconds. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with water after development.
After the development process, a post-bake process can be performed as necessary. Post-baking is a heat treatment after development to complete curing, and can be usually performed at a temperature of about 200 to 220 ° C. (hard baking). The post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so that the layer after the development satisfies the above-mentioned conditions.

[Inkjet system]
The color filter of the present invention is characterized in that a heat treatment is performed at 150 to 250 ° C. after a pixel pattern is formed on a substrate by an inkjet method.
More specifically, in the method for producing a color filter of the present invention, droplets of the curable coloring composition of the present invention are applied to a concave portion defined by a light-shielding partition on a substrate by an ink jet method (colored region ( A pixel), and a process of heat-curing the formed colored region by heat treatment (hereinafter, also referred to as a “pixel formation process”) is provided.

  In the color filter of the present invention, by using the curable coloring composition of the present invention, there is no clogging at the tip of the ink jet nozzle, the work efficiency is excellent, and the produced color filter is also as described above. It is excellent.

  In the ink jet system, a method in which charged ink is continuously ejected and controlled by an electric field, a method in which ink is intermittently ejected using a piezoelectric element, and a method in which ink is foamed when heated is intermittently ejected. The method can be selected from known methods.

  The discharge conditions for discharging the curable coloring composition of the present invention are preferably set to a temperature of the composition of 20 to 50 ° C. to reduce the viscosity of the composition from the viewpoint of stability during discharge. It is desirable to keep the composition temperature as constant as possible in consideration of the influence on the droplet size and droplet discharge speed and the deterioration of image quality.

As the ink jet head (also simply referred to as a head), a known one can be applied. For the thermal head, a type having an operation valve as described in JP-A-9-323420 is preferable for ejection. As the piezo head, for example, heads described in European Patent A277,703, European Patent A278,590, and the like can be used. The head preferably has a temperature control function so that the temperature of the ink can be controlled. It is preferable to set the injection temperature in a range where the viscosity at the time of ejection is 5 to 25 mPa · s, and to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. Moreover, as a drive frequency, it is preferable to operate | move at 1-500 kHz.
The dried colored layer is dried (pre-baked) at 100 to 200 ° C. for 30 to 120 seconds, and then dried and cured (post-baked) at 180 to 260 ° C. During this time, a vacuum drying step may be performed as necessary. Pre-baking may be omitted.

-Board-
Examples of the substrate include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like in which a transparent conductive film is attached to these substrates, photoelectric sensors used in solid-state imaging devices, and the like. Examples include a conversion element substrate, such as a silicon substrate. Furthermore, a plastic substrate is also possible. When producing a color filter, a plurality of colored pixels and a black matrix for isolating each pixel are usually formed on these substrates.
Raw materials for the plastic substrate include amorphous polyolefin, polyethersulfone, polyglutarimide, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, norbornene polymer, bisaniline fluorene and diamine from the viewpoint of optical properties, heat resistance, mechanical strength, etc. Examples include polyimide as a component, polyester composed of bisphenolfluorene and dibasic acid, and the like. Among these, polyethersulfone, polycarbonate, polyethylene terephthalate, and norbornene polymer are preferable. Said raw materials are particularly preferred in LCD applications.
The properties required for plastic substrates include low thermal expansion (preventing deterioration of display accuracy associated with the curing process during color filter creation), gas barrier properties (ensuring liquid crystal stability), optical transmittance and optical isotropy, etc. Characteristics, surface smoothness, etc. Regarding thermal expansion, the thermal expansion coefficient is preferably 10 ⁻⁴ or less. The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on the surface thereof.

The curable coloring composition of the present invention is suitable for forming a black matrix separating colored pixels constituting a color filter, and chromatic colored pixels such as RGB.
An overcoat layer (flattening layer) can be provided on the color filter obtained using the curable coloring composition of the present invention. Examples of the resin (OC agent) forming the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition.
The black matrix is suitable for a liquid crystal display device (LCD), and is particularly suitable for applications such as televisions, personal computers, liquid crystal projectors, game machines, portable terminals such as mobile phones, digital cameras, and car navigation systems. Applicable to.

Examples of the present invention will be described below, but the present invention is not limited to these examples. Unless otherwise specified, “part” is based on mass.
In the Example of this invention, what changed the composition of the curable coloring composition which is a coating liquid was evaluated about the coating surface produced by the slit coating system, and the color filter produced by the inkjet system, respectively.

[Example 1]
<Formation of coated surface by slit coating method>
<< 1. Preparation of red curable composition >>
The following red composition A was stirred for 1 hour using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was finely dispersed for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads to obtain a dispersion. In addition, the average particle diameter of the pigment was measured by an ordinary method by SEM observation.
-Red composition A-dispersion / pigment: Pigment Red 254 (average particle size 20 nm) 11 partsPigment: Pigment Red 177 (average particle size 18 nm) 4 parts-dispersion resin (B-1-3) (following structure) 5 Parts / dispersant (trade name: Disperbyk-161, manufactured by Big Chemie) 3 parts
Propylene glycol monomethyl ether acetate of mixed solvent / alkali soluble resin of methoxybutyl acetate and butyl acetate: benzyl methacrylate / methacrylic acid copolymer 4 parts = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000) Solution (solid content: 50% by mass)
(B) Dispersing resin dissolving solvent: propylene glycol monomethyl ether acetate (SP value 9.2, boiling point 146 ° C.) 73 parts

-Red composition B-Coating liquid-Red composition A dispersion 100 parts-Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical) 2 parts-Polymerizable compound: Dipentaerythritol penta-hexaacrylate 8 parts-Polymerization initiator: 4 -(O-bromo-pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine 1 part-polymerization initiator: 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butanone-1 1 part ・ Initiator: Diethylthioxanthone 0.5 part ・ Polymerization inhibitor: p-methoxyphenol 0.001 part ・ Fluorosurfactant: (Product Name: Megafac R30, Dainippon Ink Co., Ltd.) 0.01 parts Nonionic surfactant: (Product name: Tetronic R150, manufactured by ADEKA) 0.2 parts · (A) High boiling point solvent: 1,3 butylene glycol diacetate (boiling point 232 ° C) 50 parts · (B) Dissolving resin dissolving solvent: propylene glycol monomethyl ether acetate (SP value 9.2, boiling point 146 80 ° C. 80 parts The above red composition B was mixed and stirred to obtain a coating liquid of a curable coloring composition.

[Example 2]
≪Preparation of green curable composition≫
The red composition A of Example 1 was changed to the following green composition A to obtain a dispersion.
-Green Composition A-Dispersion / Pigment: Pigment Green 36 (average particle diameter 19 nm) 11 partsPigment: Pigment Yellow 150 (average particle diameter 22 nm) 7 parts Dispersion resin (B-1-26) (following structure) 5 parts Dispersant (trade name: Disperbyk-161, 30% solution manufactured by Big Chemie) 3 parts alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer 4 parts = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)
(B) Dispersing resin dissolving solvent: 70 parts methyl 3-ethoxypropionate (SP value 9.3, boiling point 165 ° C.)

-Green composition B-Coating liquid-Green composition A dispersion 100 parts-Epoxy resin: (trade name EHPE3150 manufactured by Daicel Chemical) 2 parts-Polymerizable compound: Dipentaerythritol penta-hexaacrylate 8 parts-Polymerization initiator: 1 , 3-bistrihalomethyl-5-benzooxolantolyazine 2 parts, polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 1 part, polymerization initiator: diethyl Thioxanthone 0.5 parts ・ Polymerization inhibitor: p-methoxyphenol 0.001 part ・ Fluorosurfactant (trade name: Megafac R08 manufactured by Dainippon Ink) 0.02 parts ・ Nonionic surfactant (trade name: Emulgen A-60 Kao) 0.5 part ・ (A) High boiling point solvent: 1,3 Butylene glycol diacetate (boiling point 232 ° C.) 0 parts · (B) dispersion resin dissolved solvent: methyl 3-ethoxypropionate 100 parts (SP value 9.3, boiling point 165 ° C.)
The said green composition B was mixed and stirred and the coating liquid of the curable coloring composition was obtained.

[Example 3]
≪Preparation of blue curable composition≫
The red composition A of Example 1 was changed to the following blue composition A to obtain a dispersion.
-Blue composition A-Dispersion liquid / pigment: Pigment Blue 15: 6 (average particle diameter 15 nm) 14 partsPigment: Pigment Violet 23 (average particle diameter 23 nm in SEM observation) 1 part Dispersion resin (B-1-35) ) (The following structure 5 parts-Dispersant: (Brand name: Disperbyk-161, 30% solution manufactured by Big Chemie) 3 parts-Alkali soluble resin: benzyl methacrylate / methacrylic acid copolymer 4 parts = 75/25 [mass ratio] Propylene glycol monomethyl ether acetate solution of copolymer, weight average molecular weight Mw: 5000) (solid content: 50% by mass)
(B) Dispersing resin dissolving solvent: propylene glycol monomethyl ether acetate (SP value 9.2, boiling point 146 ° C.) 73 parts

-Blue composition B-Coating liquid-Blue composition A dispersion 100 parts-Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer 6 parts = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000) Propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)
・ Epoxy resin: (trade name: EHPE3150, manufactured by Daicel Chemical) 2 parts ・ UV curable resin: (trade name: Cyclomer P ACA-250, manufactured by Daicel Chemical) Copolymer Propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)
Polymerizable compound: 12 parts of dipentaerythritol pentahexaacrylate Polymerization initiator: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -1- (O-acetyl) Oxime) Ethanone 3 parts, Polymerization inhibitor: p-methoxyphenol 0.001 part, Fluorosurfactant: (trade name: Megafac R08, Dainippon Ink) 0.02 part, Nonionic surfactant: (trade name) : Emulgen A-60 manufactured by Kao) 1.0 parts (A) High boiling point solvent: Propylene glycol n-butyl ether acetate (boiling point 211 ° C) 20 parts (B) Dispersing resin dissolving solvent: Propylene glycol monomethyl ether acetate (SP (Value 9.2, boiling point 146 ° C.) 150 parts The blue composition B was mixed and stirred to obtain a coating liquid of a curable coloring composition. .

[Example 4]
≪Preparation of red curable composition≫
The following red composition was mixed and stirred to obtain a coating solution of a curable coloring composition.
-100 parts of dispersion of red composition A-Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical) 2 parts-Polymerizable compound: dipentaerythritol penta-hexaacrylate 8 parts-Polymerization initiator: 4- (o-bromo- pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine 1 part Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone 1 part ・ Polymerization initiator: Diethylthioxanthone 0.5 part ・ Polymerization inhibitor: 0.001 part of p-methoxyphenol ・ Fluorosurfactant (trade name: Megafac R30 Dainippon Ink Manufactured) 0.01 part nonionic surfactant (trade name: manufactured by Tetronic R150 ADEKA) 0.2 part (A) high boiling point Agent: 1,3-butylene glycol diacetate (boiling point 232 ° C.) 35 parts · (B) dispersion resin dissolving solvent: propylene glycol monomethyl ether acetate (SP value 9.2, boiling point 146 ° C.) 30 parts

[Example 5]
≪Preparation of red curable composition≫
The following red composition was mixed and stirred to obtain a coating solution of a curable coloring composition.
-100 parts of dispersion of red composition A-Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical) 2 parts-Polymerizable compound: dipentaerythritol penta-hexaacrylate 8 parts-Polymerization initiator: 4- (o-bromo- pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine 1 part Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone 1 part ・ Polymerization initiator: Diethylthioxanthone 0.5 part ・ Polymerization inhibitor: 0.001 part of p-methoxyphenol ・ Fluorosurfactant (trade name: Megafac R30 Dainippon Ink Manufactured) 0.01 part nonionic surfactant (trade name: manufactured by Tetronic R150 ADEKA) 0.2 part (A) high boiling point Agent: 1,3-butylene glycol diacetate (boiling point 232 ° C.) 102 parts · (B) dispersion resin dissolving solvent: propylene glycol monomethyl ether acetate (SP value 9.2, boiling point 146 ° C.) 28 parts

[Comparative Example 1]
≪Preparation of red curable composition≫
In the red composition B, a curable coloring composition was prepared in the same manner as the red composition B except that (A) the high-boiling solvent was replaced with propylene glycol monomethyl ether acetate. This composition does not contain the (A) high boiling point solvent of the present invention.

[Comparative Example 2]
≪Preparation of red curable composition≫
73 parts of (B) dispersion resin dissolving solvent of red composition A and 80 parts of (B) dispersion resin dissolving solvent of red composition B were respectively added to 73 parts of 1,3 butylene glycol diacetate and 80 parts of 1,3 butylene glycol diacetate. A curable coloring composition was prepared in the same manner as the red composition A and the red composition B, except that the composition was replaced with parts. This composition does not include (B) the solvent for dissolving the dispersed resin in the present invention other than the solvent contained in the dispersant and the alkali-soluble resin solution. The content of the solvent for dissolving the dispersed resin (B) in the total solvent of the coating solution is 2% by mass.

[Comparative Example 3]
≪Preparation of red curable composition≫
In the red composition A, a dispersion was prepared with a composition in which the dispersion resin (B-1-3) portion was replaced with the alkali-soluble resin 1, that is, the following red composition C.
-Red composition C-Dispersion / pigment: Pigment Red 254 (average particle size 20 nm) 11 parts / Pigment: Pigment Red 177 (average particle size 18 nm) 4 parts / dispersant (trade name: Disperbyk-161, manufactured by Big Chemie 30 % Solution) 3 parts, alkali-soluble resin 1: benzyl methacrylate / methacrylic acid copolymer 14 parts = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution (solid content) : 50% by mass)
Propylene glycol monomethyl ether acetate (SP value 9.2, boiling point 146 ° C.) 68 parts A curable coloring composition similar to the red composition B except that the red composition B was used instead of the red composition A. Produced.

[Comparative Example 4]
≪Preparation of red curable composition≫
The (B) dispersion resin dissolving solvent of the red composition A and the (B) dispersion resin dissolving solvent of the red composition B were respectively diisobutyl ketone (SP: 8.2 bp 169 ° C.) and diisobutyl ketone (SP: 8.2). A curable coloring composition was prepared in the same manner as the red composition A and the red composition B except that the composition was replaced with bp 169 ° C.

[Comparative Example 5]
≪Preparation of red curable composition≫
(B) Dispersing resin dissolving solvent of red composition A and (B) dispersing resin dissolving solvent of red composition B are respectively ethylene glycol monoethyl ether (SP value: 10.6 bp 136 ° C.) and ethylene glycol monoethyl ether. A curable coloring composition was prepared in the same manner as the red composition A and the red composition B except that the SP value was 10.6 bp 136 ° C.

[Comparative Example 6]
≪Preparation of red curable composition≫
(B) Dispersing resin dissolving solvent of red composition A and (B) dispersing resin dissolving solvent of red composition B are respectively propylene glycol monomethyl ether (SP value: 10.4 bp 120 ° C.) and propylene glycol monomethyl ether (SP value). : 10.4 bp 120 ° C.) A curable coloring composition was prepared in the same manner as the red composition A and the red composition B, except that the composition was replaced.
The compositions of Comparative Examples 4 to 6 do not contain (B) the solvent for dissolving the dispersed resin in the present invention other than the solvent contained in the resin solution. The content of propylene glycol monomethyl ether acetate is 2% by mass with respect to the total solvent of the coating solution.

[Comparative Example 7]
≪Preparation of red curable composition≫
The curable coloring composition was prepared by replacing the high-boiling solvent (A) of the red composition B with 3-ethoxyethyl propionate (bp: 169 ° C.).

<Evaluation of suitability for slit coating>
1. Coating stripe The slit coating suitability was evaluated using a slit coating apparatus equipped with a slit head having a slit interval of 100 μm and a coating effective width of 500 mm. The interval between the slit and the glass substrate and the discharge amount were adjusted so that the coating thickness after drying was 2 μm, and the application rate was 100 mm / second. After coating on 10 glass substrates (width 550 mm, length 650 mm, thickness 0.7 mm) by a normal method, the slit head is allowed to stand in the air for 5 minutes, and after waiting, a dummy dispense is performed for 3 seconds. Ten sheets were applied intermittently to the substrate. Thereafter, 10 pieces were applied in the same manner, and a total of 100 coated substrates were produced. After the application, after pre-baking at 90 ° C. for 60 seconds with a hot plate, the number of stripe-shaped unevenness on the application surface (hereinafter referred to as “application stripe” as appropriate) was visually counted using a sodium light source.
Evaluation was made with “◯” indicating no coating stripes, “Δ” indicating 1 to 5 coatings, and “X” indicating 6 or more coatings.
2. The number of foreign matters The foreign matters having a size of 20 μm or more were measured visually, and the number of foreign matters was evaluated per substrate.
3. Contrast The contrast of the coated substrate was measured with a contrast measuring device (trade name: BM-7, manufactured by Topcon Corporation), and used as an index of dispersibility. Expressed as a ratio when Example 1 is taken as 100. However, Examples 2 and 3 are omitted because they are different in spectrum and cannot be compared with Example 1.
The results are shown in Table 1.

[Example 6]
≪Preparation of red curable composition≫
A dispersion was obtained in the same manner as in the red composition A except that the red composition A was replaced with the following red composition D.
-Red composition D-dispersion / pigment: Pigment Red 254 (average particle size 20 nm) 11 partsPigment: Pigment Red 177 (average particle size 18 nm) 4 parts-dispersion resin (B-2-1) (following structure) 5 Part
(Monomer M-2 / Methacrylic acid / Terminal methacryloylated polymethyl methacrylate copolymer (10/15/75% by mass, weight average molecular weight 25000)
Dispersant (trade name: Disperbyk-161, 30% solution manufactured by Big Chemie) 3 parts alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer 4 parts = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)
・ (A) High boiling point solvent: 1,3 butylene glycol diacetate (boiling point 232 ° C.) 30 parts ・ (B) Dispersing resin dissolving solvent: propylene glycol monomethyl ether acetate (SP value 9.2, boiling point 146 ° C.) 23 parts

-Red composition E-ink, red composition D dispersion 80 parts-Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical) 2 parts-Polymerizable compound: 8.3 parts dipentaerythritol penta-hexaacrylate-Polymerization initiator: 1 , 3-bistrihalomethyl-5-benzooxolantolyazine 1.5 parts ・ Polymerization inhibitor: p-methoxyphenol 0.001 part ・ Nonionic surfactant (trade name: Emulgen A-60 manufactured by Kao Corporation) 0.8 Part ・ Fluorosurfactant (trade name: Megafac R08 manufactured by Dainippon Ink) 0.02 part ・ (A) High boiling point solvent: 1,3 butylene glycol diacetate (boiling point 232 ° C.) 40 parts Mixing the above red composition E The mixture was stirred to obtain an ink of a curable coloring composition.

[Example 7]
≪Preparation of green curable composition≫
A dispersion was obtained in the same manner as the red composition D except that the red composition D was replaced with the following green composition C.
-Green composition C-Dispersion liquid / pigment: Pigment Green 36 (average particle size 19 nm) 10 parts Pigment: Pigment Yellow 150 (average particle size 22 nm) 6 parts Dispersion resin (B-3-3) (following structure) 5 parts
(Exemplary Monomer (M-6) / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (10/15/75% by Mass, Weight Average Molecular Weight 25000)
-Dispersant (trade name: Disperbyk-161, 30% solution manufactured by Big Chemie) 3 parts-Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer 3 parts = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)
・ (A) High-boiling solvent: propylene glycol n-butyl ether acetate (boiling point 211 ° C.) 33 parts ・ (B) Dispersing resin dissolving solvent: propylene glycol monomethyl ether acetate (SP value 9.2, boiling point 146 ° C.) 20 parts

-Green composition D-Ink-Green composition C dispersion 80 parts-Epoxy resin: (trade name EHPE3150 manufactured by Daicel Chemical) 2 parts-Polymerizable compound: Dipentaerythritol penta-hexaacrylate 8 parts-Polymerization initiator: 1, 3 -Bistrihalomethyl-5-benzooxolantolyazine 1.5 parts ・ Polymerization inhibitor: p-methoxyphenol 0.001 part ・ Nonionic surfactant (trade name: Emulgen A-60 manufactured by Kao) 0.8 part ・Fluorosurfactant (trade name: Megafac R08 manufactured by Dainippon Ink) 0.02 part (A) High boiling point solvent: propylene glycol n-butyl ether acetate (boiling point 211 ° C.) 30 parts The green composition D is mixed and stirred. An ink of a curable coloring composition was obtained.

[Example 8]
≪Preparation of blue curable composition≫
A dispersion was obtained in the same manner as the red composition D except that the red composition D was replaced with the blue composition C shown below.
-Blue composition C-Dispersion / pigment: Pigment Blue 15: 6 (average particle size 15 nm) 12 parts-Pigment: Pigment Violet 23 (average particle size 23 nm) 1 part-Dispersion resin (B-1-46) (the following structure) ) 7 parts Dispersant (trade name: Disperbyk-161, 30% solution manufactured by Big Chemie) 3 parts Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer 6 parts = 75/25 [mass ratio] copolymer, Propylene glycol monomethyl ether acetate solution having a weight average molecular weight Mw of 5000 (solid content: 50% by mass)
(A) High boiling point solvent: 20 parts of propylene glycol n-butyl ether acetate (boiling point 211 ° C.)
(B) Solvent for dissolving dispersed resin: propylene glycol monomethyl ether acetate (SP value 9.2, boiling point 146 ° C.) 31 parts

-Blue composition D-Ink-Blue composition C dispersion 80 parts-Epoxy resin: (trade name EHPE3150 manufactured by Daicel Chemical) 2 parts-Polymerizable compound: Dipentaerythritol penta-hexaacrylate 10 parts-Polymerization initiator: 1, 3 -Bistrihalomethyl-5-benzooxolantoliain 2 parts ・ Polymerization inhibitor: p-methoxyphenol 0.001 part ・ Nonionic surfactant (trade name: Emulgen A-60 manufactured by Kao) 0.8 part ・ Fuso series Surfactant (trade name: Megafac R08 manufactured by Dainippon Ink) 0.02 part (A) High-boiling solvent: 30 parts of propylene glycol n-butyl ether acetate (boiling point 211 ° C.)
The blue composition D was mixed and stirred to obtain an ink of a curable coloring composition.

[Example 9]
≪Preparation of red curable composition≫
The following red composition was mixed and stirred to obtain a coating solution of a curable coloring composition.
-80 parts of dispersion of red composition D-Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical) 2 parts-Polymerizable compound: 8.3 parts of dipentaerythritol pentaacrylate-Polymerization initiator: 1,3-bistrihalo Methyl-5-benzooxolantriazine 1.5 parts ・ Polymerization inhibitor: p-methoxyphenol 0.001 part ・ Nonionic surfactant (trade name: Emulgen A-60 manufactured by Kao) 0.8 part ・ Fuso interface Activator (trade name: Megafac R08, Dainippon Ink) 0.02 part (A) High boiling point solvent: 1,3 butylene glycol diacetate (boiling point 232 ° C.) 70 part (B) Dispersing resin dissolving solvent: Propylene 15 parts of glycol monomethyl ether acetate (SP value 9.2, boiling point 146 ° C.)

[Example 10]
≪Preparation of red curable composition≫
A red composition F dispersion was obtained in the same manner as in the red composition D except that the solvent composition of the red composition D was replaced as follows.
-Solvent composition of red composition F-Dispersion liquid (A) High-boiling solvent: 1,3 butylene glycol diacetate (boiling point 232 ° C) 10 parts (B) Dispersing resin dissolving solvent: propylene glycol monomethyl ether acetate (SP value) (9.2, boiling point: 146 ° C.) 43 parts The following red composition was mixed and stirred to obtain a coating solution of a curable coloring composition.
-80 parts of dispersion of red composition F-Epoxy resin: (trade name EHPE3150 manufactured by Daicel Chemical) 2 parts-Polymerizable compound: 8.3 parts of dipentaerythritol pentaacrylate-Polymerization initiator: 1,3-bistrihalo Methyl-5-benzooxolantriazine 1.5 parts ・ Polymerization inhibitor: p-methoxyphenol 0.001 part ・ Nonionic surfactant (trade name: Emulgen A-60 manufactured by Kao) 0.8 part ・ Fuso interface Activator (trade name: Megafac R08 manufactured by Dainippon Ink) 0.02 parts · (A) High boiling point solvent: 1,3 butylene glycol diacetate (boiling point 232 ° C) 10 parts · (B) Dissolving solvent for dispersed resin: Propylene Glycol monomethyl ether acetate (SP value 9.2, boiling point 146 ° C.) 30 parts

[Comparative Example 8]
≪Preparation of red curable composition≫
A curable coloring composition was prepared in the same manner as in the red composition E, except that 1,3-butylene glycol diacetate of the red composition D and the red composition E was replaced with propylene glycol monomethyl ether acetate. This composition does not contain the (A) high boiling point solvent of the present invention.

[Comparative Example 9]
≪Preparation of red curable composition≫
A curable coloring composition was prepared in the same manner as in the red composition E except that the solvent for dissolving the dispersed resin (B) of the red composition D and the red composition E was replaced with 1,3-butylene glycol diacetate. This composition does not contain the solvent for dissolving the (B) dispersed resin of the present invention other than the solvent contained in the dispersant and the resin solution. The content of propylene glycol monomethyl ether acetate is 4% by mass with respect to the total solvent of the coating solution.

[Comparative Example 10]
≪Preparation of red curable composition≫
In the red composition D, a dispersion liquid of the following red composition G was prepared in the same manner as the red composition D except that the dispersion resin (B-2-1) was replaced with the alkali-soluble resin 2.
-Red composition G-dispersion / pigment: Pigment Red 254 (average particle size 20 nm) 11 parts-Pigment: Pigment Red 177 (average particle size 18 nm) 4 parts / dispersant (trade name: Disperbyk-161, manufactured by Big Chemie 30 % Solution) 3 parts, alkali-soluble resin 2: benzyl methacrylate / methacrylic acid copolymer 14 parts = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution (solid content) : 50% by mass)
・ (A) High boiling point solvent: 1,3 butylene glycol diacetate (boiling point 232 ° C.) 30 parts ・ (B) Dispersing resin dissolving solvent: propylene glycol monomethyl ether acetate (SP value 9.2, boiling point 146 ° C.) 18 parts A curable coloring composition was prepared in the same manner as the red composition E, except that the red composition dispersion G was used instead of the red composition dispersion D.

[Comparative Example 11]
≪Preparation of red curable composition≫
A curable coloring composition was prepared in the same manner as the red composition D, except that the solvent for dissolving the (B) dispersed resin of the red composition D was replaced with diisobutyl ketone. This composition does not contain the solvent for dissolving the (B) dispersed resin of the present invention other than the solvent contained in the dispersant and the resin solution. The content of propylene glycol monomethyl ether acetate is 4% by mass with respect to the total solvent of the coating solution.

[Comparative Example 12]
≪Preparation of red curable composition≫
A curable coloring composition was prepared in the same manner as the red composition D, except that the solvent for dissolving the dispersed resin (B) of the red composition D and the red composition E was replaced with ethylene glycol monoethyl ether. This composition does not contain the solvent for dissolving the (B) dispersed resin of the present invention other than the solvent contained in the dispersant and the resin solution. The content of propylene glycol monomethyl ether acetate is 4% by mass with respect to the total solvent of the coating solution.

<Production of color filter and evaluation of flatness and dischargeability of colored layer>
-Fabrication of color filter-
Resin black (thickness: 2.0 μm) having a width of 20 μm was arranged on a glass substrate in a lattice shape (opening portion: 100 μm × 200 μm) by a photolithography method. The ink was ejected into the opening using an ink jet droplet ejection tester having a piezo element having a nozzle (hole diameter 30 umφ). Discharge was carried out for 1 minute, paused for 1 minute, discharged for 1 minute, and intermittent discharge test was performed 20 times (total discharge time was 20 minutes) in a sequence of pause for 1 minute. The discharged substrate was heat-treated at 70 ° C. for 30 minutes, subjected to initial drying, and further subjected to heat treatment at 220 ° C. for 30 minutes to produce a color filter.
-Evaluation-
1. Flatness The thickness in the vicinity of the resin black and the thickness in the center of the pixel were measured with DECTAK-III (manufactured by ULVAC), and the thickness in the vicinity when the center was 100% was calculated.
2. Dischargeability The above-described intermittently discharged substrate was observed, and the droplet ejection time until the appearance of uncolored pixels was measured, which was used as an indicator of nozzle drying property and clogging.
3. Contrast The above ink was deposited on a glass substrate without a resin black partition so that the colored layer was 2.0 μm, and the contrast was measured with a contrast measuring device (trade name: BM-7, manufactured by Topcon Corporation). . The numerical values in the table are ratios when Example 11 is set to 100. Examples 12 and 13 were omitted because they were different in spectrum and could not be compared.
The results are shown in Table 2.

  From the results of Tables 1 and 2, the color filter formed by the slit coating method and the inkjet method using the solvent and the dispersion resin in the present invention has streaky unevenness on the coating surface compared to the comparative example. In addition, it was found that the film was excellent in slit coating suitability, had excellent droplet ejection properties, good flatness, and excellent color filter contrast.

Claims (7)

A curable coloring composition containing a colorant, a dispersion resin, a polymerization initiator, a polymerizable compound, and a solvent, wherein the solvent has (A) a boiling point of 180 ° C. or higher and 280 at normal pressure. A solvent having a solubility parameter of 8.5 to 10.5 and a boiling point of 130 to 170 ° C. at normal pressure, and the dispersion resin is represented by the following general formula (1): The polymer compound represented, the polymer containing the copolymer unit derived from the monomer represented by the following general formula (I), and the polymer comprising the structural unit represented by the following general formula (a) The curable coloring composition characterized by containing 1 or more types.

[In General Formula (1), R ¹ represents an (m + n) -valent organic linking group, and R ² represents a single bond or a divalent organic linking group. A ¹ is a monovalent organic group containing an organic dye structure or a heterocyclic ring, or an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms Represents a monovalent organic group having a group selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ¹ may be the same or different. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer skeleton. ]

[In General Formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (═O ) Represents one selected from S-, -OC (= O)-, -OCONH-, and -NHCO-. Y represents any one selected from NR ⁰³ , O, and S, and R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group. In the formula, N and Y are connected to each other to form a cyclic structure. m and n are each independently 0 or 1. ]

[In General Formula (a), R ^1a represents hydrogen or a methyl group, R ^2a represents an alkylene group, and Z ¹ represents a nitrogen-containing heterocyclic structure. ] One type selected from the compounds represented by the following general formula (i), general formula (ii), and general formula (iii) as the solvent (A) having a boiling point of 180 ° C. or higher and 280 ° C. or lower at normal pressure The curable coloring composition according to claim 1, comprising 5% by mass to 80% by mass with respect to the total mass of the solvent contained in the curable coloring composition.
R ¹ —O— (C ₂ H ₄ O) _n —R ² general formula (i)
R ¹ —O— (C ₃ H ₆ O) _n —R ² general formula (ii)
R ¹ —O— (C ₄ H ₈ O) _n —R ² general formula (iii)

[In General Formula (i), General Formula (ii), and General Formula (iii), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or an aralkyl group. Represents a carbonyl group. R ¹ and R ² do not represent a hydrogen atom at the same time. n represents an integer of 1 to 4. ]   One or more selected from (meth) acrylic acid, maleic acid, maleic anhydride, crotonic acid, and one or more selected from butyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene, 1 or more types of alkali-soluble resin chosen from the copolymer containing this is 5 mass%-50 mass% with respect to the total mass of the resin component containing the said dispersion resin, or characterized by the above-mentioned. The curable coloring composition according to claim 2.   The polymerization initiator contained in the curable coloring composition is a photopolymerization initiator, and the mass of the total solid content of the curable coloring composition is 10% by mass to the total amount of the curable coloring composition. The curable coloring composition according to any one of claims 1 to 3, which is 16% by mass and is applied by a slit coating method.   The polymerization initiator contained in the curable coloring composition is a thermal polymerization initiator, and the total solid content of the curable coloring composition is 25% by mass to the total amount of the curable coloring composition. It is 60 mass%, and is applied by the inkjet system, The curable coloring composition of any one of Claim 1 thru | or 3 characterized by the above-mentioned.   A color filter comprising a colored layer produced using the curable coloring composition according to any one of claims 1 to 5.   A liquid crystal display device comprising the color filter according to claim 6.