JP2005281351A - Fine particle dispersion, ink using the same and inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a fine particle dispersion that has excellent discharge stability, dispersion stability and storage stability of dispersion and ink that has excellent printing properties and image fastness (water resistance, light resistance, scratch resistance and ozone resistance) after recording by using the fine particle dispersion and to provide an inkjet recording method for recording with excellent printing properties and image fastness (water resistance, light resistance, scratch resistance and ozone resistance) after recording by using the ink. <P>SOLUTION: In the fine particle dispersion in which a fine particle containing an oil-soluble compound and a hydrophobic polymer is dispersed into an aqueous medium, the fine particle is dispersed into the aqueous medium by using a surfactant, the surfactant is an anionic surfactant and its content is 0.5-30 mass % based on the fine particle. The ink contains the fine particle dispersion. The inkjet recording method comprises using the ink. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a dispersion containing water-based fine particles containing an oil-soluble compound, an ink containing a dispersion containing the fine particles, and an ink jet recording method using the ink.

  In recent years, with the spread of computers, ink jet printers are widely used not only in offices but also in homes for printing on paper, films, cloths, and the like. As inks for inkjet recording, oil-based inks, water-based inks, and solid inks are known, but among these, water-based inks are advantageous in terms of manufacturability, handleability, odor, safety, etc. Water-based ink has become mainstream.

However, since many of the water-based inks use water-soluble dyes that dissolve in a molecular state, there are advantages that transparency and color density are high, but the water resistance is poor because the dyes are water-soluble. When printing on paper, bleeding (bleeding) occurs and the printing quality is remarkably deteriorated, the light resistance is poor, and furthermore, a recording paper (hereinafter referred to as “photographic quality paper”) provided with an ink receiving layer containing porous inorganic fine particles on the surface. In some cases, the image storability is extremely poor due to the influence of an oxidizing gas (SO _x , NO _x , ozone, etc.).

  Therefore, water-based inks using pigments and disperse dyes have been proposed for the purpose of solving the above problems (see, for example, Patent Document 1). However, there are problems such as lack of storage stability of the dispersion of pigments and disperse dyes in the water-based ink, and clogging at the ink discharge port. Furthermore, in photographic image quality paper, inks using the pigments and dyes have poor penetration, and there is a problem that the pigments and dyes are easily peeled off from the surface when rubbed by hand.

  On the other hand, a method in which an oil-soluble dye is included in a polymer has been proposed (see, for example, Patent Documents 2 to 3), but the color tone is insufficient, color reproducibility is not sufficient, and particularly due to an oxidizing gas or the like. The image durability is not sufficient, and when printed on photographic quality paper, the scratch resistance is not sufficient. By introducing a salt-forming group and a polyalkylene oxide group into the polymer, an ink having excellent colorability and scratch resistance has been proposed (for example, see Patent Document 4), but the scratch resistance by fingers is good, A high level of scratch resistance, such as eraser scrubbing, is insufficient. In addition, a method for improving color tone and scratch resistance by using a high-boiling organic solvent and a dye has been proposed (see, for example, Patent Document 5), but when a high level of image durability is required. It is insufficient.

As described above, it has handleability, odor, and safety, and the dispersed particle size is small, and the dispersion is excellent in dispersion stability and storage stability. Therefore, when applied to ink, at the tip of the nozzle. No clogging, excellent ejection stability, no paper dependency, excellent color development and color tone (hue), excellent ink penetration even when using the above photographic quality paper, water resistance after printing, especially image storage stability At present, a fine particle dispersion that has excellent scratch resistance and enables high-quality recording at a high concentration has not yet been provided.
JP 56-157468 A (all pages) JP 58-45272 A (all pages) JP-A-62-241901 (all pages) JP 2001-123097 (all pages) JP 2001-262018 A (all pages)

An object of the present invention is to solve the conventional problems and achieve the following objects. That is,
The present invention provides a fine particle dispersion that is excellent in ejection stability and excellent in dispersion stability and storage stability of the dispersion, and by using the fine particle dispersion, printing characteristics and image fastness after recording are provided. An object is to provide an ink excellent in (water resistance, light resistance, scratch resistance, and ozone resistance).
Furthermore, the present invention provides an ink jet recording method capable of recording with excellent printing characteristics and image fastness after recording (water resistance, light resistance, scratch resistance, ozone resistance) by using the ink. With the goal.

<1> In a fine particle dispersion in which fine particles containing an oil-soluble compound and a hydrophobic polymer are dispersed in an aqueous medium, the fine particles are dispersed in the aqueous medium using a surfactant. A fine particle dispersion comprising an anionic surfactant and having an anionic surfactant content of 0.5% by mass or more and 30% by mass or less based on the fine particles.
<2> The fine particle dispersion according to <1>, wherein the surfactant further contains a nonionic surfactant.

<3> The fine particle dispersion according to <1> or <2>, wherein the anionic surfactant is alkyl polyoxyethylene sulfate or aryl polyoxyethylene sulfate.
<4> The fine particle dispersion according to any one of <1> to <3>, wherein the oil-soluble compound is an oil-soluble dye.
<5> The oil-soluble compound is selected from the group consisting of compounds represented by the following general formulas (I), (II), (Y-I), (M-I), and (C-I). The fine particle dispersion according to any one of <1> to <4>, wherein the fine particle dispersion contains at least one compound.

[In General Formula (I) and General Formula (II), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano Group, hydroxy group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfone Amido group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic ring Thio group, sulfinyl group, phosphoryl group, acyl group, carboxyl group Or a sulfo group. A represents —NR ⁵ R ⁶ or a hydroxy group. R ⁵ and R ⁶ each independently represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. R ⁵ and R ⁶ may be bonded to each other to form a ring. B ¹ represents ═C (R ³ ) — or ═N—. B ² represents —C (R ⁴ ) ═ or —N═. R ¹ and R ⁵ , R ³ and R ⁶ , and R ¹ and R ² may be independently bonded to each other to form an aromatic ring or a heterocyclic ring. X represents a color coupler residue, and Y represents an unsaturated heterocyclic group. ]

[In General Formula (Y-I), A and B each independently represents an optionally substituted heterocyclic group. ]

[In General Formula (MI), A represents a residue of a 5-membered heterocyclic diazo component (A-NH ₂ ). In B ¹ and B ² , B ¹ represents = CR ¹ -and B ² represents -CR ² =, or one of them represents a nitrogen atom and the other represents = CR ¹ -or -CR ² =. R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. Each group may further have a substituent. G, R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Substituted with acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl group or heterocyclic group Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylarylsulfonylamino group, arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkylthio Represents a group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group. Each group may be further substituted. R ¹ and R ⁵ , and R ⁵ and R ⁶ may be independently bonded to form a 5- to 6-membered ring. ]

[In General Formula (CI), X ¹ , X ² , X ³ and X ⁴ are each independently —SO—Z ¹ , —SO ₂ —Z ¹ , or —SO ₂ —N (R ²¹ ). R ²² is represented. Z ¹ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group. Each may further have a substituent. R ²¹ and R ²² each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group. Each may further have a substituent. Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro Group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, An acyl group, a carboxyl group, or Represents a sulfo group, and each may further have a substituent. a1 to a4, b1.about.b4 each represent a number of substituents ^{X 1 ~X 4, Y 1 ~Y} 4, a1~a4 each independently represents an integer of 0 to 4, b1.about.b4 each independently Represents an integer of 0 to 4; However, the sum of a1 to a4 is 2 or more. Here, when representing an integer of 2 or more in each independently a1~a4 and b1.about.b4, a plurality of X ¹ to X ⁴ and Y ¹ to Y ⁴ may be the different from each other in the same. a1 and b1 each independently represent an integer of 0 to 4 that satisfies the relationship of a1 + b1 = 4. a2 and b2 each independently represent an integer of 0 to 4 that satisfies the relationship of a2 + b2 = 4. a3 and b3 each independently represent an integer of 0 to 4 that satisfies the relationship of a3 + b3 = 4. a4 and b4 each independently represent an integer of 0 to 4 that satisfies the relationship of a4 + b4 = 4. M represents a hydrogen atom, a metal element or an oxide thereof, a hydroxide, or a halide. ]

<6> An ink comprising the fine particle dispersion described in any one of the above items <1> to <5>.
<7> An ink jet recording method comprising a step of recording an image on a recording material using the ink according to the above <6>.

<8> The inkjet recording method according to <7>, wherein the recording material is a recording paper provided with a color material receiving layer having a porous structure containing at least polymer fine particles.

The fine particle dispersion of the present invention has handleability, low odor, and safety, and is suitable for aqueous ink for writing, aqueous printing ink, and information recording ink (thermal, piezoelectric, electric field or acoustic ink jet method). The particle size is small, and the dispersion is excellent in dispersion stability and storage stability.
The ink of the present invention has handleability, low odor, and safety, and is suitable for water-based ink for writing, water-based printing ink, information recording ink (thermal, piezoelectric, electric field, or acoustic ink jet method) and dispersed. Small particle size, excellent dispersion stability and storage stability of the dispersion, less clogging at the nozzle tip, no paper dependence, and printing characteristics such as ink permeability to photographic quality paper Also excellent in image fastness after recording (water resistance, light resistance, scratch resistance, ozone resistance).
Furthermore, the ink jet recording method of the present invention is a method that is excellent in the printing characteristics by using the ink, and excellent in the image fastness after recording.

  Hereinafter, a dispersion containing fine particles of the present invention (hereinafter also referred to as “fine particle dispersion”), an ink, an inkjet recording method, and the like will be described.

(Fine particle dispersion)
The fine particle dispersion of the present invention is a fine particle dispersion in which fine particles containing an oil-soluble compound and a hydrophobic polymer are dispersed in an aqueous medium, and the fine particles are dispersed in the aqueous medium using a surfactant. The surfactant includes an anionic surfactant, and the content of the anionic surfactant is from 0.5% by mass to 30% by mass with respect to the fine particles.
The fine particle dispersion means that fine particles containing an oil-soluble compound and a hydrophobic polymer use an anionic surfactant in an amount of not less than 0.5% by mass and not more than 30% by mass with respect to the fine particles. It is in a state of so-called emulsification dispersion dispersed as droplets. Furthermore, a hydrophobic high boiling point organic solvent and other colorants can be added as necessary.
In addition, the “aqueous medium” in the present invention means a mixture of water or a mixture of water and a small amount of a water-miscible organic solvent with additives and the like added as necessary.

(Hydrophobic polymer)
An example of the hydrophobic polymer is an oil-soluble polymer.
Here, the hydrophobic polymer is a polymer having a low affinity for water.
There is no restriction | limiting in particular as said oil-soluble polymer, Although it can select suitably according to the objective, A vinyl polymer is mentioned suitably. Examples of the vinyl polymer include conventionally known ones, which may be any of a water-insoluble type, a water-dispersed (self-emulsifying) type, and a water-soluble type. In this respect, a water dispersion type is preferable.

The water-dispersed vinyl polymer may be any of an ion dissociation type, a non-ionic dispersible group-containing type, or a mixed type thereof. Examples of the ion dissociation type vinyl polymer include a vinyl polymer containing a cationic dissociable group such as a tertiary amino group, and a vinyl polymer containing an anionic dissociative group such as a carboxylic acid and a sulfonic acid. . Examples of the nonionic dispersible group-containing vinyl polymer include vinyl polymers containing a nonionic dispersible group such as a polyethyleneoxy chain. Among these, from the viewpoint of dispersion stability of the fine particles, an ion dissociation type vinyl polymer containing an anionic dissociable group, a nonionic dispersible group containing type vinyl polymer, and a mixed type vinyl polymer are preferable.
As a monomer which forms the said vinyl polymer, the following are mentioned, for example.

  That is, acrylic esters, specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chloro Cyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahi Rofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, glycidyl acrylate, 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, 2,2 , 2-tetrafluoroethyl acrylate, 1H, 1H, 2H, 2H-perfluorodecyl acrylate and the like.

  Methacrylic acid esters, specifically, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydro Sibutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, allyl methacrylate, glycidyl methacrylate, 2,2,2-tetrafluoroethyl methacrylate, 1H, 1H, 2H, 2H-perfluorodecyl methacrylate Such as theft and the like. Vinyl esters, specifically vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, etc. Is mentioned.

  Acrylamides, specifically, acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, tert-butyl acrylamide, tert-octyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxymethyl acrylamide, butoxymethyl acrylamide, Examples include methoxyethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, diethyl acrylamide, β-cyanoethyl acrylamide, N- (2-acetoacetoxyethyl) acrylamide, diacetone acrylamide, and the like.

  Methacrylamide, specifically, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacryl Examples include amide, phenylmethacrylamide, dimethylmethacrylamide, β-cyanoethylmethacrylamide, N- (2-acetoacetoxyethyl) methacrylamide.

  Olefins, specifically dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene, styrenes such as styrene Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, vinyl benzoic acid methyl ester and the like.

  Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Other monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl Vinyl ketone, methoxyethyl vinyl ketone, N-vinyl oxazolidone, N-vinyl pyrrolidone, vinylidene chloride, methylenemalonnitrile, vinylidene, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyl Examples thereof include oxyethyl phosphate and dioctyl-2-methacryloyloxyethyl phosphate.

  Examples of the monomer having a dissociable group include a monomer having an anionic dissociable group and a monomer having a cationic dissociable group.

  Examples of the monomer having an anionic dissociable group include a carboxylic acid monomer, a sulfonic acid monomer, and a phosphoric acid monomer.

  Examples of the carboxylic acid monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, crotonic acid, itaconic acid monoalkyl esters (for example, itaconic acid monomethyl, itaconic acid monoethyl, itaconic acid monobutyl, etc. ), Maleic acid monoalkyl esters (for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.).

  Examples of the sulfonic acid monomer include styrene sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid (for example, acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid, etc.), methacryloyloxyalkyl sulfonic acid. (For example, methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.), acrylamide alkylsulfonic acid (for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfone, etc.) Acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.), methacrylamide alkylsulfonic acid (for example, 2-methacrylic acid) 2-methyl-ethanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylbutanesulfonic acid).

  Examples of the phosphoric acid monomer include vinylphosphonic acid and methacryloyloxyethylphosphonic acid.

  Among these, acrylic acid, methacrylic acid, styrene sulfonic acid, vinyl sulfonic acid, acrylamide alkyl sulfonic acid, and methacrylamide alkyl sulfonic acid are preferable. Acrylic acid, methacrylic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfone Acid, 2-acrylamido-2-methylbutanesulfonic acid is more preferable.

  Examples of the monomer having a cationic dissociable group include monomers having a tertiary amino group such as dialkylaminoethyl methacrylate and dialkylaminoethyl atacrylate.

  Examples of the monomer containing a nonionic dispersible group include an ester of polyethylene glycol monoalkyl ether and a carboxylic acid monomer, an ester of polyethylene glycol monoalkyl ether and a sulfonic acid monomer, polyethylene glycol monoalkyl ether and phosphorus. Examples thereof include an ester with an acid monomer, a vinyl group-containing urethane formed from a polyethylene glycol monoalkyl ether and an isocyanate group-containing monomer, and a macromonomer containing a polyvinyl alcohol structure. As a repeating number of the ethyleneoxy part of the said polyethylene glycol monoalkyl ether, 8-50 are preferable and 10-30 are more preferable. The number of carbon atoms in the alkyl group of the polyethylene glycol monoalkyl ether is preferably 1-20, and more preferably 1-12.

  These monomers may be used alone to form a vinyl polymer, or two or more may be used in combination to form a vinyl polymer. The purpose of the vinyl polymer (Tg adjustment, dissolution) For example, property improvement, dispersion stability, etc.).

  In the present invention, among the vinyl polymers, those having the dissociable group are preferable from the viewpoint of dispersion stability and storage stability of the fine particle dispersion, and at least one of a carboxyl group and a sulfonic acid group is used as the dissociable group. Those having a carboxyl group as the dissociable group are particularly preferable.

  The content of the dissociable group in the vinyl polymer is preferably 0.1 to 3.0 mmol / g, and more preferably 0.2 to 2.0 mmol / g. When the content of the dissociable group is small, the self-emulsifying property of the vinyl polymer is small. In addition, as the dissociating group, the anionic dissociating group may be an alkali metal (for example, Na, K, etc.) or a salt of ammonium ion, and the cationic dissociating group is further It may be a salt of an organic acid (for example, acetic acid, propionic acid, methanesulfonic acid) or an inorganic acid (hydrochloric acid, sulfuric acid, etc.).

Specific examples (P-1) to P-105)) of the vinyl polymer are listed below. The ratio in parentheses means the mass ratio. The present invention is not limited to these specific examples.
P-1) Methyl methacrylate-ethyl acrylate copolymer (50:50)
P-2) Methyl methacrylate-methyl acrylate copolymer (65:35)
P-3) Butyl acrylate-styrene copolymer (50:50)
P-4) Polyethylmethacrylate
P-5) Poly n-butyl methacrylate
P-6) Polyisobutyl methacrylate
P-7) Polyisopropyl methacrylate
P-8) Polymethylchloroacrylate
P-9) Poly (2-tert-butylphenyl acrylate)
P-10) Poly (4-tert-butylphenyl acrylate)

P-11) n-butyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10)
P-12) Methyl methacrylate-vinyl chloride copolymer (70:30)
P-13) Methyl methacrylate-styrene copolymer (50:50)
P-14) Isobutyl methacrylate-butyl acrylate copolymer (55:45)
P-15) n-butyl methacrylate-methyl methacrylate-styrene copolymer (50:30:20)
P-16) Vinyl acetate-acrylamide copolymer (85:15)
P-17) Vinyl chloride-vinyl acetate copolymer (65:35)
P-18) n-butyl acrylate-methyl methacrylate-n-butyl methacrylate copolymer (35:35:30)
P-19) Diacetone acrylamide-methyl methacrylate copolymer (50:50)
P-20) Ethyl methacrylate-n-butyl acrylate copolymer (70:30)

P-21) Methyl methacrylate-cyclohexyl acrylate copolymer (50:50)
P-22) tert-Butyl methacrylamide-methyl methacrylate-acrylic acid copolymer (60:30:10)
P-23) n-Butyl acrylate-acrylic acid copolymer (80:20)
P-24) Methyl methacrylate-isobutyl methacrylate-acrylic acid copolymer (52:28:20)
P-25) sec-butyl acrylate-acrylic acid copolymer (85:15)
P-26) n-Butyl methacrylate-Pentyl methacrylate-Methacrylic acid copolymer (38:38:24)
P-27) Ethyl acrylate-acrylic acid (95: 5)
P-28) Isopropyl acrylate-acrylic acid copolymer (90:10)
P-29) Butyl methacrylate-2-hydroxyethyl methacrylate-acrylic acid copolymer (85: 5: 10)
P-30) Cyanoethyl acrylate-benzyl methacrylate-acrylic acid copolymer (60:30:10)

P-31) Isobutyl methacrylate-tetrahydrofurfuryl acrylate-acrylic acid copolymer (60:30:10)
P-32) n-Butyl methacrylate-tert-butylacrylamide-acrylic acid copolymer (55: 37: 8)
P-33) n-Butyl methacrylate-1H, 1H, 2H, 2H-perfluorodecyl acrylate-acrylic acid copolymer (75: 20: 5)
P-34) Methyl methacrylate-n-butyl acrylate-acrylic acid copolymer (50: 45: 5)
P-35) 2-ethylhexyl methacrylate-methyl acrylate-acrylic acid copolymer (40: 55: 5)
P-36) 3-methoxybutyl methacrylate-styrene-acrylic acid copolymer (35:50:15)
P-37) Cyclohexyl methacrylate-allyl methacrylate-acrylic acid copolymer (35:50:15)
P-38) Isopropyl methacrylate-furfuryl methacrylate-acrylic acid copolymer (80:10:10)
P-39) Isopropyl methacrylate-2-butoxyethyl methacrylate-acrylic acid copolymer (75:15:10)
P-40) Ethyl acrylate-phenyl methacrylate-acrylic acid copolymer (72:15:13)

P-41) Isobutyl methacrylate-2- (2-ethoxyethoxy) ethyl methacrylate-acrylic acid copolymer (80:10:10)
P-42) Methacrylic acid ester-acrylic acid copolymer of isobutyl methacrylate-polyethylene glycol monomethyl ether (ethyleneoxy chain repeat number 23) (70:20:10)
P-43) Isobutyl methacrylate-dipropylene glycol monomethacrylate-acrylic acid copolymer (85: 5: 10)
P-44) Methacrylic acid ester-acrylic acid copolymer of isobutyl methacrylate-polyethylene glycol monomethyl ether (ethyleneoxy chain repeat number 9) (80:10:10)
P-45) Isobutyl acrylate-glycidyl methacrylate-acrylic acid copolymer (75:15:10)
P-46) Isobutyl acrylate-methoxystyrene-acrylic acid copolymer (75:15:10)
P-47) Isobutyl acrylate-N-vinylpyrrolidone-acrylic acid copolymer (60:30:10)
P-48) tert-butyl acrylate-methacrylic acid copolymer (88:12)
P-49) Hexyl acrylate-styrene-methacrylic acid copolymer (80: 5: 15)
P-50) 2,2,2-Tetrafluoroethyl methacrylate-methyl methacrylate copolymer-methacrylic acid copolymer (25:60:15)

P-51) Ethyl methacrylate-2-methoxyethyl methacrylate-methacrylic acid copolymer (70:15:15)
P-52) Ethyl methacrylate-2-ethoxyethyl methacrylate-methacrylic acid copolymer (70:15:15)
P-53) Vinyl acetate-methacrylic acid copolymer (85:15)
P-54) n-Butyl methacrylate-acrylamide-methacrylic acid copolymer (70:15:15)
P-55) tert-octylacrylamide-propyl methacrylate-methacrylic acid copolymer (20:65:15)
P-56) n-Butylmethacrylate-butoxymethylacrylamide-methacrylic acid copolymer (80: 5: 15)
P-57) n-Butyl methacrylate-diphenyl-2-methacryloyloxyethyl phosphate-methacrylic acid copolymer (80: 5: 15)
P-58) Isobutyl methacrylate-dimethylacrylamide-methacrylic acid copolymer (70:15:15)
P-59) n-Butyl methacrylate-Butylacrylamide-Methacrylic acid copolymer (70:15:15)
P-60) n-Butyl methacrylate-Phenylacrylamide-Methacrylic acid copolymer (70:15:15)

P-61) n-Butyl methacrylate-methacrylamide-methacrylic acid copolymer (70:15:15)
P-62) n-Butyl methacrylate-methoxyethyl methacrylamide-methacrylic acid copolymer (70:15:15)
P-63) n-Butyl methacrylate-N-vinyl pyrrolidone-methacrylic acid copolymer (70:15:15)
P-64) Isobutyl methacrylate-1H, 1H, 2H, 2H-perfluorodecyl acrylate-methacrylic acid copolymer (55:30:15)
P-65) Isobutyl methacrylate-2- (2-methoxyethoxy) ethyl methacrylate-methacrylic acid copolymer (50:35:15)
P-66) n-Butyl methacrylate-styrene sulfonic acid copolymer (90:10)
P-67) Ethyl methacrylate-styrene sulfonic acid copolymer (90:10)
P-68) n-Butyl acrylate-styrene-styrene sulfonic acid copolymer (80:10:10)
P-69) Isobutyl methacrylate-styrene sulfonic acid copolymer (90:10)
P-70) Isobutyl acrylate-triethylene glycol monomethacrylate-styrene sulfonic acid copolymer (80:10:10)

P-71) n-butyl acrylate-1H, 1H, 2H, 2H-perfluorodecyl methacrylate-styrene sulfonic acid copolymer (80:10:10)
P-72) n-Butyl acrylate-2-butoxyethyl methacrylate-styrene sulfonic acid copolymer (70:20:10)
P-73) n-Butyl methacrylate-2-acrylamido-2-methylethanesulfonic acid copolymer (90:10)
P-74) n-Butyl acrylate-2-butoxyethyl methacrylate-2-acrylamido-2-methylethanesulfonic acid copolymer (70:20:10)
P-75) Isobutyl methacrylate-2-acrylamido-2-methylethanesulfonic acid copolymer (90:10)
P-76) Isobutyl acrylate-n-butyl methacrylate-2-acrylamido-2-methylethanesulfonic acid copolymer (70:20:10)
P-77) Ethyl acrylate-tert-butyl methacrylate-2-acrylamido-2-methylethanesulfonic acid copolymer (60:30:10)
P-78) n-Butylmethacrylate-2-acrylamido-2-methylpropanesulfonic acid copolymer (90:10)
P-79) Ethyl methacrylate-2-acrylamido-2-methylpropanesulfonic acid copolymer (90:10)
P-80) Ethyl acrylate-tert-butyl methacrylate-2-acrylamido-2-methylpropanesulfonic acid copolymer (60:30:10)

P-81) n-Butyl acrylate-tert-butyl methacrylate-2-acrylamido-2-methylpropanesulfonic acid copolymer (60:30:10)
P-82) tert-butyl acrylate-tetrahydrofurfuryl acrylate-2-methylpropane sulfonic acid copolymer (50:40:10)
P-83) tert-butyl acrylate-1H, 1H, 2H, 2H-perfluorodecyl methacrylate-2-
Acrylamide-2-methylpropanesulfonic acid copolymer (60:30:10)
P-84) Methacrylate-2-acrylamide-2-methylpropanesulfonic acid copolymer of tert-butyl acrylate-polyethylene glycol monomethyl ether (ethyleneoxy chain repeat number 23) (60:30:10)
P-85) Isobutyl acrylate-N-vinylpyrrolidone-2-acrylamido-2-methylpropanesulfonic acid copolymer (60:30:10)
P-86) Ethyl methacrylate-2-acrylamido-2-methylpropane sulfonic acid soda copolymer (90.4: 9.6)
P-87) n-Butyl methacrylate-2-acrylamido-2-methylpropanesulfonic acid soda copolymer (98:12)
P-88) Isobutyl methacrylate-2-acrylamido-2-methylpropanesulfonic acid soda copolymer (90.4: 9.6)
P-89) n-Butyl methacrylate-tert-butyl methacrylate-2-acrylamido-2-methylpropanesulfonic acid soda copolymer (50:35:15)
P-90) Vinylpyrrolidone-isobutylmethacrylate-2-acrylamido-2-methylpropanesulfonic acid soda copolymer (50:35:15)

P-91) n-Butylmethacrylate-2-methacrylamide-2-methylpropanesulfonic acid copolymer (90:10)
P-92) n-butyl acrylate-tert-butyl methacrylate-2-methacrylamide-2-methylpropanesulfonic acid copolymer (60:30:10)
P-93) Isobutyl acrylate-hydroxymethylacrylamide-2-methacrylamide-2-methylpropanesulfonic acid copolymer (80:10:10)
P-94) n-butyl acrylate-tert-butyl methacrylate-vinyl sulfonic acid copolymer (60:30:10)
P-95) Hexyl methacrylate-methyl methacrylate-vinyl sulfonic acid copolymer (40:45:15)
P-96) Ethyl acrylate-tert-butyl methacrylate-vinyl sulfonic acid copolymer (60:30:10)
P-97) n-Butyl methacrylate-2-acrylamido-2-methylbutanesulfonic acid copolymer (90:10)
P-98) Ethyl methacrylate-2-acrylamido-2-methylbutanesulfonic acid copolymer (90:10)
P-99) Ethyl acrylate-tert-butyl methacrylate-2-acrylamido-2-methylbutanesulfonic acid copolymer (60:30:10)
P-100) n-butyl acrylate-tert-butyl methacrylate-2-acrylamido-2-methylbutanesulfonic acid copolymer (60:30:10)

P-101) Ethyl methacrylate-2-acrylamido-2-methylbutane sulfonic acid soda copolymer (90.4: 9.6)
P-102) n-Butyl methacrylate-2-acrylamido-2-methylbutanesulfonic acid soda copolymer (98:12)
P-103) Isobutyl methacrylate-2-acrylamido-2-methylbutane sulfonate copolymer (90.4: 9.6)
P-104) n-butyl methacrylate-tert-butyl methacrylate-2-acrylamido-2-methylbutanesulfonic acid soda copolymer (50:35:15)
P-105) n-Butyl methacrylate-2-methacrylamide-2-methylbutanesulfonic acid copolymer (90:10)

  The molecular weight (Mw) of the vinyl polymer is usually 1000 to 100,000, preferably 3000 to 50,000. When the molecular weight is 1000 to 10000, a stable dispersion of fine particles can be obtained, the solubility in an organic solvent is good, and the viscosity of the organic solvent is moderate and easy to disperse.

(Oil-soluble compounds)
The oil-soluble compound that is one of the components constituting the fine particle dispersion of the present invention is not particularly limited as long as it is a water-insoluble compound. It can be selected appropriately. For example, an ultraviolet absorber, an antioxidant, a light fading inhibitor, a liquid crystal compound, a fluorescent compound, an oil-soluble dye, an electron-donating colorless dye, an organic EL material, and respective polymers and oil-soluble polymers can be used.
The oil-soluble compound in the present invention means a compound that is substantially insoluble in water. More specifically, the solubility in water at 25 ° C. (the mass of the compound that can be dissolved in 100 g of water) is 1 g or less, Preferably it is 0.5 g or less, more preferably 0.1 g or less.
Among these, examples of the oil-soluble compound in the present invention include water-insoluble pigments and oil-soluble dyes, and oil-soluble dyes are particularly preferable.

The oil-soluble compound preferably has a melting point of 200 ° C. or lower, more preferably has a melting point of 150 ° C. or lower, and still more preferably has a melting point of 100 ° C. or lower. By using an oil-soluble compound having a low melting point, dye precipitation in the fine particle dispersion and the ink described later is suppressed, and the storage stability of the ink is improved.
In the fine particle dispersion and ink of the present invention, the oil-soluble compound may be used alone or in combination of several kinds. In addition, other water-soluble dyes, disperse dyes, pigments, and other colorants may be contained as necessary as long as the effects of the present invention are not impaired.

  Examples of oil-soluble compounds that can be used in the present invention include anthraquinone, naphthoquinone, styryl, indoaniline, azo, nitro, coumarin, methine, porphyrin, azaporphyrin, and phthalocyanine dyes. Is mentioned. In order to complete an inkjet ink for full-color printing, usually, at least four colors of dyes are required, which are the three primary colors of yellow (Y), magenta (M), and cyan (C) plus black.

  Of the oil-soluble compounds that can be used in the present invention, any yellow dye can be used. For example, phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components; for example, azomethine dyes having open-chain active methylene compounds as coupling components; Methine dyes such as benzylidene dyes and monomethine oxonol dyes; for example, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dye species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, Examples include acridinone dyes.

  Of the oil-soluble compounds usable in the present invention, any magenta dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines as coupling components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles as coupling components; for example arylidene dyes, styryl dyes, merocyanine dyes, oxonol dyes Methine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycyclic dyes such as dioxazine dyes, etc. Can be mentioned.

  Of the oil-soluble compounds that can be used in the present invention, any cyan dye can be used. For example, indoaniline dyes, indophenol dyes or azomethine dyes having pyrrolotriazoles as coupling components; polymethine dyes such as cyanine dyes, oxonol dyes, merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes Phthalocyanine dyes; anthraquinone dyes; for example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components, and indigo / thioindigo dyes.

  Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated. In this case, the counter cation is an alkali metal or an inorganic cation such as ammonium. Alternatively, it may be an organic cation such as pyridinium or quaternary ammonium salt, and may further be a polymer cation having these in a partial structure.

Among the oil-soluble compounds, preferred specific examples include the following, but the present invention is not limited to these.
For example, C.I. I. Solvent Black 3, 7, 27, 29 and 34; I. Solvent Yellow 14, 16, 19, 29, 30, 56, 82, 93 and 162; I. Solvent Red 1, 3, 8, 18, 24, 27, 43, 49, 51, 72, 73, 109, 122, 132 and 218; I. Solvent Violet 3; C.I. I. Solvent Blue 2, 11, 25, 35, 38, 67 and 70; C.I. I. Solvent Green 3 and 7; I. Solvent Orange 2 and the like are preferable.
Among these, the Nubian Black PC-0850, Oil Black HBB, Oil Yellow 129, Oil Yellow 105, Oil Pink 312, Oil Red 5B, Oil Scallet 308, Vali Fast Blue 2606, Oil Blue Blu (Oil S) Hodogaya Chemical Co., Ltd.), Neopen Yellow 075, Neopen Magenta SE1378, Neopen Blue 808, Neopen Blue FF4012, Neopen Cyan FF4238 (manufactured by BASF) and the like are more preferable.

In the present invention, a disperse dye can be used as long as it is soluble in a water-immiscible organic solvent. Preferred examples thereof include the following, but the present invention is not limited to these.
For example, C.I. I. Disperse Yellow 5,42,54,64,79,82,83,93,99,100,119,122,124,126,160,184: 1,186,198,199,201,204,224 and 237 C. I. Disperse Orange 13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119 and 163; I. Disperse Red 54, 60, 72, 73, 86, 88, 91, 92, 93, 111, 126, 127, 134, 135, 143, 145, 152, 153, 154, 159, 164, 167: 1,177 , 181, 204, 206, 207, 221, 239, 240, 258, 277, 278, 283, 311, 323, 343, 348, 356 and 362; I. Disperse violet 33; C.I. I. Disperse Blue 56, 60, 73, 87, 113, 128, 143, 148, 154, 158, 165, 165: 1, 165: 2, 176, 183, 185, 197, 198, 201, 214, 224, 225 , 257, 266, 267, 287, 354, 358, 365 and 368; I. Disperse green 6: 1 and 9 are preferable.

Among the oil-soluble compounds, preferred are compounds represented by the following general formula (I) (azo dyes) and compounds represented by the following general formula (II) (azomethine dyes). An azomethine dye represented by the following general formula (II) is known as a dye formed by oxidation from a coupler and a developing agent in a photographic material.
Hereinafter, the compounds represented by the general formula (I) and the general formula (II) will be described. At least one of the groups represented by the following general formula (I) and the general formula (II) is described below. A compound having a preferable range shown is preferable, a compound having more groups in a preferable range is more preferable, and a compound in which all groups are in a preferable range is particularly preferable.

In the above general formula (I) and general formula (II), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano Group, hydroxy group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfone Amido group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic ring Thio group, sulfinyl group, phosphoryl group, acyl group, carboxyl group It represents a sulfo group.
Among these, R ² is preferably a hydrogen atom, a halogen atom, an aliphatic group, an alkoxy group, an aryloxy group, an amide group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, or a sulfonamide group.

In the general formula (I) and general formula (II), A represents —NR ⁵ R ⁶ or a hydroxy group. A is preferably —NR ⁵ R ⁶ .
R ⁵ and R ⁶ each independently represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Among these, as R ⁵ and R ⁶ , each independently is preferably a hydrogen atom, an alkyl group and a substituted alkyl group, an aryl group and a substituted aryl group, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, And a substituted alkyl group having 1 to 18 carbon atoms is most preferred. R ⁵ and R ⁶ may be bonded to each other to form a ring.

In the general formula (II), B ¹ represents ═C (R ³ ) — or ═N—. B ² represents —C (R ⁴ ) ═ or —N═. B ¹ and B ² are preferably not simultaneously -N =, more preferably B ¹ is = C (R ³ )-and B ² is -C (R ⁴ ) =.

In the general formula (I) and general formula (II), R ¹ and R ⁵ , R ³ and R ⁶ , and R ¹ and R ² are each independently bonded to each other to form an aromatic ring or a heterocyclic ring. May be formed.

In this specification, an aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group.
The aliphatic group may be branched or cyclic. 1-20 are preferable and, as for the carbon atom number in the said aliphatic group, 1-18 are more preferable.
The aryl moiety of the aralkyl group and substituted aralkyl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
Examples of the substituent of the alkyl moiety in the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, and the substituted aralkyl group are the same as the examples of the substituents mentioned for R ¹ , R ² , R ³ and R ^4. It is done.
Examples of the substituent of the aryl moiety in the substituted aralkyl group include the same substituents as those in the following substituted aryl group.

In this specification, the aromatic group means an aryl group and a substituted aryl group. As the aryl group, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
The aryl moiety in the substituted aryl group is the same as in the above aryl group.
Examples of the substituent in the substituted aryl group include the same substituents as those exemplified for R ¹ , R ² , R ³ and R ⁴ .

In the general formula (I), Y represents an unsaturated heterocyclic group. Y is preferably a 5-membered or 6-membered unsaturated heterocyclic ring. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. N, O, and S can be mentioned as an example of the hetero atom of a heterocyclic ring.
Examples of the unsaturated heterocyclic ring include pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazole ring, thiophene ring, benzothiazole ring, benzoxazole ring, benzoisothiazole ring, pyrimidine ring, pyridine ring, and quinoline. A ring or the like is preferable. In addition, the unsaturated heterocyclic group may have the substituents exemplified in R ^{1 to} R ⁴ .

In the general formula (II), X represents a color coupler residue. As the coupler, the following couplers are preferable.
As yellow couplers, U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, 4,248,961, JP-B 58- 10739, British Patents 1,425,020, 1,476,760, U.S. Patents 3,973,968, 4,314,023, 4,511,649, European Patent 249,473A Couplers represented by formulas (I) and (II) of No. 502,424A, couplers represented by formulas (1) and (2) of No. 513,496A (particularly Y-28 on page 18). A coupler represented by the formula (I) of claim 1 of US Pat. No. 568,037A, a coupler represented by the general formula (I) of lines 45 to 55 of column 1 of US Pat. No. 5,066,576, 4-274425 of paragraph 0008 A coupler represented by the general formula (I), a coupler described in claim 1 on page 40 of European Patent 498,381A1 (particularly D-35 on page 18), and a formula (Y) on page 4 of 447,969A1. (Especially Y-1 (page 17), Y-54 (page 41)), US Pat. No. 4,476,219, column 7, lines 36 to 58, formulas (II) to (IV) (Especially II-17, 19 (column 17), II-24 (column 19)) and the like.

  As magenta couplers, there are US Pat. Nos. 4,310,619, 4,351,897, European Patent 73,636, US Pat. Nos. 3,061,432, 3,725,067, Research Disclosure No. . 24220 (June 1984), ibid. 24230 (June 1984), JP-A-60-33552, JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, U.S. Pat. No. 500,630, No. 4,540,654, No. 4,556,630, International Publication No. WO88 / 04795, JP-A-3-39737 (L-57 (lower right of page 11), L-68 (12) (Lower right of page), L-77 (lower right of page 13), [A-4] -63 (page 134), [A-4] -73, -75 (page 139) of European Patent 456,257, 486, 965, M-4, -6 (page 26), M-7 (page 27), 571, 959A, M-45 (page 19), JP-A-5-204106, (M-1) (Page 6), M-22 in paragraph 0237 of 4-36263 And the like.

  Examples of cyan couplers include U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, European Patent 73,636, and JP-A-4-204843. CX-1,3,4,5,11,12,14,15 (pages 14-16); C-7,10 (page 35), 34,35 (page 37) of JP-A-4-43345 , (I-1), (I-17) (pages 42 to 43); couplers represented by general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385.

  In addition, couplers described in JP-A-62-215272 (page 91), JP-A-2-33144 (pages 3, 30), and EP355,660A (pages 4, 5, 45, 47) are also useful. is there.

  Among the dyes represented by the general formula (I), the magenta dye is particularly preferably a dye represented by the following general formula (III).

In the general formula (III), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ¹ is preferably an electron withdrawing group having a σp value of 0.30 or more and 1.0 or less. Preferable specific substituents may include an electron-withdrawing substituent described later, among which an acyl group having 2 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, a nitro group, More preferred are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, and a halogenated alkyl group having 1 to 12 carbon atoms. An alkylsulfonyl group having 1 to 12 carbon atoms and an arylsulfonyl group having 6 to 18 carbon atoms are more preferable, and a cyano group is particularly preferable.

R < ¹ > -R < ⁶ > is synonymous with the said general formula (I), and those preferable ranges are also the same.
Z ² represents a hydrogen atom, an aliphatic group, or an aromatic group.
Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Among them, Q is preferably a group composed of a nonmetallic atom group necessary for forming a 5-membered ring to an 8-membered ring, and more preferably an aromatic group or a heterocyclic group. The 5-membered ring to 8-membered ring may be substituted, may be a saturated ring, or may have an unsaturated bond. As said nonmetallic atom group, a nitrogen atom, an oxygen atom, a sulfur atom, or a carbon atom is preferable.
Examples of the 5-membered ring to 8-membered ring include benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole. Preferred examples include a ring, a benzimidazole ring, an oxazole ring, a benzoxazole ring, an oxane ring, a sulfolane ring, and a thiane ring. When these rings further have a substituent, the substituent may be the above R ^{1 to} R ^The groups exemplified in ⁴ are preferred.
A preferable structure of the dye represented by the general formula (III) is described in JP-A No. 2001-335714.

  Among the dyes represented by the general formula (II), the magenta dye is particularly preferably a dye represented by the following general formula (IV).

In the general formula (IV), G represents a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, alkoxy group, aryloxy group, alkylthio group, arylthio group, ester group, amino group, carbamoyl group. Represents a sulfonyl group, a sulfamoyl group, a ureido group, a urethane group, an acyl group, an amide group, or a sulfonamide group.
R ¹ , R ² , A, B ¹ and B ² have the same meaning as in the general formula (II), and preferred ranges thereof are also the same as in the general formula (II).
L represents an atomic group that forms a 5- or 6-membered nitrogen-containing heterocyclic ring, and the atomic group that forms the nitrogen-containing heterocyclic ring includes an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, and an alkoxy group. , Aryl group, oxy group, alkylthio group, arylthio group, ester group, amino group, carbamoyl group, sulfonyl group, sulfamoyl group, ureido group, urethane group, acyl group, amide group, or sulfonamide group Or a condensed ring may be formed with another ring.

In the dye represented by the general formula (IV), A is preferably —NR ⁵ R ⁶ , and L is preferably a 5-membered nitrogen-containing heterocycle, and preferably 5-membered nitrogen-containing heterocycle. For example, an imidazole ring, a triazole ring, a tetrazole ring and the like are preferable.

  Of the dyes represented by the general formula (I) and the general formula (II), examples of the magenta dye include compounds (M-1 to M70) described in Japanese Patent Application No. 2002-10361. However, the present invention is not limited to these.

  The compounds that can be used in the present invention are described in Japanese Patent Application No. 11-365187, Japanese Patent Application Laid-Open No. 2001-181549, and Japanese Patent Application Laid-Open No. 2001-335714 in addition to the above exemplified compounds, but are not limited thereto. Absent.

The dye represented by the formula (III) of the present invention can be synthesized with reference to, for example, methods described in JP-A Nos. 2001-335714 and 55-161856.
The coloring matter represented by the formula (IV) of the present invention can be synthesized by referring to the methods described in, for example, JP-A-4-1267772, JP-B-7-94180 and JP-A-2001-246763. it can.

  Of the dyes represented by the general formula (II), a pyrrolotriazole azomethine dye represented by the following general formula (V) is particularly preferable as the cyan dye.

In the general formula (V), A, R ¹ , R ² , B ¹ and B ² are synonymous with the general formula (II), and their preferred ranges are also the same as the general formula (II). .
Z ³ and Z ⁴ are each independently synonymous with G in the general formula (IV). Z ³ and Z ⁴ may be bonded to each other to form a ring structure.
M is an atomic group capable of forming a 1,2,4-triazole ring condensed with the 5-membered ring of the general formula (V), and one of the two atoms B ³ and B ^{4 in} the condensed part is A nitrogen atom and the other a carbon atom.

Furthermore, among the pyrrolotriazole azomethine dyes represented by the general formula (V), those in which Z ³ is an electron-attracting group having a Hammett substituent constant σ _p value of 0.30 or more are sharply absorbed. Preferably, those having an electron withdrawing group having a Hammett substituent constant σ _p value of 0.45 or more are more preferable, and those having an Hammett substituent constant σ _p value of 0.60 or more are particularly preferable.
And the sum of Hammett's substituent constant σ _p values of Z ³ and Z ⁴ of 0.70 or more exhibits an excellent hue as cyan, and is most preferable.

  The pyrrolotriazole azomethine dye represented by the general formula (V) can be used as a magenta dye by changing a substituent, but is preferably used as a cyan dye.

Here, Hammett's substituent constant σp value used in this specification will be described.
Hammett's rule is a method for determining the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today.
Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (McGraw-Hill), “Chemical domain” special edition, 122, 96-103, 1979 (Nankodo).

In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, but this means that it is limited to only a substituent having a known value that can be found in the above-mentioned book. Needless to say, even if the value is unknown in the literature, it also includes a substituent that would be included in the range when measured based on Hammett's law.
In addition, the general formula (I) to the general formula (V) of the present invention include those that are not benzene derivatives. However, as a measure of the electronic effect of the substituent, the σp value is independent of the substitution position. Is used. Therefore, in the present invention, the σp value is used in this sense.

Examples of the electron withdrawing group having a Hammett substituent constant σ _p value of 0.60 or more include a cyano group, a nitro group, an alkylsulfonyl group (for example, a methanesulfonyl group, an arylsulfonyl group (for example, a benzenesulfonyl group), and the like.

In addition to the above, the electron withdrawing group having a Hammett σ _p value of 0.45 or more includes an acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, m- Chlorophenoxycarbonyl), alkylsulfinyl groups (eg n-propylsulfinyl), arylsulfinyl groups (eg phenylsulfinyl), sulfamoyl groups (eg N-ethylsulfamoyl, N, N-dimethylsulfamoyl), halogenated An alkyl group (for example, trifluoromethyl) etc. are mentioned.

As an electron withdrawing group having a Hammett substituent constant σ _p value of 0.30 or more, in addition to the above, an acyloxy group (for example, acetoxy), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl) , Halogenated alkoxy groups (for example, trifluoromethyloxy), halogenated aryloxy groups (for example, pentafluorophenyloxy), sulfonyloxy groups (for example, methylsulfonyloxy group), halogenated alkylthio groups (for example, difluoromethylthio) An aryl group (eg, 2,4-dinitrophenyl, pentachlorophenyl) substituted with an electron withdrawing group having two or more σ _p values of 0.15 or more, and a heterocyclic ring (eg, 2-benzoxazolyl) , 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl), etc. .

  In addition to the above, examples of the electron withdrawing group having a σp value of 0.20 or more include a halogen atom.

  Among the pyrrolotriazole azomethine dyes in the present invention, preferred examples of cyan dyes include compounds (C-1 to C-9) described in Japanese Patent Application No. 2002-10361, but the present invention is limited thereto. Is not to be done.

  Examples of the dye that can be used in the present invention further include exemplary compounds described in JP-A No. 2001-181547, but the present invention is not limited thereto.

  As a yellow pigment | dye used as an oil-soluble compound of this invention, the compound (dye) represented by the following general formula (YI) is preferable.

  In the general formula (Y-I), A and B each independently represent an optionally substituted heterocyclic group. The heterocyclic ring is preferably a heterocyclic ring composed of a 5-membered ring or a 6-membered ring, and may be a monocyclic structure or a polycyclic structure in which two or more rings are condensed. It may be a ring or a non-aromatic heterocyclic ring. As a hetero atom constituting the heterocyclic ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable.

In the general formula (Y-I), examples of the heterocyclic ring represented by A include 5-pyrazolone, pyrazole, oxazolone, isoxazolone, barbituric acid, pyridone, rhodanine, pyrazolidinedione, pyrazolopyridone, meldrum acid, and these A condensed heterocyclic ring in which a hydrocarbon aromatic ring or a heterocyclic ring is further condensed to the heterocyclic ring is preferred. Among these, 5-pyrazolone, 5-aminopyrazole, pyridone and pyrazoloazoles are preferable, and 5-aminopyrazole, 2-hydroxy-6-pyridone and pyrazolotriazole are particularly preferable.

  In the general formula (Y-I), the heterocyclic ring represented by B includes pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, Thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, benzoisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline Etc. are preferable. Of these, pyridine, quinoline, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzoisothiazole, thiadiazole, and benzoisoxazole are preferable. Thiophene, pyrazole, thiazole, benzoxazole, benzisoxazole, isothiazole, imidazole, benzothiazole, thiadiazole are more preferable, and pyrazole, benzothiazole, benzoxazole, imidazole, 1,2,4-thiadiazole, 1,3,4 -Thiadiazole is particularly preferred.

  Substituents substituted for A and B are halogen atoms, alkyl groups, cycloalkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, alkoxy groups, aryls. Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, Sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfo group Group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group ,, an imide group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a silyl group.

  Among the dyes represented by the general formula (Y-I), dyes represented by the following general formulas (Y-II), (Y-III), and (Y-IV) are more preferable.

In the general formula (Y-II), R ¹ and R ³ are a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aryl group, or an ionic hydrophilic group. Represents. R ² represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, a carbamoyl group, an acyl group, an aryl group or a heterocyclic group. R ⁴ represents a heterocyclic group.

In the general formula (Y-III), R ⁵ represents a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aryl group, or an ionic hydrophilic group. Za represents -N =, - NH-, or C (R ¹¹⁾ = represents, Zb and Zc each independently, -N =, or C (R ¹¹⁾ = represents the R ¹¹ is a hydrogen atom Or represents a non-metallic substituent. R ⁶ represents a heterocyclic group.

In the general formula (Y-IV), R ⁷ and R ⁹ are each independently a hydrogen atom, cyano group, alkyl group, cycloalkyl group, aralkyl group, aryl group, alkylthio group, arylthio group, alkoxycarbonyl group, A carbamoyl group or an ionic hydrophilic group is represented. R ⁸ is a hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, cyano group, acylamino group, sulfonylamino group, alkoxycarbonylamino group, ureido group, alkylthio group, arylthio group, alkoxycarbonyl group, It represents a carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, alkylamino group, arylamino group, hydroxy group, or ionic hydrophilic group. R ¹⁰ represents a heterocyclic group.

The substituents represented by R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ⁸ and R ^{9 in the} general formulas (Y-II), (Y-III), and (Y-IV) are described in detail below. Describe.

The alkyl group represented by R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ⁸ and R ⁹ includes an alkyl group having a substituent and an unsubstituted alkyl group.
The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.
Preferable examples of the alkyl group include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, and 4-sulfobutyl.

The cycloalkyl group represented by R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ⁸ and R ⁹ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group.
The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms, and examples of the substituent include ionic hydrophilic groups.
Suitable examples of the cycloalkyl group include cyclohexyl.

The aralkyl group represented by R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ⁸ and R ⁹ includes an aralkyl group having a substituent and an unsubstituted aralkyl group.
The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and examples of the substituent include an ionic hydrophilic group.
Suitable examples of the aralkyl group include benzyl and 2-phenethyl.

The aryl group represented by R ¹ , R ² , R ³ , R ⁵ , R ⁷ , and R ⁹ includes an aryl group having a substituent and an unsubstituted aryl group.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group.
Preferable examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl, and m- (3-sulfopropylamino) phenyl.

The alkylthio group represented by R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ⁸ and R ⁹ includes an alkylthio group having a substituent and an unsubstituted alkylthio group.
The alkylthio group is preferably an alkylthio group having 1 to 20 carbon atoms, and examples of the substituent include ionic hydrophilic groups.
Preferable examples of the alkylthio group include methylthio and ethylthio.

The arylthio group represented by R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ⁸ and R ⁹ includes an arylthio group having a substituent and an unsubstituted arylthio group.
The arylthio group is preferably an arylthio group having 6 to 20 carbon atoms, and examples of the substituent include an alkyl group and an ionic hydrophilic group.
As said arylthio group, a phenylthio group and p-tolylthio are mentioned suitably, for example.

The heterocyclic group represented by R ² is preferably a 5-membered or 6-membered heterocyclic ring, which may be further condensed. As a hetero atom constituting the heterocyclic ring, a nitrogen atom, a sulfur atom and an oxygen atom are preferable. Further, it may be an aromatic heterocyclic ring or a non-aromatic heterocyclic ring. The heterocyclic ring may be further substituted, and examples of the substituent preferably include the same substituents as those described later for the aryl group. Preferred heterocycles include 6-membered nitrogen-containing aromatic heterocycles, among which triazine, pyrimidine and phthalazine are particularly preferred.

Preferred examples of the halogen atom represented by R ⁸ include a fluorine atom, a chlorine atom, and a bromine atom.
The alkoxy group represented by R ¹ , R ³ , R ⁵ , and R ⁸ includes an alkoxy group having a substituent and an unsubstituted alkoxy group.
As the alkoxy group, an alkoxy group having 1 to 20 carbon atoms is preferable, and examples of the substituent include a hydroxyl group and an ionic hydrophilic group.
Suitable examples of the alkoxy group include methoxy, ethoxy, isopropoxy, methoxyethoxy, hydroxyethoxy, and 3-carboxypropoxy.

The aryloxy group represented by R ⁸ includes an aryloxy group having a substituent and an unsubstituted aryloxy group.
The aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms, and examples of the substituent include an alkoxy group and an ionic hydrophilic group.
Preferable examples of the aryloxy group include phenoxy, p-methoxyphenoxy, and o-methoxyphenoxy.
The acylamino group represented by R ⁸ includes an acylamino group having a substituent and an unsubstituted acylamino group.
The acylamino group is preferably an acylamino group having 2 to 20 carbon atoms, and examples of the substituent include an ionic hydrophilic group.
Preferable examples of the acylamino group include acetamido, propionamido, benzamido and 3,5-disulfobenzamido.

The sulfonylamino group represented by R ⁸ includes a sulfonylamino group having a substituent and an unsubstituted sulfonylamino group.
The sulfonylamino group is preferably a sulfonylamino group having 1 to 20 carbon atoms.
Suitable examples of the sulfonylamino group include methylsulfonylamino and ethylsulfonylamino.

The alkoxycarbonylamino group represented by R ⁸ includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group.
The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms, and examples of the substituent include an ionic hydrophilic group.
Preferred examples of the alkoxycarbonylamino group include ethoxycarbonylamino.

The ureido group represented by R ⁸ includes a ureido group having a substituent and an unsubstituted ureido group.
The ureido group is preferably a ureido group having 1 to 20 carbon atoms,
Examples of the substituent include an alkyl group and an aryl group.
Suitable examples of the ureido group include 3-methylureido, 3,3-dimethylureido and 3-phenylureido.

The alkoxycarbonyl group represented by R ⁷ , R ⁸ and R ⁹ includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group.
The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and examples of the substituent include an ionic hydrophilic group.
Suitable examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl.

The carbamoyl group represented by R ² , R ⁷ , R ⁸ and R ⁹ includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group.
Preferred examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.
The sulfamoyl group represented by R ⁸ includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group.
Preferred examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

Preferable examples of the sulfonyl group represented by R ⁸ include methanesulfonyl and phenylsulfonyl.
The acyl group represented by R ² and R ⁸ includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 20 carbon atoms, and examples of the substituent include an ionic hydrophilic group.
Preferred examples of the acyl group include acetyl and benzoyl.

The amino group represented by R ⁸ includes an amino group having a substituent and an unsubstituted amino group. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group.
Preferable examples of the amino group include methylamino, diethylamino, anilino and 2-chloroanilino.

The heterocyclic group represented by R ⁴ , R ⁶ , and R ¹⁰ is the same as the optionally substituted heterocyclic group represented by B in the general formula (YI), and is preferably a preferable example. Examples, particularly preferred examples are the same as described above.
Examples of the substituent include an ionic hydrophilic group, an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkyl or arylthio group, a halogen atom, a cyano group, a sulfamoyl group, a sulfonamino group, a carbamoyl group, and an acylamino group. And the alkyl group and aryl group may further have a substituent.

In the general formula (Y-III), Za represents —N═, —NH—, or C (R ¹¹ ) ═. Zb and Zc each independently represent —N═ or C (R ¹¹ ) ═. R ¹¹ represents a hydrogen atom or a nonmetallic substituent. As the nonmetallic substituent represented by R ¹¹ , a cyano group, a cycloalkyl group, an aralkyl group, an aryl group, an alkylthio group, an arylthio group, or an ionic hydrophilic group is preferable. Each of the substituents is synonymous with each substituent represented by R ¹ , and preferred examples are also the same. Examples of the skeleton of a heterocyclic ring composed of two 5-membered rings contained in the general formula (Y-III) are shown below.

  Examples of the substituent in the case where each substituent described above may further have a substituent include a substituent that may be substituted on the heterocyclic rings A and B of the general formula (Y-I). Can be mentioned.

  Specific examples of the dye represented by the general formula (Y-I) include compounds (Y-101 to Y-155) described in Japanese Patent Application No. 2002-10361. It is not limited. These compounds can be synthesized with reference to JP-A-2-24191 and JP-A-2001-279145.

  Furthermore, as the oil-soluble dye suitably used as the oil-soluble compound of the present invention, a compound represented by the following general formula (MI) (hereinafter sometimes referred to as “azo dye”) is preferable. Below, the compound represented by general formula (MI) of this invention is demonstrated.

In the general formula (M-I), A represents a residue of a 5-membered heterocyclic diazo component (A-NH ₂ ).
In B ¹ and B ² , B ¹ represents = CR ¹ -and B ² represents -CR ² =, or one of them represents a nitrogen atom and the other represents = CR ¹ -or -CR ² =.
R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. Each group may further have a substituent.
G, R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Substituted with acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group, aryl group or heterocyclic group Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylarylsulfonylamino group, arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkylthio , An arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group. Each group may be further substituted.
R ¹ and R ⁵ , or R ⁵ and R ⁶ may be bonded to form a 5- to 6-membered ring.

The compound represented by the general formula (MI) of the present invention will be described in detail.
In the general formula (M-I), A represents a residue of a 5-membered heterocyclic diazo component (A-NH ₂ ). Examples of the hetero atom of the 5-membered heterocyclic ring include N, O, and S. Preferably, it is a nitrogen-containing 5-membered heterocyclic ring, and the heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring.
Examples of preferable heterocyclic ring for A include pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazole ring, benzothiazole ring, benzoxazole ring, and benzoisothiazole ring. Each heterocyclic group may further have a substituent. Of these, pyrazole rings, imidazole rings, isothiazole rings, thiadiazole rings, and benzothiazole rings represented by the following general formulas (Ma) to (Mf) are preferable.

R ^{7 to} R ²⁰ in the general formulas (Ma) to (Mf) represent the same substituents as the substituents G, R ^1, and R ² described later.
Among the general formulas (Ma) to (Mf), the pyrazole ring and the isothiazole ring represented by the general formulas (Ma) and (Mb) are preferable, and the most preferable is It is a pyrazole ring represented by the general formula (M-a).
B ¹ and B ² are those in which B ¹ represents = CR ¹ -and B ² represents -CR ² =, or one of them represents a nitrogen atom and the other represents = CR ¹ -or -CR ² =. More preferably, B ¹ represents = CR ¹ -and B ² represents -CR ² =.
R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or It represents a sulfamoyl group, and each group may further have a substituent. Preferable substituents represented by R ⁵ and R ⁶ include a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, and an arylsulfonyl group. More preferably, they are a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. Most preferably, they are a hydrogen atom, an aryl group, or a heterocyclic group. Each group may further have a substituent. However, R ⁵ and R ⁶ are not simultaneously hydrogen atoms.

G, R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl Substituted with a group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group, aryl group or heterocyclic group Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio group, arylthio group, heterocyclic thio group , It represents an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, or a sulfo group, and each group may be further substituted.

  Preferred substituents represented by G include hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, alkyl group, aryl group or hetero group. And an amino group substituted with a cyclic group, an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylthio group, an arylthio group, and a heterocyclic thio group, more preferably , A hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group substituted with an alkyl group, an aryl group or a heterocyclic group, or an acylamino group, among which a hydrogen atom, an aryl group An amino group and an amide group are most preferred. Each group may further have a substituent.

Preferable substituents represented by R ¹ and R ² include a hydrogen atom, an alkyl group, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group, and a cyano group. Each group may further have a substituent.
R ¹ and R ⁵ , or R ⁵ and R ⁶ may combine to form a 5- to 6-membered ring.
Examples of the substituent in the case where each substituent represented by A, R ¹ , R ² , R ⁵ , R ⁶ , or G further has a substituent include the substituents exemplified for G, R ¹ , and R ^2. be able to.

Hereinafter, the substituents represented by G, R ¹ and R ² will be described in detail.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
An aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The aliphatic group may have a branch and may form a ring. The number of carbon atoms in the aliphatic group is preferably 1-20, and more preferably 1-16. The aryl part of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, particularly preferably phenyl. Examples of aliphatic groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl. Group, cyclohexyl group, benzyl group, 2-phenethyl group, vinyl group, and allyl group.

In this specification, an aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The number of carbon atoms of the aromatic group is preferably 6-20, and more preferably 6-16.
Examples of the aromatic group include a phenyl group, a p-tolyl group, a p-methoxyphenyl group, an o-chlorophenyl group, and an m- (3-sulfopropylamino) phenyl group.
The heterocyclic group includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring, or another heterocyclic ring. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent include an aliphatic group, a halogen atom, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acylamino group, a sulfamoyl group, a carbamoyl group, and an ionic hydrophilic group. Examples of the heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group, and 2-furyl group.

Examples of the alkylsulfonyl group and arylsulfonyl group include a methanesulfonyl group and a phenylsulfonyl group, respectively.
Examples of the alkylsulfinyl group and arylsulfinyl group include a methanesulfinyl group and a phenylsulfinyl group, respectively.

  The acyl group includes an acyl group having a substituent and an unsubstituted acyl group. As the acyl group, an acyl group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

The amino group includes an amino group substituted with an alkyl group, an aryl group, and a heterocyclic group, and the alkyl group, the aryl group, and the heterocyclic group may further have a substituent. Unsubstituted amino groups are not included. As the alkylamino group, an alkylamino group having 1 to 6 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.
The arylamino group includes an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 12 carbon atoms. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.

  The alkoxy group includes an alkoxy group having a substituent and an unsubstituted alkoxy group. As the alkoxy group, an alkoxy group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

  The aryloxy group includes an aryloxy group having a substituent and an unsubstituted aryloxy group. As the aryloxy group, an aryloxy group having 6 to 12 carbon atoms is preferable. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

  The acylamino group includes an acylamino group having a substituent. The acylamino group is preferably an acylamino group having 2 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-disulfobenzoylamino group.

  The ureido group includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 12 carbon atoms. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

  The sulfamoylamino group includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino group.

  The alkoxycarbonylamino group includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. As the alkoxycarbonylamino group, an alkoxycarbonylamino group having 2 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

  The alkylsulfonylamino group and arylsulfonylamino group include a substituted alkyl and arylsulfonylamino group, an unsubstituted alkyl and arylsulfonylamino group. As the alkyl and arylsulfonylamino groups, alkyl and arylsulfonylamino groups having 1 to 12 carbon atoms are preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkyl and arylsulfonylamino groups include a methanesulfonylamino group, an N-phenylmethanesulfonylamino group, a benzenesulfonylamino group, and a 3-carboxybenzenesulfonylamino group.

  The carbamoyl group includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

  The sulfamoyl group includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

  The alkoxycarbonyl group includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  The acyloxy group includes an acyloxy group having a substituent and an unsubstituted acyloxy group. As the acyloxy group, an acyloxy group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

  The carbamoyloxy group includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

  The aryloxycarbonyl group includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. As the aryloxycarbonyl group, an aryloxycarbonyl group having 7 to 12 carbon atoms is preferable. Substituents include ionic hydrophilic groups. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

  The aryloxycarbonylamino group includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

  The alkyl, aryl, and heterocyclic thio groups include substituted alkyl, aryl, and heterocyclic thio groups, and unsubstituted alkyl, aryl, and heterocyclic thio groups. As the alkyl, aryl and heterocyclic thio groups, those having 1 to 12 carbon atoms are preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the alkyl, aryl and heterocyclic thio groups include a methylthio group, a phenylthio group, and a 2-pyridylthio group.

  In the present invention, particularly preferred azo dyes are compounds represented by the following general formula (M-II).

In the general formula (M-II), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. Z ¹ is preferably an electron withdrawing group having a σ _p value of 0.30 to 1.0. Specific examples of preferred substituents include the electron-withdrawing substituents described later, among which an acyl group having 2 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, a nitro group, and a cyano group. , An alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, and a halogenated alkyl group having 1 to 12 carbon atoms are preferable. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, and an arylsulfonyl group having 6 to 18 carbon atoms, and most preferred is a cyano group.

R ¹ , R ² , R ⁵ and R ⁶ have the same meaning as in the general formula (MI).
R ³ and R ⁴ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. Among these, a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, and an arylsulfonyl group are preferable, and a hydrogen atom, an aromatic group, and a heterocyclic group are particularly preferable.
Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.
Q represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. Among them, Q is preferably a group composed of a nonmetallic atom group necessary for forming a 5- to 8-membered ring. This 5- to 8-membered ring may be substituted, may be a saturated ring, or may have an unsaturated bond. Among these, an aromatic group and a heterocyclic group are particularly preferable. Preferred nonmetallic atoms include nitrogen atoms, oxygen atoms, sulfur atoms and carbon atoms. Specific examples of the 5- to 8-membered ring include, for example, a benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole. A ring, a benzimidazole ring, an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, an oxane ring, a sulfolane ring, and a thiane ring.

Each group described in the general formula (M-II) may further have a substituent. When each of these groups further has a substituent, examples of the substituent include the substituents described in the general formula (MI), the groups exemplified for G, R ¹ and R ² , and ionic hydrophilic groups. Can be mentioned.

Here, Hammett's substituent constant σ _p value used in the present specification will be described in relation to the substituent Z ¹ .
Hammett's rule was established in 1935 by L.L. to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σ _p value and a σ _m value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (McGraw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σ _p, but this is limited to only a substituent having a known value that can be found in the above-mentioned book. Needless to say, it also includes substituents that would be included in the range when measured based on Hammett's rule even if the value is unknown. The general formulas (M-I) and (M-II) of the present invention include those that are not benzene derivatives. However, as a measure of the electronic effect of the substituent, σ _p Use the value. In the present invention, the σ _p value is used in this sense.

Examples of electron-withdrawing groups having a Hammett substituent constant σ _p value of 0.60 or more include a cyano group, a nitro group, and an alkylsulfonyl group (for example, a methanesulfonyl group, an arylsulfonyl group (for example, a benzenesulfonyl group)). Can be mentioned.
Examples of the electron withdrawing group having a Hammett σ _p value of 0.45 or more include an acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, m -Chlorophenoxycarbonyl group), alkylsulfinyl group (for example, n-propylsulfinyl group), arylsulfinyl group (for example, phenylsulfinyl group), sulfamoyl group (for example, N-ethylsulfamoyl group, N, N-dimethylsulfuryl group) (Famoyl group) and halogenated alkyl groups (for example, trifluoromethyl group).

The electron withdrawing group having a Hammett substituent constant σ _p value of 0.30 or more includes, in addition to the above, an acyloxy group (for example, acetoxy group), a carbamoyl group (for example, N-ethylcarbamoyl group, N, N-dibutyl). Rucarbamoyl group), halogenated alkoxy group (for example, trifluoromethyloxy group), halogenated aryloxy group (for example, pentafluorophenyloxy group), sulfonyloxy group (for example, methylsulfonyloxy group), halogenated alkylthio group ( For example, a difluoromethylthio group), an aryl group (for example, 2,4-dinitrophenyl group, pentachlorophenyl group) substituted with an electron withdrawing group having two or more σ _p values of 0.15 or more, and a complex A ring (for example, 2-benzoxazolyl group, 2-benzothiazolyl group, 1-phenyl-2-benzimidazole It can be mentioned Lil group).
Specific examples of the electron withdrawing group having a σ _p value of 0.20 or more include a halogen atom in addition to the above.

As the compound represented by the general formula (MI), particularly preferred combinations of substituents are as follows.
(I) R ⁵ and R ⁶ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group, or an acyl group, and more preferably a hydrogen atom, an aryl group, a heterocyclic group, or a sulfonyl group. And most preferably a hydrogen atom, an aryl group, or a heterocyclic group. However, R ⁵ and R ⁶ are not both hydrogen atoms.
(B) G is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an amino group or an amide group, more preferably a hydrogen atom, a halogen atom, an amino group or an amide group, most preferably a hydrogen atom. An amino group or an amide group. (C) A is preferably a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring, or a benzothiazole ring, more preferably a pyrazole ring or an isothiazole ring, and most preferably a pyrazole ring.
(D) B ¹ and B ² are each ═CR ¹ —, —CR ² ═, and R ¹ and R ² are each preferably a hydrogen atom, a halogen atom, a cyano group, a carbamoyl group, or a carboxyl group. , An alkyl group, a hydroxyl group and an alkoxy group, more preferably a hydrogen atom, a cyano group, a carbamoyl group and an alkoxy group.

  In addition, with respect to a preferable combination of substituents of the compound represented by the general formula (MI), a compound in which at least one of various substituents is the above-described preferable group is preferable, and more various substituents are A compound that is a preferred group is more preferred, and a compound in which all substituents are the preferred groups is most preferred.

  Examples of the compound represented by the general formula (M-I) include compounds described in Japanese Patent Application No. 2002-10361 (a-1 to a-27, b-1 to b-6, c-1 to c-3, d-1 to d-4, and e-1 to e-4) are preferable, but the present invention is not limited to these.

  As the oil-soluble compound in the present invention, a compound represented by the following general formula (CI) (hereinafter sometimes referred to as “phthalocyanine dye”) is preferably used. Below, the compound represented by general formula (CI) is demonstrated.

In the general formula (CI), X ¹ , X ² , X ³ and X ⁴ each independently represent —SO—Z ¹ , —SO ₂ —Z ¹ or —SO ₂ NR ²¹ R ²² . .

Z ¹ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, particularly preferably an alkyl group, an aryl group or a heterocyclic group, and among them, an alkyl group, an aryl group or a heterocyclic ring Groups are most preferred. Each may further have a substituent.

R ²¹ and R ²² each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, and particularly preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Of these, a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group are most preferable. However, both R ²¹ and R ²² are not hydrogen atoms. Each may further have a substituent.

The substituted or unsubstituted alkyl group represented by R ²¹ , R ²² and Z ¹ is preferably an alkyl group having 1 to 30 carbon atoms. Examples of the substituent include the same substituents as those described later when Z ¹ , R ²¹ , R ²² , Y ¹ , Y ² , Y ³ and Y ⁴ can further have a substituent. Among these, a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom are preferable.

The cycloalkyl group having a substituent or the unsubstituted cycloalkyl group represented by R ²¹ , R ²² and Z ¹ is preferably a cycloalkyl group having 5 to 30 carbon atoms. Examples of the substituent include the same substituents as those described later when Z ¹ , R ²¹ , R ²² , Y ¹ , Y ² , Y ³ and Y ⁴ can further have a substituent. Of these, a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom are preferable.

The alkenyl group having a substituent or the unsubstituted alkenyl group represented by R ²¹ , R ²² and Z ¹ is preferably an alkenyl group having 2 to 30 carbon atoms. Examples of the substituent include the same substituents as those described later when Z ¹ , R ²¹ , R ²² , Y ¹ , Y ² , Y ³ and Y ⁴ can further have a substituent. Of these, a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom are preferable.

The aralkyl group having a substituent or the unsubstituted aralkyl group represented by R ²¹ , R ²² and Z ¹ is preferably an aralkyl group having 7 to 30 carbon atoms. Examples of the substituent include the same substituents as those described later when Z ¹ , R ²¹ , R ²² , Y ¹ , Y ² , Y ³ and Y ⁴ can further have a substituent. Of these, a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom are preferable.

As the substituent of the aryl group represented by R ²¹ , R ²² and Z ¹ , Z ¹ , R ²¹ , R ²² , Y ¹ , Y ² , Y ³ and Y ⁴ described later can further have a substituent. The same as the substituent in the case. Preferred substituents include halogen atoms, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, acylamino groups, ureido groups, sulfamoylamino groups, alkyloxycarbonyl groups, alkyloxycarbonylamino groups, sulfonamides. Groups, sulfamoyl groups, carbamoyl groups, sulfonyl groups, acyloxy groups, carbamoyloxy groups, imide groups, heterocyclic thio groups, acyl groups, sulfo groups, quaternary ammonium groups, among them heterocyclic groups, cyano groups, carboxyl groups An acylamino group, a sulfonamido group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an imide group, and an acyl group are preferable, and a cyano group, a carboxyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an imide group, and an acyl group are more preferable.

The heterocyclic group represented by R ²¹ , R ²² and Z ¹ is preferably a 5-membered or 6-membered ring, and they may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle.
In the following, the heterocyclic groups represented by R ²¹ , R ²² and Z ¹ are exemplified in the form of a heterocyclic ring with the substitution position omitted, but the substitution position is not limited, and for example, pyridine It is possible to substitute at the 2nd, 3rd and 4th positions.
Pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole Benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. Among these, an aromatic heterocyclic group is preferable, and preferable examples thereof are exemplified in the same manner as described above. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benz Examples include isothiazole and thiadiazole. These may have a substituent.

Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro Group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, An acyl group, a carboxyl group, or Represents a sulfo group, and each may further have a substituent.

  Among these, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, and an alkoxycarbonyl group are preferable. An atom and a cyano group are preferable, and a hydrogen atom is most preferable.

When Z ¹ , R ²¹ , R ²² , Y ¹ , Y ² , Y ³ and Y ⁴ are groups capable of further having a substituent, they may further have a substituent as listed below. Good.

  A halogen atom (for example, a chlorine atom or a bromine atom), a linear or branched alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkyl group having 2 to 30 carbon atoms A linear or branched alkynyl group, a linear or branched cycloalkyl group having 3 to 30 carbon atoms, a linear or branched cycloalkenyl group having 3 to 30 carbon atoms, and more specifically (for example, methyl, ethyl, propyl, Isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), an aryl group (eg, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl), A heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), Ano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino groups (eg, acetamide, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) Butanamide), alkylamino groups (eg, methylamino, butylamino, diethylamino, methylbutylamino), anilino groups (eg, phenylamino, 2-chloroanilino, ureido groups (eg, phenylureido, methylureido, N, N-) Butylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoylamino), alkylthio group (eg, methylthio, octylthio, 2-phenoxyethylthio), arylthio group (eg, phenylthio, 2-butoxy- 5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino group (for example, methoxycarbonylamino), sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), carbamoyl Groups (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl groups (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), sulfonyl groups (eg, For example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkyloxycarbonyl groups (for example, methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy groups (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyrani) Ruoxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), carbamoyloxy group ( For example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxy) Rubonylamino), imide group (for example, N-succinimide, N-phthalimide), heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6- Thio, 2-pyridylthio), sulfinyl group (eg 3-phenoxypropylsulfinyl), phosphonyl group (eg phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (eg phenoxycarbonyl), acyl Groups (for example, acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (for example, carboxyl group, sulfo group, and quaternary ammonium group) and the like.

a ^{1 to} a ⁴ and b ^{1 to} b ⁴ each represent the number of substituents X ^{1 to} X ⁴ and Y ^{1 to} Y ⁴ ; a ^{1 to} a ⁴ each independently represents an integer of 0 to 4; ¹ ~b ⁴ each independently represent an integer of 0-4. However, the sum of a ^{1 to} a ⁴ is 2 or more. Here, when a ¹ ~a ⁴ and b ¹ ~b ⁴ is an integer of 2 or more, or different in each plurality of X ¹ to X ⁴ and Y ¹ to Y ⁴ are the same.

a ¹ and b ¹ each independently represents an integer of 0 to 4 satisfying the relationship of a ¹ + b ¹ = 4, and particularly preferably, a ¹ represents 1 or 2, and b ¹ represents 3 or 2. Of these, a combination in which a ¹ represents 1 and b ¹ represents 3 is the most preferable.

a ² and b ² each independently represents an integer of 0 to 4 satisfying the relationship of a ² + b ² = 4, and particularly preferably, a ² represents 1 or 2 and b ² represents 3 or 2. Of these, a combination in which a ² represents 1 and b ² represents 3 is the most preferable.

a ³ and b ³ each independently represents an integer of 0 to 4 satisfying the relationship of a ³ + b ³ = 4, and particularly preferably, a ³ represents 1 or 2 and b ³ represents 3 or 2. Of these, a combination in which a ³ represents 1 and b ³ represents ³ is the most preferable.

a ⁴ and b ⁴ each independently represents an integer of 0 to 4 satisfying the relationship of a ⁴ + b ⁴ = 4, and particularly preferably, a ⁴ represents 1 or 2, and b ⁴ represents 3 or 2. Of these, a combination in which a ⁴ represents 1 and b ⁴ represents 3 is the most preferable.

M represents a hydrogen atom, a metal element or an oxide thereof, a hydroxide, or a halide.
Preferable examples of M include hydrogen atoms and metal atoms such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi and the like can be mentioned. Examples of the oxide include VO and GeO. Examples of the hydroxide include Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _{2 and the} like. Further, examples of the halide include AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl, FeCl, GaCl, and ZrCl. Among these, Cu, Ni, Zn, Al and the like are particularly preferable, and Cu is most preferable.

  In addition, Pc (phthalocyanine ring) may form a dimer (for example, Pc-MLM-Pc) or a trimer via L (a divalent linking group). May be the same or different.

The divalent linking group represented by L includes an oxy group (—O—), a thio group (—S—), a carbonyl group (—CO—), a sulfonyl group (—SO ₂ —), an imino group (—NH -), or a methylene group (-CH ₂ -) is preferred.

  As the compound represented by the general formula (CI), particularly preferred combinations are as follows.

X ^{1 to} X ⁴ are each particularly preferably —SO ₂ —Z ¹ or —SO ₂ NR ²¹ R ²² .

Z ¹ is preferably each independently an alkyl group, an aryl group or a heterocyclic group, and most preferably an alkyl group, an aryl group or a heterocyclic group. Each may further have a substituent.

R ²¹ and R ²² are each independently preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and most preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Each may further have a substituent.

Y ^{1 to} Y ⁴ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a carboxyl group, and a sulfo group. In particular, a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, and a sulfo group are preferable, and a hydrogen atom is most preferable.

a ^{1 to} a ⁴ are each independently preferably 1 or 2, and particularly preferably 1. b ^{1 to} b ⁴ are each independently preferably 3 or 2, and particularly preferably 3.

  M represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof, and Cu, Ni, Zn, and Al are particularly preferable, and Cu is particularly preferable.

  As for the preferred combination of substituents of the compound represented by the general formula (CI), a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  Among the compounds represented by the general formula (CI), a compound having a structure represented by the following general formula (C-II) is more preferable.

In Formula ^{(C-II), X 11} ~X 14, Y 11 ~Y 18 are each synonymous with ^{X 1 ~X 4, Y 1 ~Y} 4 in the formula (C-I) The preferred examples are also the same. Moreover, M < ¹ > is synonymous with M in the said general formula (CI), and its preferable example is also the same.

Specifically, in the general formula (C-II), X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently —SO—Z ¹¹ , —SO ₂ —Z ¹¹ or —SO ₂ NR. ²³ represents R ²⁴ .
Z ¹¹ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group. Each may further have a substituent.
R ²³ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ²⁴ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, Or represents a heterocyclic group. Each may further have a substituent.
Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ , Y ¹⁵ , Y ¹⁶ , Y ¹⁷ and Y ¹⁸ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, Alkoxycarbonylamino group, sulfonamido group, carbamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic ring A thio group, a phosphoryl group, an acyl group, a carboxyl group, or Represents a sulfo group, each group may further have a substituent.
a ¹¹ ~a ¹⁴ each represent a number of substituents X ¹¹ to X ^14, each independently represents an integer of 0 to 2, never all 0 at the same time. Incidentally, when a ¹¹ ~a ¹⁴ represents 2, two X ¹¹ to X ¹⁴ may each be the same or different.
M ¹ is a hydrogen atom, a metal element or an oxide thereof, a hydroxide, or a halide.

In the general formula (C-II), preferably a ^{11 to} a ¹⁴ each independently represent an integer of 1 or 2 in the range of 4 ≦ a ¹¹ + a ¹² + a ¹³ + a ¹⁴ ≦ 8, 4 ≦ a ¹¹ + a ¹² + a ¹³ + a ¹⁴ ≦ 6, and particularly preferred is when a ¹¹ = a ¹² = a ¹³ = a ¹⁴ = 1.

  Among the compounds represented by the general formula (C-II), particularly preferred combinations of substituents are as follows.

As X ^{11 to} X ¹⁴ , —SO ₂ —Z ¹¹ or —SO ₂ NR ²³ R ²⁴ is particularly preferable.

Z ¹¹ is preferably each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group Is most preferred.

R ²³ is preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom, a substituted alkyl group, or a substituted aryl group Substituted heterocyclic groups are most preferred.

R ²⁴ is preferably each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group Is most preferred.

Y ^{11 to} Y ¹⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or an alkoxycarbonyl group. Particularly preferred are a hydrogen atom, a halogen atom and a cyano group, and a hydrogen atom is most preferred.

a ^{11 to} a ¹⁴ are preferably each independently 1 or 2, particularly preferably all 1.

M ¹ represents a hydrogen atom, a metal element or oxide thereof, a hydroxide, or a halide, and Cu, Ni, Zn, and Al are particularly preferable, and Cu is most preferable among them.

  As for the preferred combination of substituents of the compound represented by the general formula (C-II), a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  The compound represented by the general formula (C-I) is inevitably different in the introduction position and number of substituents Rn (n = 1 to 4) and Yq (q = 1 to 4) depending on the synthesis method. In general, it is a body mixture, and these analog mixtures are often represented by a statistical average. The present invention has found that a specific mixture is particularly preferable when these analog mixtures are classified into the following three types.

  In the present invention, the phthalocyanine dye analog mixture, which is a compound represented by the general formulas (CI) and (C-II), is defined by classifying into the following three types based on the substitution position.

(1) β-position substitution type: (phthalocyanine dye having a specific substituent at the 2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and / or 15 position)

(2) α-position substitution type: (phthalocyanine dye having a specific substituent at positions 1 and / or 4, 5 and / or 8, 9 and / or 12, 13 and / or 16)

(3) α, β-position mixed substitution type: (phthalocyanine dye having a specific substituent without regularity at positions 1 to 16)

  In the present specification, when a derivative of a phthalocyanine dye having a different structure (especially a substitution position) is described, the β-position substitution type, α-position substitution type, and α, β-position mixed substitution type are used.

  Examples of the phthalocyanine derivative used in the present invention include “Phthalocyanine—Chemistry and Function” (P. 1-62), C.K. C. Leznoff-A. B. P. Lever co-authored by VCH and published in 'Phthalogicanes-Properties and Applications' (P. 1-54), etc., can be synthesized by combining quoted or similar methods.

The compound represented by the general formula (CI) of the present invention is WO00 / 17275, 0
0/08103, 00/08101, 98/41853, and JP-A-10-36471, for example, sulfonation, sulfonyl chlorideation, amidation reaction of unsubstituted phthalocyanine compounds It can be synthesized via. In this case, sulfonation can occur at any position of the phthalocyanine nucleus, and the number of sulfonation is difficult to control. Therefore, when a sulfo group is introduced under such reaction conditions, the position and number of the sulfo group introduced into the product cannot be specified, and a mixture in which the number of substituents and the substitution position are different is always given. Therefore, when synthesizing the compound of the present invention using it as a raw material, the number and substitution position of the heterocyclic substituted sulfamoyl group cannot be specified, so the compound of the present invention includes several types of compounds having different numbers of substituents and substitution positions. Α, β-position mixed substitution mixture.

  As described above, for example, when a large number of electron-withdrawing groups such as sulfamoyl groups are introduced into the phthalocyanine nucleus, the oxidation potential becomes more noble and ozone resistance increases. According to the above synthesis method, it is inevitable that a small amount of electron-withdrawing groups are introduced, that is, a phthalocyanine dye having a lower oxidation potential is mixed. Therefore, in order to improve ozone resistance, it is more preferable to use a synthesis method that suppresses the formation of a compound having a lower oxidation potential.

  On the other hand, the compound represented by the general formula (C-II) of the present invention includes, for example, a phthalonitrile derivative (compound P) and / or a diiminoisoindoline derivative (compound Q) represented by the following formula: It can derive from the compound obtained by making it react with the metal derivative represented by general formula (C-III).

  In the compounds P and Q, p represents 11 to 14, and q and q 'each independently represents 11 to 18.

General formula (C-III)
M- (Y) _d
In the general formula (C-III), M is synonymous with M in the compounds represented by the general formulas (CI) and (C-II), and Y is a halogen atom, acetate anion, acetylacetate. Represents a monovalent or divalent ligand such as nate or oxygen, and d represents an integer of 1 to 4.

  That is, according to the above synthesis method, a specific number of desired substituents can be introduced. In particular, when a large number of electron withdrawing groups are to be introduced to increase the oxidation potential as in the present invention, the above synthesis method is compared with the synthesis method of the compound represented by the general formula (CI). Very good.

Thus the general formula obtained (C-II) compound represented by the normal, by the following general formula which are isomers with respect to the substitution site of each ^{X p (C-II-1} ) ~ (C-II-4) A mixture of the compounds represented, that is, β-position substituted type (phthalocyanine type having specific substituents at the 2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and / or 15 position) Dye).

In the general formulas (C-II-1) to (C-II-4), R ^{1 to} R ⁴ represent (X ¹¹ ) a ¹¹ to (X ¹⁴ ) a ^{14 in the} general formula (C-II). It is synonymous.

  In the present invention, it has been found that it is very important for improving the robustness that the oxidation potential is higher than 1.0 V (vs SCE) in any substitution type. Among these, the β-position substitution type tends to be superior in hue, light fastness, ozone gas resistance and the like than the α, β-position mixed substitution type.

  Preferred examples of the compound represented by the general formula (CI) or (C-II) include compounds (C-101 to C-120) described in Japanese Patent Application No. 2002-10361. However, the present invention is not limited to these.

  The compound represented by the general formula (CI) can be synthesized according to the aforementioned patent. In addition, the compound represented by the general formula (C-II) was synthesized by the method described in each specification of JP-A Nos. 2000-292645, 2001-237090, 2001-243524, and 2001-280387. can do. Further, the starting material, the dye intermediate and the synthesis route are not limited by these.

  As content in the ink of the oil-soluble compound used for this invention, 0.05-50 mass% is preferable with respect to ink, and 0.1-10 mass% is more preferable.

-Production of fine particle dispersion-
The fine particle dispersion of the present invention is produced by dispersing the oil-soluble compound and the hydrophobic polymer in the form of fine particles in an aqueous medium (a liquid containing at least water). Specifically, for example, a method of preparing a latex of the hydrophobic polymer in advance and impregnating the latex with the oil-soluble compound, a co-emulsification dispersion method, or the like can be given. Among these, the co-emulsification dispersion method is preferable.
As the co-emulsification dispersion method, the organic solvent is added by either adding water to the organic solvent containing the hydrophobic polymer and the oil-soluble compound, or adding the organic solvent in water. A preferred method is emulsification to form fine particles.

  The latex means a dispersion of the hydrophobic polymer insoluble in the aqueous medium as fine particles in the aqueous medium. Examples of the dispersion state include those in which the hydrophobic polymer is emulsified in the aqueous medium, emulsion polymerized, micelle-dispersed, or the hydrophobic polymer is partially hydrophilic in the molecule. Any of those having a structure and having molecular chains dispersed in a molecular form may be used.

Here, a method of preparing the hydrophobic polymer latex in advance and impregnating the latex with the oil-soluble compound will be described.
A first example of this method includes a first step of preparing a hydrophobic polymer latex, a second step of preparing a dye solution in which the oil-soluble compound is dissolved in an organic solvent, the dye solution and the hydrophobic A third step of mixing the polymer latex and preparing a fine particle dispersion.
A second example of this method comprises a first step of preparing a hydrophobic polymer latex, a dye solution in which the oil-soluble compound is dissolved in an organic solvent, and a solution containing this dye solution and at least water. A second step of preparing a dye fine particle dispersion by mixing, and a third step of preparing a fine particle dispersion by mixing the hydrophobic polymer latex and the dye fine particle dispersion.
As a third example of this method, there is a method described in JP-A No. 55-139471.
In addition, a high boiling point organic solvent can be used with an oil-soluble compound.

Next, the co-emulsification dispersion method will be described.
A first example of this method is a first step of preparing a solution in which the oil-soluble compound and the hydrophobic polymer are dissolved in an organic solvent, and the organic solvent solution containing the hydrophobic polymer and the dye. And a second step of preparing a fine particle dispersion by mixing at least a liquid containing water. The high boiling point organic solvent may be used in the first step.
A second example of this method is a first step of preparing a dye solution in which the oil-soluble compound is dissolved in an organic solvent, and a second step of preparing a hydrophobic polymer solution in which the hydrophobic polymer is dissolved in an organic solvent. And a third step of preparing a fine particle dispersion by mixing the dye solution, the hydrophobic polymer solution and a liquid containing at least water. A hydrophobic high boiling organic solvent may be used in the first and / or second step. The same applies to the following third to fourth examples.

A third example of this method is a first step of preparing a dye fine particle dispersion by preparing a dye solution in which the oil-soluble compound is dissolved in an organic solvent, and mixing the dye solution and a liquid containing at least water. And preparing a polymer solution in which the hydrophobic polymer is dissolved in an organic solvent, and mixing the hydrophobic polymer solution and a liquid containing at least water to produce a hydrophobic polymer fine particle dispersion; and A third step of preparing a fine particle dispersion by mixing the dye fine particle dispersion and the hydrophobic polymer fine particle dispersion.
A fourth example of this method is a first step of preparing a dye solution in which the oil-soluble compound is dissolved in an organic solvent, and mixing the dye and a liquid containing at least water to prepare a dye fine particle dispersion. A second step of preparing a hydrophobic polymer solution in which the hydrophobic polymer is dissolved in an organic solvent; and a third step of preparing a fine particle dispersion by mixing the dye fine particle dispersion and the hydrophobic polymer solution. Including.
A fifth example of this method is a step of directly preparing a fine particle dispersion by mixing a liquid containing at least water with the oil-soluble compound and the hydrophobic polymer.

  As an emulsifier used in the co-emulsification dispersion method, a known apparatus such as a simple stirrer or impeller stirring method, an in-line stirring method, a mill method such as a colloid mill, or an ultrasonic method can be used, but a high-pressure homogenizer is used. Is particularly preferred. The detailed mechanism of the high-pressure homogenizer is described in U.S. Pat. No. 4,533,254, JP-A-6-47264, etc., but as a commercially available apparatus, a gorin homogenizer (APV GAULIN INC.), A microfluidizer (MICROFLUIDEX INC.), An optimizer (Sugino Machine Co., Ltd.), etc. can be used. In recent years, a high-pressure homogenizer having a mechanism for atomizing in an ultrahigh-pressure jet stream as described in US Pat. No. 5,720,551 is particularly effective for emulsification dispersion of the present invention. DeBEE2000 (BEE INTERNIONAL LTD.) Is an example of an emulsifying apparatus using this ultra-high pressure jet stream.

  The pressure during emulsification with a high-pressure emulsifying dispersion device is generally 500 bar or more, preferably 600 bar or more, more preferably 1800 bar or more. For example, it is a particularly preferable method that two or more types of emulsifiers are used in combination by a method such as emulsification with a stirring emulsifier and then passing through a high-pressure homogenizer. Also preferred is a method of once emulsifying and dispersing with these emulsifiers, adding an additive such as a wetting agent or a surfactant, and then passing the high-pressure homogenizer again while filling the cartridge with ink. In addition to high-boiling organic solvents, low-boiling organic solvents can be used. When using a low boiling point organic solvent, it is preferable to remove the low boiling point solvent from the viewpoint of stability of the emulsion and safety and health. Various known methods can be used as the method for removing the low boiling point solvent depending on the type of the solvent. That is, an evaporation method, a vacuum evaporation method, an ultrafiltration method, and the like. This step of removing the low-boiling organic solvent is preferably performed as soon as possible immediately after emulsification.

-Surfactant-
In the present invention, an anionic surfactant is used when emulsifying and dispersing, but it is preferable to use a nonionic surfactant in combination. Further, other surfactants can be used as long as the effects of the present invention are not impaired.

  Examples of the anionic surfactant include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, Examples thereof include oxyethylene sulfate ester salt and aryl polyoxyethylene sulfate ester salt. Among them, alkyl polyoxyethylene sulfate ester salt and aryl polyoxyethylene sulfate ester salt are preferable, and alkyl polyoxyethylene sulfate ester salt is particularly preferable. Aryl polyoxyethylene sulfate salts are preferred.

The content of the anionic surfactant is required to be 0.5 to 30% by mass with respect to the fine particles, but from the viewpoint of stability, 0.7 to 9% by mass is particularly preferable, and further preferable. 0.8-8 mass% is preferable.
Even when a surfactant other than the anionic surfactant is used in combination, the total content of the surfactant is preferably in the above range.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxy An ethylene oxypropylene block copolymer etc. are mentioned.

  As another surfactant, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Further, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. Those listed as surfactants described in 308119 (1989) can also be used.

  In order to stabilize immediately after emulsification, a water-soluble polymer can be added in combination with the surfactant. As the water-soluble polymer, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, polyacrylic acid, polyacrylamide or a copolymer thereof is preferably used. It is also preferable to use natural water-soluble polymers such as polysaccharides, casein, and gelatin.

  When a water-based ink is prepared by dispersing fine particles containing a hydrophobic polymer and an oil-soluble compound in an aqueous medium by a co-emulsion dispersion method, the control of the particle size is particularly important. In order to increase color purity and density when an image is formed by inkjet, it is preferable to reduce the average particle diameter of the fine particles. Specifically, the volume average particle diameter of the fine particles is preferably 100 nm or less, and more preferably 1 nm or more and 80 nm or less. Further, if the fine particles have coarse particles, printing performance may be deteriorated. For example, when the coarse particles clog the nozzles of the head, and even if the clogs are not clogged, the ink may not be ejected or the ejection may be misaligned. Therefore, it is preferable that the ratio of coarse particles is low, and when an ink is prepared, it is preferable that 10 μm or less particles of 5 μm or more are contained in 1 μl of ink and 1000 particles or less of 1 μm or more. As a method for removing coarse particles, a known centrifugal separation method, microfiltration method, or the like can be used. These separation means may be performed immediately after the emulsification dispersion, or may be performed immediately before filling the ink cartridge after various additives such as a wetting agent and a surfactant are added to the emulsification dispersion. In order to reduce the average particle diameter of the fine particles and reduce the coarse particles, it is effective to use a mechanical emulsifier.

-Organic solvent-
The organic solvent used for producing the fine particle dispersion is not particularly limited and can be appropriately selected based on the solubility of the oil-soluble compound or the hydrophobic polymer. For example, acetone, methyl ethyl ketone, diethyl ketone Ketone solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, tert-butanol and the like, chlorine solvents such as chloroform and methylene chloride, and aromatic solvents such as benzene and toluene And ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, and glycol ether solvents such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether.
An organic solvent may be used independently or may use 2 or more types together. Depending on the solubility of the oil-soluble compound or hydrophobic polymer, a mixed solvent with water may be used.

The amount of the organic solvent used is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 10 to 2000 parts by weight, and 100 to 1000 parts by weight with respect to 100 parts by weight of the hydrophobic polymer. Is more preferable.
When the amount of the organic solvent used is less than 10 parts by mass, fine and stable dispersion of fine particles tends to be difficult. When the amount exceeds 2000 parts by mass, solvent removal and concentration for removing the organic solvent are performed. The process becomes indispensable and complicated, and there is a tendency that there is no room for formulation design.
When the vapor pressure of the organic solvent is higher than that of water, the organic solvent is preferably removed from the viewpoint of stability of the fine particle dispersion and safety and hygiene. As a method for removing the organic solvent, various known methods can be used according to the type of the solvent. That is, an evaporation method, a vacuum evaporation method, an ultrafiltration method, and the like. This organic solvent removal step is preferably performed as soon as possible immediately after emulsification.

-Additives-
The fine particle dispersion in the present invention may contain an additive appropriately selected according to the purpose within a range not impairing the effects of the present invention. Examples of the additive include a neutralizing agent, a high boiling point organic solvent, a dispersing agent, and a dispersion stabilizer.

When the dispersible polymer has an unneutralized dissociative group, the neutralizing agent can be suitably used in terms of adjusting the pH of the fine particle dispersion, adjusting the self-emulsifying property, imparting dispersion stability, etc. . Examples of the neutralizing agent include organic bases and inorganic alkalis. Examples of the organic base include triethanolamine, diethanolamine, N-methyldiethanolamine, dimethylethanolamine and the like. Examples of the inorganic alkali include alkali metal hydroxides (for example, sodium hydroxide, lithium hydroxide, potassium hydroxide, etc.), carbonates (for example, sodium carbonate, sodium hydrogencarbonate, etc.), ammonia and the like.
From the viewpoint of improving the dispersion stability in the fine particle dispersion, the neutralizing agent is preferably added so as to have a pH of 4.5 to 10.0, and is preferably added so as to have a pH of 6.0 to 10.0. More preferred.

The hydrophobic high boiling point organic solvent is used for adjusting the viscosity, specific gravity, and printing performance of the fine particle dispersion. The hydrophobic high boiling point organic solvent is hydrophobic and preferably has a boiling point of 150 ° C. or higher, more preferably 170 ° C. or higher. Here, “hydrophobic” means that the solubility in distilled water at 25 ° C. is 3% or less. The dielectric constant of the hydrophobic high boiling point organic solvent is preferably 3 to 12, more preferably 4 to 10. Here, the dielectric constant means a relative dielectric constant with respect to a vacuum at 25 ° C. As the hydrophobic high boiling point organic solvent, compounds described in U.S. Pat. No. 2,322,027 and Japanese Patent Application No. 2000-78531 can be used. Specific examples include phosphoric acid triesters, phthalic acid diesters, alkylnaphthalenes, benzoic acid esters, and the like. Depending on the purpose, these can be either liquid or solid at room temperature.
The amount of the high-boiling solvent used is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 0 to 1000 parts by weight, and 0 to 300 parts by weight with respect to 100 parts by weight of the polymer. More preferred.

The dispersant and / or dispersion stabilizer is added to any of the polymer latex, the colorant-containing liquid, the polymer colorant mixed liquid, the colorant fine particle dispersion, the polymer solution, a liquid containing at least water, and the like. However, it is preferably added to the solution containing the colorant-containing liquid and water in the previous step of preparing the polymer latex and / or colorant fine particle dispersion.
Examples of the dispersant and dispersion stabilizer include cation, anion, and nonionic surfactants, water-soluble or water-dispersible low molecular compounds, oligomers, and the like. As addition amount of the said dispersing agent and a dispersion stabilizer, it is 0-100 mass% with respect to the sum total of the said oil-soluble compound and the said polymer, and 0-20 mass% is preferable.

(Ink, inkjet recording method, and recording material)
The ink of the present invention comprises the fine particle dispersion, and may further contain other appropriately selected additives as necessary.

-Other additives-
Other additives include water-soluble organic solvents, surface tension modifiers, drying inhibitors, penetration enhancers, antioxidants, antifungal agents, pH modifiers, antifoaming agents, viscosity modifiers, dispersants, and dispersion stabilizers. Agents, rust inhibitors, chelating agents, ultraviolet absorbers, and the like. These are those described in paragraphs [0217]-[0226] and [0247] of JP-A-2001-279141, JP-A-2001-2001. Known compounds described in JP-A-181549 can be used.

The water-soluble organic solvent is used in the ink for the purpose of an anti-drying agent or a penetration accelerator. The water-soluble organic solvent is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, glycerin, trimethylolpropane. Polyhydric alcohols typified by diethanolamine, amyl alcohol, furfuryl alcohol, diacetone alcohol, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether and the like substituted or unsubstituted fat Heterocyclic monohydric alcohols, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane Dimethyl sulfoxide, sulfur-containing compounds such as 3-sulfolene and the like.
These water-soluble organic solvents are preferably contained in the ink in an amount of 5 to 60% by mass, more preferably 7 to 50% by mass, and particularly preferably 10 to 40% by mass. Is adjusted according to the target viscosity.

Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. For example, anionic surfactants include fatty acid salts, alkyl sulfate esters, alkylaryl sulfonates (eg, alkylbenzene sulfonates, petroleum sulfonates, etc.), dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfones. Acid formalin condensate, polyoxyethylene alkyl sulfate ester salt and the like. Nonionic surfactants include acetylene diols (for example, 2,4,7,9-tetramethyl-5-decyne-4, 7-diol, etc.), polyoxyethylene alkyl ether (eg, polyoxyethylene decyl ether, ethylene oxide adduct of acetylenic diol), polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid Ester, polyoxyethylene alkylamine, glycerin fatty acid esters, and oxyethylene oxypropylene block copolymer.
An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Furthermore, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. 308119 (1989) The listed surfactants can also be used.
Precipitation and separation from ink do not occur easily and foaming property is low, so that hydrophobic sites are double-stranded or anionic surfactants with hydrophobic sites branched or hydrophilic groups near the center of hydrophobic sites. Anionic surfactants having a hydrophobic structure, nonionic surfactants in which the hydrophobic part is double-stranded or the hydrophobic part is branched (for example, one-terminal ester of polyethylene oxide of 2-butyloctanoic acid, undecan-6-ol Polyethylene oxide adducts), nonionic surfactants having a hydrophilic group near the center of the hydrophobic site (for example, ethylene oxide adducts of acetylenic diols (SURFYNOL series (Air Products & Chemicals), etc.)) are preferred, Those having a molecular weight of 200 or more and 1000 or less are preferred, and a molecular weight of 300 Top 900 more preferably less ones, having a molecular weight of 400 or more 900 or less is particularly preferred.

  The surface tension of the ink of the present invention is preferably in the range of 20 to 60 mN / m, and more preferably in the range of 25 to 45 mN / m, with or without the use of the surface tension adjusting agent. . The dynamic surface tension is preferably in the range of 20 to 40 mN / m, more preferably 25 to 35 mN / m, with or without the use of the surface tension modifier.

  About additives, such as a dispersing agent, a dispersion stabilizer, antioxidant, an antifungal agent, a rust preventive agent, a pH adjuster, an antifoamer, a chelating agent, and an ultraviolet absorber, it describes in Unexamined-Japanese-Patent No. 2001-181549 etc. Known compounds can be used.

  The ink of the present invention can be used as a water-based ink for writing, a water-based printing ink, an information recording ink, and the like.

  Further, the ink of the present invention can be applied to those described in paragraph No. (0247) of JP-A No. 2001-279141, in addition to the inkjet recording method of the present invention described later.

  The ink jet recording method of the present invention includes a step of recording an image on a recording material using the ink of the present invention.

-Recording material-
As a recording material used in the ink jet recording method using the ink of the present invention, a recording paper provided with an ink receiving layer containing porous inorganic fine particles containing at least polymer fine particles, plain paper, art paper, coated paper, Examples include plastic films (for example, OHP sheets), canvas, glass, various plastics, metals, ceramics, fibers, and the like.
Use of coated paper as the recording material is preferable because the image quality is improved.
As the recording material, those described in paragraph numbers (0228) to (0246) of JP-A Nos. 2001-181549 and 2001-279141 can be used.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “parts” and “%” represent “parts by mass” and “% by mass” unless otherwise specified.

[Example 1]
-Production Example 1 (Preparation of fine particle dispersion (B-1))
A mixed solution of 10 parts of ethyl acetate, 1.8 parts of butyl acrylate-styrene copolymer (P-3) and 0.6 part of the following oil-soluble dye (M-1) was prepared. Separately, 0.8 part of a surfactant “Emar 20C” (polyoxyethylene alkyl ether sulfate ester Kao Co., Ltd.) was added to 15 parts of water to prepare an aqueous solution.
The above mixed solution is put into the aqueous solution, and emulsified and dispersed at 10000 rpm for 10 minutes using “ACE Homogenizer” manufactured by Nippon Seiki Co., Ltd., and then concentrated under reduced pressure at a temperature of 30 ° C. A fine particle dispersion (B-1) having a solid content of 16% was obtained.
When the particle size of the fine particle dispersion was measured using a particle size distribution measuring device “LB-500” (manufactured by HORIBA Ltd.), the volume average particle size was 82 nm.

-Production Example 2 (Preparation of fine particle dispersion (B-2))-
In Production Example 1, instead of the surfactant “Emar 20C” (polyoxyethylene alkyl ether sulfate ester salt manufactured by Kao Corporation), the surfactant “Neopelex GS” (alkylbenzene sulfonate salt manufactured by Kao Corporation) A fine particle dispersion was obtained in a similar manner except that
When the particle diameter of the obtained fine particles was measured in the same manner, the volume average particle diameter was 68 nm.

-Production Example 3 (Preparation of fine particle dispersion (B-3))-
In Production Example 1, instead of the surfactant “Emar 20C” (polyoxyethylene alkyl ether sulfate ester salt manufactured by Kao Corporation), the surfactant “Perex OT-P” (alkyl sulfosuccinate salt manufactured by Kao Corporation) Except for the change to), the same procedure was followed to obtain a fine particle dispersion.
When the particle diameter of the obtained fine particles was measured in the same manner, the volume average particle diameter was 75 nm.

-Production Example 4 (Preparation of fine particle dispersion (B-4))-
A mixed solution of 10 parts of ethyl acetate, 1.8 parts of ethyl methacrylate-n-butyl acrylate (P-20) and 0.6 part of oil-soluble dye (C-114) was prepared. Separately, 0.2 parts of surfactant “Emar 20C” (manufactured by Kao Corporation) and 0.8 parts of “Emulgen 108” (polyoxyalkyl ether nonion) (manufactured by Kao Corporation) are added to 15 parts of water. An aqueous solution was prepared.
The above mixed solution is put into the aqueous solution, and emulsified and dispersed at 10000 rpm for 10 minutes using “ACE Homogenizer” manufactured by Nippon Seiki Co., Ltd., and then concentrated under reduced pressure at a temperature of 30 ° C. A fine particle dispersion (B-4) having a solid content of 16% was obtained.
When the particle size of the fine particle dispersion was measured using a particle size distribution measuring device “LB-500” (manufactured by HORIBA Ltd.), the volume average particle size was 55 nm.

-Production Example 5 (Preparation of fine particle dispersion (B-5))-
In Production Example 4, instead of the surfactant “Emulgen 108” (polyoxyalkyl ether nonion) (manufactured by Kao Corp.), the surfactant “Leodol SP-L10” (sorbitan fatty acid ester nonion) (Kao Corp.) A fine particle dispersion was obtained in the same manner except that the change was made to
When the particle diameter of the obtained fine particles was measured in the same manner, the volume average particle diameter was 60 nm.

-Production Example 6 (Preparation of fine particle dispersion (B-6))-
In Production Example 1, the surfactant “Emar 20C” (polyoxyethylene alkyl ether sulfate ester) instead of 0.8 part of the surfactant “Emar 20C” (polyoxyethylene alkyl ether sulfate salt Kao Co., Ltd.) A fine particle dispersion was obtained in the same manner except that the content was changed to 0.2 part (manufactured by Shio Kao Co., Ltd.).
When the particle diameter of the obtained fine particles was measured in the same manner, the volume average particle diameter was 258 nm.

-Production Example 7 (Preparation of fine particle dispersion (B-7))-
A fine particle dispersion was obtained in the same manner as in Production Example 4 except that the surfactant “Emar 20C” was omitted.
When the particle diameter of the obtained fine particles was measured in the same manner, the volume average particle diameter was 325 nm.
Table 1 shows the results of the polymers and oil-soluble dyes used in Production Examples 1 to 7 and the resulting fine particle dispersions. Evaluation of the obtained fine particle dispersion was performed as follows.

<Dispersed state evaluation>
1) Dispersion stability The fine particle dispersions obtained in Production Examples 1 to 5 were confirmed to have a particle size of 0.2 μm or less by a particle size measurement test using a particle size measuring device, and there was no aggregate by visual observation. Judged whether or not.

2) Storage stability Whether the particle size of the fine particle dispersion obtained in Production Examples 1 to 5 is increased due to aggregation or the particle size distribution is not expanded by a storage test at room temperature for 7 days. It was judged.
The dispersion stability and storage stability test results were evaluated according to the following criteria.
○: There is almost no aggregation in dispersion, and the particle size is 0.2 μm or less.
X: Aggregation occurs during dispersion holding and storage, and the particle size distribution spreads.

  As is clear from the results in Table 1, a fine particle dispersion having a small particle size, no aggregation, and excellent dispersion stability and storage stability can be produced.

[Example 2]
<Preparation of ink 01>
The following components were mixed and filtered through a 0.45 μm filter to prepare an aqueous inkjet recording ink 01.
-Fine particle dispersion (B-1) 50 parts-Diethylene glycol 10 parts-Glycerin 20 parts-Triethylene glycol monobutyl ether 5 parts-Diethanolamine 1 part-Olphine E1010 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.) 1.0 Amount of water and 100 parts in total

<Preparation of inks 02 to 05>
The ink 01 was prepared except that the fine particle dispersion (B-1) was replaced with the fine particle dispersions (B-2) to (B-5) prepared in Production Examples 2 to 5 in the production of the ink 01. Water-based inkjet recording inks 02 to 05 were produced in the same manner as in the above.

[Comparative Example 1]
<Preparation of inks 06 and 07>
The ink 01 was prepared except that the fine particle dispersion (B-1) was replaced with the fine particle dispersions (B-6) to (B-7) prepared in Production Examples 06 to 07 in the production of the ink 01. Water-based inkjet recording inks 06 to 07 were produced in the same manner as in the above.

(Evaluation)
The ink 01 to the ink 07 obtained as described above were evaluated for image recording.

≪Image recording and evaluation≫
The prepared inks 01 to 07 are filled into a cartridge of an ink jet printer MC-2000 (manufactured by EPSON), and using this machine, as a sample (recording material), plain paper for PPC, ink jet paper photo glossy paper EX Images were recorded on (manufactured by Fuji Photo Film Co., Ltd.), and evaluation relating to image recording was performed as follows. The evaluation results are shown in Table 2.

<Print performance evaluation>
After setting the cartridge in the printer and confirming the ejection of ink from all the nozzles, an image was output on each of the 10 A4-sized samples, and the disorder of the printed image was evaluated according to the following criteria.
A: The printed image was not disturbed from the start to the end of printing. (Printed neatly)
B: Disturbance of the printed image occurred occasionally from the start to the end of printing. (Occasionally print images appear)
C: The printed image was disturbed from the start to the end of printing. (Almost no print)

<Support dependency evaluation>
The color tones between the images formed on the respective samples are compared, and A is set when there is almost no difference between the two images, B is set when the difference between the two images is small, and C is set when the difference between the two images is large. Rated by stage.

<Water resistance evaluation>
Each recording material on which the image was formed was dried at room temperature for 1 hour, then immersed in water for 30 seconds, naturally dried at room temperature, and bleeding was observed.
Evaluation was made in three stages, with A indicating no bleeding, B indicating slight bleeding, and C indicating large bleeding.

<Abrasion resistance evaluation>
Each sample on which the image was formed was rubbed 10 times with an eraser for the image that had passed 30 minutes after image printing, and the change was observed.
Evaluation was made in three stages, with A indicating no decrease in concentration, B indicating a slight decrease in concentration, and C indicating a large decrease in concentration.

<Light resistance evaluation>
Each sample on which the image was formed was irradiated with xenon light (85000 lx) for 4 days using a weather meter (Atlas C.I65), and the image density before and after the xenon irradiation was measured using a reflection densitometer (X-Rite310TR, X-Rite). ) And evaluated as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0.
The evaluation was made in three stages, with A being a dye residual ratio of 80% or more at any concentration, A being 1 or 2 points being less than 80% B, and C being less than 80% at all concentrations.

<Ozone resistance evaluation>
For ozone resistance, the concentration of the sample before and after storage for 3 days under conditions of an ozone concentration of 1.0 ppm was measured with a reflection densitometer (X-rite 310, manufactured by X-Rite), and the residual dye rate Was evaluated.
When the residual ratio of the dye was 90% or more, the evaluation was made in five stages: A, 89-80% as B, 79-70% as C, 69-50% as D, and less than 49% as E.

  As is apparent from the results in Table 2, the ink jet recording inks of the examples have excellent printing performance, are not dependent on the support, can be printed on a non-penetrating support, and are water resistant and highly scratch resistant. Excellent in light resistance and ozone resistance.

Claims (8)

In a fine particle dispersion in which fine particles containing an oil-soluble compound and a hydrophobic polymer are dispersed in an aqueous medium, the fine particles are dispersed in the aqueous medium using a surfactant, and the surfactant is an anionic interface. A fine particle dispersion comprising an activator, and the content of the anionic surfactant is from 0.5% by mass to 30% by mass with respect to the fine particles. The fine particle dispersion according to claim 1, wherein the surfactant further contains a nonionic surfactant. The fine particle dispersion according to claim 1 or 2, wherein the anionic surfactant is alkyl polyoxyethylene sulfate or aryl polyoxyethylene sulfate. The fine particle dispersion according to any one of claims 1 to 3, wherein the oil-soluble compound is an oil-soluble dye. The oil-soluble compound is at least one selected from the group consisting of compounds represented by the following general formulas (I), (II), (Y-I), (M-I), and (C-I). The fine particle dispersion according to any one of claims 1 to 4, comprising a compound.

[In General Formula (I) and General Formula (II), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano Group, hydroxy group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfone Amido group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic ring Thio group, sulfinyl group, phosphoryl group, acyl group, carboxyl group Or a sulfo group. A represents —NR ⁵ R ⁶ or a hydroxy group. R ⁵ and R ⁶ each independently represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. R ⁵ and R ⁶ may be bonded to each other to form a ring. B ¹ represents ═C (R ³ ) — or ═N—. B ² represents —C (R ⁴ ) ═ or —N═. R ¹ and R ⁵ , R ³ and R ⁶ , and R ¹ and R ² may be independently bonded to each other to form an aromatic ring or a heterocyclic ring. X represents a color coupler residue, and Y represents an unsaturated heterocyclic group. ]

[In General Formula (Y-I), A and B each independently represents an optionally substituted heterocyclic group. ]

[In General Formula (MI), A represents a residue of a 5-membered heterocyclic diazo component (A-NH ₂ ). In B ¹ and B ² , B ¹ represents = CR ¹ -and B ² represents -CR ² =, or one of them represents a nitrogen atom and the other represents = CR ¹ -or -CR ² =. R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. Each group may further have a substituent. G, R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Substituted with acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl group or heterocyclic group Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylarylsulfonylamino group, arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkylthio Represents a group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group. Each group may be further substituted. R ¹ and R ⁵ , and R ⁵ and R ⁶ may be independently bonded to form a 5- to 6-membered ring. ]

[In General Formula (CI), X ¹ , X ² , X ³ and X ⁴ are each independently —SO—Z ¹ , —SO ₂ —Z ¹ , or —SO ₂ —N (R ²¹ ). R ²² is represented. Z ¹ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group. Each may further have a substituent. R ²¹ and R ²² each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group. Each may further have a substituent. Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro Group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, An acyl group, a carboxyl group, or Represents a sulfo group, and each may further have a substituent. a1 to a4, b1.about.b4 each represent a number of substituents ^{X 1 ~X 4, Y 1 ~Y} 4, a1~a4 each independently represents an integer of 0 to 4, b1.about.b4 each independently Represents an integer of 0 to 4; However, the sum of a1 to a4 is 2 or more. Here, when representing an integer of 2 or more in each independently a1~a4 and b1.about.b4, a plurality of X ¹ to X ⁴ and Y ¹ to Y ⁴ may be the different from each other in the same. a1 and b1 each independently represent an integer of 0 to 4 that satisfies the relationship of a1 + b1 = 4. a2 and b2 each independently represent an integer of 0 to 4 that satisfies the relationship of a2 + b2 = 4. a3 and b3 each independently represent an integer of 0 to 4 that satisfies the relationship of a3 + b3 = 4. a4 and b4 each independently represent an integer of 0 to 4 that satisfies the relationship of a4 + b4 = 4. M represents a hydrogen atom, a metal element or an oxide thereof, a hydroxide, or a halide. ] An ink comprising the fine particle dispersion according to any one of claims 1 to 5. An inkjet recording method comprising a step of recording an image on a recording material using the ink according to claim 6. 8. The ink jet recording method according to claim 7, wherein the recording material is a recording paper provided with an ink receiving layer having a porous structure containing at least porous inorganic fine particles.