JP2001226613A - Colored particulate dispersion, ink for ink jet printing use, and ink jet printing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored particulate dispersion excellent in color developability/color tone and water resistance/light resistance as well, therefore favorably usable for ink. SOLUTION: This colored particulate dispersion is characterized by comprising colored particulate comprising at least one polymer selected from among polyurethanes, polyesters, polyamides, polyurea and polycarbonates and an oil-soluble dye shown by general formula (I), (II), (III) or (IV); wherein R1, R2, R3 and R4 are each H or a nonmetallic atomic group; X is OH or NR5R6; R5 and R6 are each H, an alkyl, aryl or heterocyclic group; and R7, R8 and R9 are each H or a nonmetallic atomic group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a colored fine particle dispersion,
And an ink jet recording ink containing the colored fine particle dispersion and an ink jet recording method using the same, more specifically, good color reproducibility,
The present invention relates to a colored fine particle dispersion suitable for an aqueous ink for writing, an aqueous printing ink, an information recording ink, and the like, and an ink jet recording ink and an ink jet recording method suitable for a thermal, piezoelectric, electric field, or acoustic ink jet system.

[0002]

2. Description of the Related Art In recent years, with the spread of computers, ink jet printers have been widely used not only in offices but also at home for printing on paper, film, cloth and the like. Oil-based, aqueous,
Solid inks are known, but water-based inks are mainly used in terms of manufacturing, handling, odor, safety, and the like.

However, most of the aqueous inks use water-soluble dyes that dissolve in a molecular state, and thus have the advantage of high transparency and color density. However, since the dyes are water-soluble, they have poor water resistance. When printing on so-called plain paper, there is a problem that bleeding occurs and the printing quality is remarkably deteriorated, and light resistance is poor.

In order to solve the above-mentioned problem, an aqueous ink using a pigment or a disperse dye has been disclosed in, for example, JP-A-56-1.
57468, JP-A-4-18468, 8-183
No. 920, No. 10-110126, No. 10-1953
No. 55 and other publications. However, in the case of these water-based inks, the water resistance is improved to some extent, but it is not sufficient, and the storage stability of the dispersion of the pigment or the disperse dye in the water-based ink is lacking, causing clogging at the ink ejection port. There is a problem such as easy. In addition, these aqueous inks generally have insufficient hue and have a problem in color reproducibility based on insufficient color tone.

Further, Japanese Patent Application Laid-Open No. 58-45272,
-340835, 7-268254, 7-26
Nos. 8257 and 7-268260 propose a method of encapsulating a dye in polyurethane or polyester dispersion particles. However, the dispersions described above have not only the problem of color reproducibility due to insufficient color tone as described above, but also the dispersion stability of the dye-containing polymer dispersion when the dye is included at a desired concentration. Also, there is a problem that the water resistance is not always sufficient.

On the other hand, JP-A-9-59552 and 9-1
No. 11163, No. 9-255887, No. 10-367
No. 28 proposes to improve the color tone by using a dye obtained by coupling an aromatic diamine to pyrazolotriazole. However, in these cases, there are problems that the color tone changes depending on the type of the image receiving paper and that the water resistance is not sufficient.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention has excellent dispersion stability of colored fine particles, is independent of paper, has excellent color development and color tone (particularly, cyan color reproduction) when printed on arbitrarily selected paper, and has excellent water resistance and light resistance. An object of the present invention is to provide a colored fine particle dispersion suitable for aqueous ink for writing, aqueous printing ink, ink for information recording and the like. Further, the present invention is suitable for thermal, piezoelectric, electric field or acoustic ink jet system, when performing printing using a nozzle or the like, does not cause clogging at the nozzle tip, there is no paper dependence, Provided are an ink jet recording ink and an ink jet recording method capable of forming an image having excellent color developability and color tone (particularly, cyan color reproduction) and excellent water resistance and light resistance when printed on arbitrarily selected paper. With the goal.

[0008]

Means for solving the above problems are as follows. That is, <1> at least one selected from polyurethane, polyester, polyamide, polyurea and polycarbonate
One kind of polymer and the following general formulas (I), (II) and (III)
And (IV). A colored fine particle dispersion comprising colored fine particles containing an oil-soluble dye represented by any of (IV) and (IV).

[0009]

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The general formulas (I), (II), (III) and (I)
V) Medium, R¹, R^Two, R^ThreeAnd R^FourAre each independently a hydrogen atom
Or X represents -OH or -N
R ^FiveR⁶And R^FiveAnd R⁶Are each independently a hydrogen atom,
Represents an alkyl group, an aryl group or a heterocyclic group,
R⁷, R⁸And R⁹Are each independently a hydrogen atom or a nonmetallic
Represents an atomic group. R¹And R^Two, R^TwoAnd R^Five, R^FiveAnd R⁶, R⁶
And R^Three, And R^ThreeAnd R^FourAt least one of each other
May form a ring structure;⁷And R⁸Are connected to each other
Together, they may form a ring structure. R¹And R^Two, R^TwoWhen
R^Five, R^FiveAnd R⁶, R⁶And R^Three, And R^ThreeAnd R^FourAt least
Any of which may form a ring structure with each other;⁷
And R⁸May be linked to each other to form a ring structure
No.

<2> The general formulas (I), (II) and (II)
R ⁷ in I) and (IV) is the Hammett substituent constant σ _p
An acyl group having a value of 0.30 or more, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, Halogenated alkyl group, halogenated alkoxy group, halogenated aryloxy group or halogenated alkylthio group,
sigma _p value is a colored fine particle dispersion according to <1>, wherein the representing two or more substituted aryl group or a heterocyclic group, with 0.15 or more electron withdrawing groups.

<3> Formulas (I), (II) and (II)
The colored fine particle dispersion according to <1> or <2>, wherein the sum of Hammett substituent constants of R ⁷ and R ⁸ in I) and (IV) is 0.70 or more.

<4> At least one polymer selected from polyurethane, polyester, polyamide, polyurea and polycarbonate is 0.01 to 3.0 m
The colored fine particle dispersion according to any one of <1> to <3>, which is a polymer having a dissociable group of mol / g.

<5> The dissociative group is at least one of a carboxyl group and a sulfonic acid group.
4>.

<6> water is added to an organic solvent phase in which the colored fine particles contain at least one polymer selected from polyurethane, polyester, polyamide, polyurea and polycarbonate and an oil-soluble dye;
The dispersion of colored fine particles according to any one of <1> to <5>, wherein the dispersion is obtained by emulsifying the organic solvent phase by adding the organic solvent phase to water. Things.

<7> There is a maximum absorption wavelength (λmax (nm)) within the wavelength range of 580 to 700 nm, and when the absorbance at the maximum absorption wavelength (λmax (nm)) is 1, the wavelength (λmax−100 (λmax−100)) <1> to <6, wherein the absorbance at (nm)) is 0.35 or less.
The colored fine particle dispersion described in any one of the above-mentioned items.

<8> An ink jet recording ink comprising the colored fine particle dispersion according to any one of <1> to <7>.

<9> An ink jet recording method comprising: applying energy to the ink jet recording ink described in <8> to discharge droplets of the ink onto an image receiving material, thereby recording an image on the image receiving material. Is the way.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The colored fine particle dispersion, ink for ink jet recording and ink jet recording method of the present invention will be described below. (Colored fine particle dispersion) The colored fine particle dispersion of the present invention comprises an oil-soluble dye, polyurethane, polyester, polyamide,
Colored fine particles containing at least one polymer selected from polyurea and polycarbonate are dispersed in an aqueous medium.

-Oil-Soluble Dye- The oil-soluble dye is represented by the general formula (I), (II) or (II)
At least one selected from oil-soluble dyes (pyrrolotriazole azomethine compounds) represented by I) and (IV)
Is a seed. Formulas (I), (II), (III) and (I)
In V), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a nonmetallic atomic group. Examples of the nonmetallic atomic group include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an amino group (including a substituted amino group), an alkoxy group, an aryloxy group, and an acylamino group. Group, aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy Group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, imide group, heterocyclic thio group, sulfinyl group, phosphoryl group, acyl group and the like.

Specific examples of the nonmetallic atomic group include an alkyl group (preferably having 1 to 20 carbon atoms, for example, methyl,
Ethyl, propyl, butyl), an alkoxy group (preferably having 1 to 20 carbon atoms, for example, methoxy, ethoxy, methoxyethoxy, isopropoxy), a halogen atom (eg, bromine, fluorine, chlorine), an acylamino group [preferably having 1 to carbon atoms. 20 alkylcarbonylamino groups (for example, formylamino, acetylamino, propionylamino,
Cyanoacetylamino), preferably an arylcarbonylamino group having 7 to 20 carbon atoms (eg, benzoylamino, p-toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino),

An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl), a cyano group, a sulfonylamino group (preferably having 1 to 20 carbon atoms, methanesulfonylamino, ethanesulfonylamino, N-methylmethane) Sulfonylamino),
A carbamoyl group [preferably an alkylcarbamoyl group having 2 to 20 carbon atoms (for example, methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, butylcarbamoyl, isopropylcarbamoyl, t-butylcarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, methoxyethylcarbamoyl, chloroethylcarbamoyl, Cyanoethylcarbamoyl, ethylcyanoethylcarbamoyl, benzylcarbamoyl, ethoxycarbonylmethylcarbamoyl, furfurylcarbamoyl, tetrahydrofurfurylcarbamoyl, phenoxymethylcarbamoyl, allylcarbamoyl, crotylcarbamoyl, prenylcarbamoyl, 2,3-dimethyl-2-butenylcarbamoyl, homoallylcarbamoyl , Homocrotirca Rubamoyl, homoprenylcarbamoyl), preferably an arylcarbamoyl group having 7 to 20 carbon atoms (eg, phenylcarbamoyl, p-tolylcarbamoyl, m-methoxyphenylcarbamoyl,
5-dichlorophenylcarbamoyl, p-cyanophenylcarbamoyl, p-acetylaminophenylcarbamoyl, p-methoxycarbonylphenylcarbamoyl,
m-trifluoromethylphenylcarbamoyl, o-fluorophenylcarbamoyl, 1-naphthylcarbamoyl), preferably a hetenylcarbamoyl group having 4 to 20 carbon atoms (eg, 2-pyridylcarbamoyl, 3-pyridylcarbamoyl, 4-pyridylcarbamoyl, 2- Thiazolylcarbamoyl, 2-benzthiazolylcarbamoyl, 2-benzimidazolylcarbamoyl, 2- (4-
Methylphenyl) 1,3,4-thiadiazolylcarbamoyl),

A sulfamoyl group (preferably having a carbon number of 0 to 0)
20, for example, methylsulfamoyl and dimethylsulfamoyl), an aminocarbonylamino group (preferably having 1 to 20 carbon atoms, for example, methylaminocarbonylamino and dimethylaminocarbonylamino), and an alkoxycarbonylamino group (preferably having 2 to 2 carbon atoms) 20, for example, methoxycarbonylamino, ethoxycarbonylamino), a hydroxy group, an amino group (preferably having 0 to 20 carbon atoms such as amino, methylamino, dimethylamino, anilino), an aryl group (preferably having 6 to 20 carbon atoms such as phenyl) , M-acetylphenyl, p-methoxyphenyl), a heterocyclic group (preferably having 3 to 20 carbon atoms, for example, 2-pyridyl, 2-furyl, 2-tetrahydrofuryl), a nitro group, an aryloxy group (preferably having carbon atoms) 6 to 20, for example, fenoki , P-methoxyphenoxy, o-chlorophenoxy), a sulfamoylamino group (preferably having 0 to 20 carbon atoms, for example, methylsulfamoylamino, dimethylsulfamoylamino), and an alkylthio group (preferably having 1 to 20 carbon atoms) For example, methylthio, ethylthio), an arylthio group (preferably having 6 to 20 carbon atoms, for example, phenylthio, p-methoxyphenylthio, o-chlorophenylthio),

A sulfonyl group (preferably having 1 to 2 carbon atoms)
0, for example, methanesulfonyl, p-toluenesulfonyl), an acyl group (preferably having 1 to 20 carbon atoms, such as formyl, acetyl, benzoyl, p-toluyl), a heterocyclic oxy group (preferably having 3 to 20 carbon atoms), azo Groups (preferably having 3 to 20 carbon atoms, for example, p-nitrophenylazo), and acyloxy groups (preferably having 1 to 2 carbon atoms).
0, for example, acetyloxy, benzoyloxy), a carbamoyloxy group (preferably having 1 to 20 carbon atoms, for example, methylcarbamoyloxy), a silyloxy group (preferably having 3 to 20 carbon atoms, for example, trimethylsiloxy), an aryloxycarbonyl group (preferably, Has 7 to 2 carbon atoms
0, such as phenoxycarbonyl), an imide group (preferably having 4 to 20 carbon atoms, such as phthalimide), a heterocyclic thio group (preferably having 3 to 20 carbon atoms), a sulfinyl group (preferably having 1 to 20 carbon atoms, such as diethylaminosulfinyl) ), A phosphoryl group (preferably having 0 to 2 carbon atoms)
0, for example, diaminophosphoryl) and the like.

Among the substituents exemplified above, R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
An alkoxy group, a halogen atom (fluorine, chlorine, bromine), an acylamino group having 1 to 20 carbon atoms, and 1 to 2 carbon atoms
It is preferably a sulfonylamino group having 0, an aminocarbonylamino group having 1 to 20 carbon atoms, or an alkoxycarbonylamino group having 2 to 20 carbon atoms, and more preferably a hydrogen atom, an alkyl group, or an acylamino group. R ² , R ³
And R ⁴ is preferably a hydrogen atom.

In the above general formulas (I), (II), (III) and (IV), X represents -OH or -NR ⁵ R ⁶ ,
It is preferably R ⁵ R ⁶ .

R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 20 carbon atoms, for example, methyl,
Ethyl, propyl, isopropyl, butyl, 2-methoxyethyl, 3-methoxypropyl, ethoxyethyl, 2
-Phenylethyl, 2-cyanoethyl, cyanomethyl,
2-methylsulfonylaminoethyl, 2-chloroethyl, 3-bromopropyl, 2-methoxycarbonylethyl, 3-ethoxycarbonylpropyl, 2- (N-methylaminocarbonyl) ethyl, 3- (N, N-dimethylaminocarbonyl) Propyl, 2-acetylaminoethyl, 3- (ethylcarbonylamino) propyl, 2-acetyloxyethyl, allyl, homoallyl, prenyl,
n-dodecyl, 2-hydroxyethyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 2,
3,4,5,6-pentahydroxyhexyl, 2- (2
-Hydroxyethoxy) ethyl, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl, 2- (2- [2-
(2-hydroxyethoxy) ethoxy] ethoxy) ethyl, carboxymethyl, 2-carboxyethyl), an aryl group (preferably having 6 to 20 carbon atoms, for example, phenyl,
p-tolyl, p-methoxyphenyl, 2,4-dichlorophenyl, p-nitrophenyl, 2,4-dicyanophenyl, 2-naphthyl) or a heterocyclic group (including those having a substituent; preferably having 3 to 3 carbon atoms) 20, for example, the groups shown below).

[0028]

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Among the substituents exemplified above, R ⁵ and R ⁶
Is an optionally substituted alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl, 2-cyanoethyl, cyanomethyl, 2- (N-methylaminocarbonyl) ethyl, 2-acetylaminoethyl , 2-acetyloxyethyl, allyl, n-dodecyl, 2-hydroxyethyl, 2,3-dihydroxypropyl, 2,3,4,5,6-pentahydroxyhexyl, 2- (2-hydroxyethoxy) ethyl, -Carboxyethyl, 2-methylsulfonylaminoethyl).

In the above general formulas (I), (II), (III) and (IV), R ⁷ , R ⁸ and R ⁹ represent a hydrogen atom or a nonmetallic atomic group.

Examples of the nonmetallic atomic group include an aryl group, a heterocyclic group, an alkyl group, a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, an alkoxycarbonylamino group, and an aryl group. Oxycarbonylamino group, sulfonylamino group, aminocarbonylamino group,
Sulfamoylamino group, amino group (including anilino group), alkoxy group, aryloxy group, silyloxy group, heteryloxy group, alkthio group, arylthio group, heterylthio group, halogen atom, hydroxy group, nitro group, sulfamoyl group, sulfonyl And an azo group, an acyloxy group, a carbamoyloxy group, an imide group, a sulfinyl group, and a phosphoryl group.

Specific examples of the nonmetallic atomic group include an aryl group (preferably having 6 to 36 carbon atoms, for example, phenyl, 4-t-butylphenyl, 2,4-di-amylphenyl, 2,4,4 6-trimethylphenyl, 2-tetradecanamidophenyl, 2-methoxyphenyl), alkyl group (preferably having 1 to 36 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, tridecyl, t- Amyl, t-octyl, 2-methanesulfonylethyl 3- (3-pentadecylphenoxy) propyl, cyclohexyl, 3- (2,
4-di-t-amylphenoxy) propyl), a cyano group, an acyl group (preferably having 1 to 36 carbon atoms such as acetyl and benzoyl), and a carbamoyl group (preferably having 1 to 36 carbon atoms such as N, N-dibutylcarbamoyl) ),
An alkoxycarbonyl group (preferably having 1 to 36 carbon atoms;
For example, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, 2,6-di-t-butyl-4-
Methylcyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably having 7 to 36 carbon atoms, for example, phenoxycarbonyl, p-methoxyphenoxycarbonyl, m-chlorophenoxycarbonyl, o-methoxyphenoxycarbonyl),

An acylamino group [preferably having 1 to 3 carbon atoms;
6 alkylcarbonylamino groups (eg, formylamino, acetylamino, propionylamino, cyanoacetylamino), preferably an arylcarbonylamino group having 7 to 36 carbon atoms (eg, benzoylamino, p-toluylamino, pentafluorobenzoylamino, m-
Methoxybenzoylamino), preferably having 4 to 3 carbon atoms
6 hetenylcarbonylamino group (for example, 2-pyridylcarbonylamino, 3-pyridylcarbonylamino,
Furoylamino)], an alkoxycarbonylamino group (preferably having 2 to 36 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, methoxyethoxycarbonylamino), an aryloxycarbonylamino group (preferably having 7 to 36 carbon atoms, for example, phenoxycarbonylamino) P-methoxyphenoxycarbonylamino, p-methylphenoxycarbonylamino, m-chlorophenoxycarbonylamino, o-chlorophenoxycarbonylamino), a sulfonylamino group (preferably having 1 to 36 carbon atoms, for example, methanesulfonylamino,
Benzenesulfonylamino, toluenesulfonylamino),

An aminocarbonylamino group (preferably having 1 to 36 carbon atoms, for example, methylaminocarbonylamino,
Ethylaminocarbonylamino, anilinocarbonylamino, dimethylaminocarbonylamino), sulfamoylamino group (preferably having 1 to 36 carbon atoms, for example, methylaminosulfonylamino, ethylaminosulfonylamino, anilinosulfonylamino), amino group ( It contains an anilino group, preferably having 0 to 36 carbon atoms, for example, amino, methylamino, dimethylamino, ethylamino, diethylamino, n-butylamino, anilino), an alkoxy group (preferably having 1 to 36 carbon atoms, for example, methoxy,
Ethoxy, isopropoxy, n-butoxy, methoxyethoxy, n-dodecyloxy), aryloxy group (preferably having 6 to 36 carbon atoms, for example, phenoxy, m-chlorophenoxy, p-methoxyphenoxy, o-methoxyphenoxy, 4- t-butylphenoxy, 2,6-di-
t-butylphenoxy), a silyloxy group (preferably having 3 to 36 carbon atoms such as trimethylsiloxy, t-butyldimethylsiloxy), a heteryloxy group (preferably having 3 to 36 carbon atoms such as tetrahydropyranyloxy),
3-pyridyloxy, 2- (1,3-benzimidazolyl) oxy), an alkylthio group (preferably having 1 to 1 carbon atoms)
36, e.g., methylthio, ethylthio, n-butylthio, t-butylthio), an arylthio group (preferably having 6 to 36 carbon atoms, e.g., phenylthio), a heterylthio group (preferably having 3 to 36 carbon atoms, e.g., 2-pyridylthio, 2- ( 1,3-benzoxazolyl) thio, 1-hexadecyl-1,2,3,4-tetrazolyl-5-thio, 1- (3-N-octadecylcarbamoyl) phenyl-1,2,3,4-tetrazolyl -5-thio),

A heterocyclic group (preferably having 3 to 36 carbon atoms;
For example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1-pyrazolyl, 1-pyrrolyl, 2-furanyl, 2-pyridyl, 3-pyridyl), halogen Atoms (fluorine, chlorine, bromine), hydroxy group, nitro group, sulfamoyl group (preferably having 0 to 3 carbon atoms)
6, for example, methylsulfamoyl, dimethylsulfamoyl), a sulfonyl group (preferably having 1 to 36 carbon atoms, for example, methanesulfonyl, benzenesulfonyl, toluenesulfonyl), and an azo group (preferably having 3 to 36 carbon atoms, for example, p- Nitrophenylazo), acyloxy group (preferably having 1 to 36 carbon atoms, for example, formyloxy, acetyloxy, benzoyloxy), carbamoyloxy group (preferably having 1 to 36 carbon atoms, for example, methylcarbamoyloxy, diethylcarbamoyloxy), imide Groups (preferably having 4 to 36 carbon atoms, such as succinimide,
Phthalimide), a sulfinyl group (preferably having 1 carbon atom)
To 36, for example, diethylaminosulfinyl), and a phosphoryl group (preferably having 0 to 36 carbon atoms, for example, diaminophosphoryl).

In the above general formulas (I), (II), (III) and (IV), R ¹ and R ² , R ² and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ³ ,
And at least one of R ³ and R ⁴ may form a ring structure with each other, and R ⁷ and R ⁸ may bond with each other to form a ring structure.

As the ring structure which may be formed by combining R ⁵ and R ⁶ , for example, the following ring structures are preferred.

[0038]

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As the ring structure which may be formed by combining R ² and R ⁵ and / or R ³ and R ⁶ , for example, the following ring structures are preferable (for example, the general formula (I) ) To (IV).

[0040]

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The oil-soluble dyes represented by formulas (I) to (IV) are a combination of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ . Can have various hues.

In the present invention, it is preferable that R ⁷ is an electron-withdrawing substituent in that the absorption waveform becomes sharper as compared with the other substituents. The waveform is more preferable in that it becomes sharper. Specifically, R ⁷ is preferably an electron-withdrawing group having a Hammett substitution constant σ _p value of 0.30 or more, more preferably 0.45 or more than an alkyl group or an aryl group. More preferably, an electron-withdrawing group of 0.60 or more is particularly preferable.

Specific examples thereof include an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfinyl group having a Hammett substituent constant σ _p value of 0.30 or more. An arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a halogenated alkyl group, a halogenated alkoxy group,
Examples include a halogenated aryloxy group, a halogenated alkylthio group, an aryl group substituted with two or more electron-withdrawing groups having a σ _p value of 0.15 or more, and a heterocyclic ring.

Among these specific examples, the following are particularly preferred. That is, an acyl group (eg, acetyl, 3
-Phenylpropanoyl), an acyloxy group (for example,
Acetoxy), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2
-Dodecyloxyethyl) carbamoyl, N-methyl-
N-dodecylcarbamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl), a cyano group, a nitro group, an alkylsulfinyl group (eg, , 3-phenoxypropylsulfinyl), an arylsulfinyl group (eg, 3-pentadecylphenylsulfinyl), an alkylsulfonyl group (eg, methanesulfonyl, octanesulfonyl), an arylsulfonyl group (eg, benzenesulfonyl), a sulfamoyl group (eg, N -Ethylsulfamoyl, N, N-dipropylsulfamoyl), halogenated alkyl groups (eg, trifluoromethyl, heptafluoropropyl) halo Emissions alkoxy group (e.g., trifluoromethyloxy), halogenated aryloxy group (e.g., pentafluorophenyloxy), a halogenated alkylthio group (e.g., difluoromethylthio), sigma _p
An aryl group substituted with two or more other electron-withdrawing groups having a value of 0.15 or more (for example, 2,4-dinitrophenyl,
2,4,6-trichlorophenyl, pentachlorophenyl), a heterocyclic group (for example, 2-benzoxazolyl,
-Benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1-pyrrolyl) and the like.

The Hammett substituent constant σ _p value is 0.45
Examples of the above electron-withdrawing group include an acyl group (eg, acetyl, 3-phenylpropanoyl), an alkoxycarbonyl group (eg, methoxycarbonyl), an aryloxycarbonyl group (eg, m-chlorophenoxycarbonyl), a cyano group, Nitro group, alkylsulfinyl group (eg, n-propylsulfinyl), arylsulfinyl group (eg, phenylsulfinyl), alkylsulfonyl group (eg, methanesulfonyl, n-octanesulfonyl), arylsulfonyl group (eg, benzenesulfonyl), sulfamoyl Groups (eg, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), and halogenated alkyl groups (eg, trifluoromethyl).

The Hammett substituent constant σ _p value is 0.60
Examples of the electron-withdrawing group include a cyano group (0.66),
Nitro group (0.78), methanesulfonyl group (0.7
2) and the like.

Here, Hammett's substituent constant will be described. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives,
Year L. P. A rule of thumb proposed by Hammett, which is widely accepted today. The substituent constants determined by the 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 edition "Lange's
Handbook of Chemistry "12
Editions, 1979 (McGraw-Hill) and "Regions of Chemistry," Special Issue, No. 122, pp. 96-103, 1979 (Nankodo). In the present invention, each substituent is defined or described by Hammett's substituent constant σ _p, but this is limited only to a substituent having a known value in the literature, as in the above-mentioned textbook. It does not mean that 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 the Hammett rule. In the present invention, the σ _p value and the σ _m value are used in the above meaning.

In the present invention, the above-mentioned general formula (I)
An oil-soluble dye (pyrrolotriazole azomethine compound) represented by any of (II), (III) and (IV) can be used, and its hue is not particularly limited. Good cyan hue. Also,
The oil-soluble dye (pyrrolotriazole azomethine compound) represented by any of the general formulas (I) and (II) is
Not only the cyan hue but also the magenta hue are good.

In order for the oil-soluble dye to exhibit a good cyan hue, the compounds represented by the general formulas (I), (II), (III) and (I)
In V), the sum of Hammett substituent constant σ _p values of R ⁷ and R ⁸ is 0.
It is preferably at least 70, more preferably from 0.7 to 2.0, and the Hammett's substituent constant σ _p value of R ⁸ is 0.3.
It is particularly preferred that it is 30 or more. When the sum of the Hammett substituent constant σ _p values of R ⁷ and R ⁸ is less than 0.70, the absorption maximum wavelength becomes a short wavelength as a cyan dye,
It looks blue to the human eye and is undesirable.

As a combination in which the sum of the Hammett substituent constants σ _p values of R ⁷ and R ⁸ is 0.70 or more, R ⁷ is a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyl halide And R ⁸ is preferably selected from an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, and a halogenated alkyl group. .

In the present invention, the above-mentioned general formula (I)
Oil solution represented by any of (II), (III) and (IV)
Among the dyes (pyrrolotriazole azomethine compounds)
Also, a compound represented by the above general formula (I) is preferable.
But R¹Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
An alkoxy group having 1 to 10 carbon atoms, a halogen atom (fluorine)
Element, chlorine, bromine), an acylamino group having 1 to 10 carbon atoms,
An aminocarbonylamino group having 1 to 10 carbon atoms, or charcoal
Represents an alkoxycarbonylamino group having a prime number of 1 to 10,
R^Two, R^Three, R^FourEach represents a hydrogen atom, and X represents -NR^FiveR
⁶And R^FiveAnd R ⁶Are each independently substituted with 1 to 10 carbon atoms.
Represents an alkyl group which may be substituted,⁷And R⁸But each
Independently Hammett substituent constant σ_pIf the value is 0.30 or more,
Represents a child-withdrawing group;⁹Is an alkyl group having 1 to 20 carbon atoms
Or a compound representing an aryl group having 6 to 20 carbon atoms
Preferably, R¹Represents a hydrogen atom or a methyl group;^Two,
R^Three, R^FourRepresents a hydrogen atom, and X represents -NR^FiveR⁶And R
^FiveAnd R⁶Each independently represents an alkyl group having 1 to 5 carbon atoms
Then R⁷Represents a cyano group;⁸Is alkoxycarbonyl
R represents a group⁹Are particularly preferred.
No. Further, among these, used as a cyan dye
In that case, R⁷And R⁸Substituent constant σ with_pSum of values
Is preferably 0.70 or more, more preferably σ_pSum of values
Is preferably 1.00 or more.

The following formulas (I), (II) and (II)
Specific examples (D-1 to D-1) of the oil-soluble dyes (pyrrolotriazole azomethine compounds) represented by any of I) and (IV)
45) are listed. The present invention is not limited at all by the following specific examples.

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The oil-soluble dyes (pyrrolotriazoleazomethine compounds) represented by any of the above general formulas (I), (II), (III) and (IV) are exemplified by the following couplers (A) and (B) , (C) and (D), and the following p-phenylenediamine compound (E) by oxidative coupling.

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In this case, the couplers (A), (B),
In (C) and (D), Q represents a hydrogen atom or a leaving group that leaves during the coupling reaction. The couplers ((A), (B), (C) and (D)) may be tautomers.

The compounds represented by the general formulas (I), (II) and (II)
The oil-soluble dye (pyrrolotriazole azomethine compound) represented by any one of (I) and (IV) is, for example, any one of the couplers (A), (B), (C) and (D), and the following nitroso compound Compound (F) can be synthesized by dehydration condensation.

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In this case, the couplers (A), (B),
In (C) and (D), Q represents a hydrogen atom.

The above-mentioned general formulas (I), (II) and (III)
The oil-soluble dyes (pyrrolotriazole azomethine compounds) represented by any of (IV) and (IV) are disclosed in JP-A-5-1779.
The compounds can be synthesized with reference to the methods described in JP-A-59-92 and JP-A-9-292679.

—Polymer— In the present invention, the colored fine particles contain at least one polymer selected from polyurethane, polyester, polyamide, polyurea and polycarbonate (hereinafter, may be referred to as “the polymer of the present invention”). Two or more polymers may be used. As the polymer,
Conventionally known compounds may be mentioned, and any of a water-insoluble type, a water-dispersed (self-emulsifying) type, and a water-soluble type may be used. Among them, a water-insoluble polymer and a water-dispersible polymer are preferable in terms of ease of producing colored fine particles, and a water-dispersible polymer is particularly preferable in terms of dispersion stability.

The water-dispersible polymer may be any of an ion-dissociative polymer, a nonionic dispersible group-containing polymer, and a mixed polymer thereof. Examples of the ion dissociation type polymer include a polymer having a cationic dissociative group such as a tertiary amino group and a polymer containing an anionic dissociative group such as a carboxylic acid and a sulfonic acid. Examples of the nonionic dispersible group-containing polymer include a polymer containing a nonionic dispersible group such as a polyethyleneoxy group.

Among these, in view of the dispersion stability of the colored fine particles, an ion dissociation type polymer containing an anionic dissociation group, a nonionic dissociation group containing type polymer, and a mixed type polymer thereof Is preferred.

Hereinafter, each polymer usable in the present invention will be described. —Polyurethane— The polyurethane can be basically synthesized by a polyaddition reaction using a diol compound and a diisocyanate compound as raw materials. Specific examples of the diol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3- Butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 3,3-dimethyl-1, 2-butanediol,
2-ethyl-2-methyl-1,3-propanediol,
1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,2
-Diethyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,5-dimethyl-2,5- Hexanediol, 2-ethyl-1,3-hexanediol, 1,2-
Octanediol, 1,8-octanediol, 2,
2,4-trimethyl-1,3-pentanediol, 1,
4-cyclohexanedimethanol, hydroquinone, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol (average molecular weight = 200, 300, 40)
0,600,1000,1500,4000), polypropylene glycol (average molecular weight = 200,400,1)
000), polyester polyols, 4,4'-dihydroxydiphenyl-2,2-propane, 4,4'-dihydroxyphenylsulfone and the like.

As the polyurethane, a polyurethane having a dissociable group is preferable from the viewpoint that the productivity and dispersion stability of the colored fine particles can be improved. As the dissociable group, a carboxyl group, a sulfonic acid group, a sulfuric acid monoester group,-
OPO (OH) ₂ , sulfinic acid group, or a salt thereof (for example, an alkali metal salt such as Na or K, or an ammonium salt such as ammonia, dimethylamine, ethanolamine, diethanolamine, triethanolamine, or trimethylamine). Anionic groups or cationic groups such as primary, secondary, tertiary amines and quaternary ammonium salts are mentioned, and among them, anionic groups are preferred, and carboxyl groups are particularly preferred.

The dissociable group can be introduced into the polyurethane as a substituent from the polymer main chain by using a diol containing a dissociable group during the synthesis of the polyurethane. Examples of usable diols having an anionic group include 2,2-bis (hydroxymethyl)
Propionic acid, 2,2-bis (hydroxymethyl) butanoic acid, 2,5,6-trimethoxy-3,4-dihydroxyhexanoic acid, 2,3-dihydroxy-4,5-dimethoxypentanoic acid, 2,4-di ( Examples include, but are not limited to, 2-hydroxy) ethyloxycarbonylbenzenesulfonic acid and salts thereof.

The diisocyanates constituting the polyurethane include methylene diisocyanate, ethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,4-toluene diisocyanate,
2,6-toluene diisocyanate, 1,3-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 3,3 ′ -Dimethyl biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate) and the like are preferable.

The diol compound and the diisocyanate compound that can be used in the synthesis of the polyurethane may be used alone or may be used for various purposes (for example, adjustment of the glass transition temperature (Tg) of the polymer and solubility of the polymer). , And the compatibility with the dye and the stability of the dispersion).

--Polyester-- The polyester usable in the present invention can be basically synthesized by dehydration condensation of a diol compound and a dicarboxylic acid compound. Examples of the dicarboxylic acid compound include oxalic acid, malonic acid, succinic acid, glutaric acid, dimethylmalonic acid, adipic acid, pimelic acid, α, α-dimethylsuccinic acid, acetone dicarboxylic acid, sebacic acid, and 1,9-nonanedicarboxylic acid. Acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, 2-
Butyl terephthalic acid, tetrachloroterephthalic acid, acetylenedicarboxylic acid, poly (ethylene terephthalate)
Dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid,
Examples thereof include 1,4-cyclohexanedicarboxylic acid, ω-poly (ethylene oxide) dicarboxylic acid, and p-xylylenedicarboxylic acid.

When the dicarboxylic acid compound is subjected to a polycondensation reaction with a diol compound, it may be used in the form of an alkyl ester of a dicarboxylic acid (eg, dimethyl ester) and an acid chloride of a dicarboxylic acid, or maleic anhydride. It may be used in the form of an acid anhydride such as acid, succinic anhydride and phthalic anhydride.

In addition to the carboxylic acid, the polyester of the present invention contains a sulfonic acid group, a sulfuric acid monoester group, -OP
O (OH) ₂ , a sulfinic acid group, or a salt thereof (for example, an alkali metal salt such as Na or K, or an ammonium salt such as ammonia, dimethylamine, ethanolamine, diethanolamine, triethanolamine, or trimethylamine). A dicarboxylic acid compound having an anionic group or a dissociative group such as a cationic group such as a primary, secondary, tertiary amine or quaternary ammonium salt can be used. As the dissociable group, an anionic group is preferable, and a sulfonic acid group is particularly preferable.

A dicarboxylic acid having a sulfonic acid group,
Preferred examples of the diol raw materials include sulfophthalic acids (3-sulfophthalic acid, 4-sulfophthalic acid, 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, and 2-sulfoterephthalic acid), sulfosuccinic acid, and sulfonaphthalenedicarboxylic acids (4- Sulfo 1,8-naphthalenedicarboxylic acid, 7-sulfo-1,5-naphthalenedicarboxylic acid, etc.), 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid, and salts thereof.

As the diol compound, the same compounds as the diols exemplified in the above polyurethane can be used.

A typical polyester synthesis method is a condensation reaction of the diol compound and the dicarboxylic acid or a derivative thereof.
2-hydroxystearic acid), and the polyester produced by this method can also be used. Further, a polyester obtained by a method such as a ring-opening polymerization method of a cyclic ether and a lactone (Course polymerization reaction theory 6: Ring-opening polymerization (I) detailed by Takeo Saegusa (Kagaku Dojin, 1971)) is also used in the present invention. be able to.

The diol compound, dicarboxylic acid, and hydroxycarboxylic acid compound used in the synthesis of the polyester may be used alone, or may be used for various purposes (for example, glass transition temperature (Tg) of polymer). , And the solubility, compatibility with the dye, and the stability of the dispersion) may be used in combination of two or more at an arbitrary ratio.

--Polyamide-- The polyamide usable in the present invention can be obtained by polycondensation of a diamine compound and a dicarboxylic acid compound, polycondensation of an aminocarboxylic acid compound, or ring-opening polymerization of lactams. Examples of the diamine compound include ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, hexamethylenediamine, octamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, piperazine, and 2,5.
-Dimethylpiperazine, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylsulfone, xylylenediamine and the like, and as the aminocarboxylic acid, glycine, alanine, phenylalanine,
ω-aminohexanoic acid, ω-aminodecanoic acid, ω-aminoundecanoic acid, and anthranilic acid. Also,
Examples of monomers that can be used for ring-opening polymerization include ε-caprolactam, azetidinone, and pyrrolidone.

As the dicarboxylic acid compound, the same compounds as the dicarboxylic acids exemplified in the polyester can be used.

The diamine compound, dicarboxylic acid, and aminocarboxylic acid compound used in the synthesis of the polyamide may be used alone or for various purposes (for example, the glass transition temperature (Tg) of a polymer). Adjustment, solubility, compatibility with dye, stability of dispersion)
Two or more of them can be used by mixing at an arbitrary ratio.

—Polyurea— The polyurea usable in the present invention can be basically obtained by polyaddition of a diamine compound and a diisocyanate compound, or a deammonification reaction of a diamine compound and urea. As the diamine compound, the same compounds as the diamines exemplified in the polyamide can be used. As the diisocyanate compound,
The same compounds as the diisocyanates exemplified in the polyurethane can be used.

The starting materials such as the diamine compound and the diisocyanate compound used for the synthesis of the polyurea are each 1
The species may be used alone, or two or more species may be used depending on various purposes (for example, adjustment of glass transition temperature (Tg) of polymer, solubility, compatibility with dye, stability of dispersion). May be mixed at an arbitrary ratio.

--Polycarbonate-- The polycarbonate usable in the present invention can be basically obtained by reacting a diol compound with a phosgene or carbonate derivative (eg, an aromatic ester such as diphenyl carbonate). As the diol compound, the same compounds as the diols exemplified in the polyurethane can be used.

As the raw materials such as the diol compound used in the synthesis of the polycarbonate, one kind may be used alone, and various kinds (for example, adjustment of glass transition temperature (Tg) of polymer, solubility, Depending on the compatibility with the dye and the stability of the dispersion), two or more of them can be mixed and used in an arbitrary ratio.

In the present invention, among the above-mentioned polymers, each polymer having a dissociable group is preferable, and each polymer having at least one of a carboxyl group and a sulfonic acid group is more preferable as the dissociable group. Each polymer having a carboxyl group as a group is particularly preferred.

The dissociable group can be introduced into each of the polymers by various methods. For example, when a polyurethane is used as the polymer of the present invention, a diol having a dissociable group can be used as a substituent from the polymer main chain during the synthesis of the polyurethane. When a polyester is used as the polymer of the present invention, it can be introduced by leaving the unreacted terminal of the dicarboxylic acid at the terminal of the polyester. Furthermore, after producing each of the above polymers by polymerization, a dissociable group may be introduced by a reaction such as an acid anhydride (for example, maleic anhydride) to a reactive group such as an —OH group or an amino group remaining at the terminal. it can.

The content of the dissociable group in the polymer of the present invention is preferably 0.1 to 3 mmol / g, and 0.2 to 2 mmol / g.
mmol / g is more preferred. Incidentally, if the content of the dissociable group is too small, the self-emulsifiability of the polymer becomes small,
If the amount is too large, the water solubility tends to be high and the dye tends to be unsuitable for dispersion.

Among the polymers of the present invention, polyurethanes and polyesters are preferred from the viewpoint of easy introduction of a dissociative group capable of improving the compatibility between the polymer and the oil-soluble dye and the dispersion stability of the polymer. That is, as the polymer of the present invention, polyurethane and polyester having a dissociable group are preferable, and polyurethane and polyester having at least one of a carboxyl group and a sulfonic acid group as the dissociable group are particularly preferable.

Regarding the synthesis of the polymer of the present invention, “Polymer Experiments (Vol. 5) Polycondensation and Polyaddition (Edited by Shu Kamihara, published by Kyoritsu Shuppan Co., Ltd. (1980))”, “Polyester Resin Handbook (Takiyama)” Eiichiro, published by Nikkan Kogyo Shimbun (1988)), "Polyurethane Resin Handbook (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun (1987))",
"Experimental method for polymer synthesis (Takashi Otsu and Masayoshi Kinoshita, published by Kagaku Doujinshi (1972))", Tokubo Sho 31-1141
Nos. 37-7641, 39-5989, 40
-27349, 42-5118, 42-241
No. 94, No. 45-10957, No. 48-25435
And JP-A-49-36942, JP-A-52-81344, JP-A-56-88454, and JP-A-6-340835.

Specific examples of the polymer of the present invention (P-1 to P-3)
8) is exemplified below using the names of the raw material monomers (however, P-23 and P-34 and thereafter are exemplified in the form of a polymer), but the polymer used in the present invention is limited to the following specific examples. Not something. In addition, all the acidic groups in each of the following polymers are represented by a non-dissociated type. Regarding polymers produced by a condensation reaction such as polyester and polyamide, the constituent components are irrespective of the raw materials,
All are represented by dicarboxylic acids, diols, diamines, hydroxycarboxylic acids, aminocarboxylic acids and the like. The ratio in parentheses means the molar percentage ratio of each component.

P-1) Toluene diisocyanate / ethylene glycol / 1,4-butanediol (50/1
5/35) P-2) 4,4'-diphenylmethane diisocyanate / 1,3-propanediol / polypropylene glycol (Mw = 1000) (50/45/5) P-3) Toluene diisocyanate / hexamethylene diisocyanate / ethylene glycol / Polyethylene glycol (Mw = 600) / 1,4-butanediol (40/10/20/10/20) P-4) 1,5-naphthylene diisocyanate / hexamethylene diisocyanate / diethylene glycol /
1,6-hexanediol (25/25/35/15)

P-5) 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / tetraethylene glycol / ethylene glycol / 2,2
-Bis (hydroxymethyl) propionic acid (40/10
/ 20/20/10) P-6) 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / butanediol / polyethylene glycol (Mw = 400) / 2,2-
Bis (hydroxymethyl) propionic acid (40/10 /
20/10/20) P-7) 1,5-Naphthylene diisocyanate / butanediol / 4,4'-dihydroxydiphenyl-2,2'-propane / polypropylene glycol (Mw
= 400) / 2,2-bis (hydroxymethyl) propionic acid (50/20/5/10/15) P-8) 1,5-naphthylene diisocyanate / hexamethylene diisocyanate / 2,2-bis (hydroxymethyl ) Butanoic acid / polybutylene oxide (Mw = 5
00) (35/15/25/25) P-9) Isophorone diisocyanate / diethylene glycol / neopentyl glycol / 2,2-bis (hydroxymethyl) propionic acid (50/20/20/1)
0) P-10) Toluene diisocyanate / 2,2-bis (hydroxymethyl) butanoic acid / polyethylene glycol (Mw = 1000) / cyclohexanedimethanol (50/10/10/30) P-11) Diphenylmethane diisocyanate / hexamethylene Diisocyanate / tetraethylene glycol / butanediol / 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid (40/10
/ 10/33/7) P-12) diphenylmethane diisocyanate / hexamethylene diisocyanate / butanediol / ethylene glycol / 2,2-bis (hydroxymethyl) butanoic acid / 2,4-di (2-hydroxy) ethyloxycarbonylbenzene Sulfonic acid (40/10/20/15 /
10/5)

P-13) Terephthalic acid / isophthalic acid / cyclohexanedimethanol / 1,4-butanediol / ethylene glycol (25/25/25/15/1)
0) P-14) Terephthalic acid / isophthalic acid / 4,4'-
Dihydroxydiphenyl-2,2-propane / tetraethylene glycol / ethylene glycol (30/20
/ 20/15/15) P-15) Terephthalic acid / isophthalic acid / cyclohexanedimethanol / neopentyl glycol / diethylene glycol (20/30/25/15/10) P-16) Terephthalic acid / isophthalic acid / 4,4 '―
Benzenedimethanol / diethylene glycol / neopentyl glycol (25/25/25/15/10)

P-17) Terephthalic acid / isophthalic acid / 5-sulfoisophthalic acid / ethylene glycol / neopentyl glycol (24/24/2/25/25) P-18) Terephthalic acid / isophthalic acid / 5-sulfoisophthalate Acid / cyclohexanedimethanol / 1,4-
Butanediol / ethylene glycol (22/22/6
/ 25/15/10) P-19) isophthalic acid / 5-sulfoisophthalic acid /
Cyclohexanedimethanol / ethylene glycol (4
0/10/40/10) P-20) cyclohexanedicarboxylic acid / isophthalic acid / 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid / cyclohexanedimethanol / ethylene glycol (30/20/5/25 / 20)

P-21) 11-aminoundecanoic acid (100) P-22) 12-Aminododecanoic acid (100) P-23) Reaction product of poly (12-aminododecanoic acid) and maleic anhydride P-24 ) 11-aminoundecanoic acid / 7-aminoheptanoic acid (50/50) P-25) hexamethylenediamine / adipic acid (5
0/50) P-26) Tetramethylenediamine / adipic acid (5
0/50) P-27) Hexamethylenediamine / sebacic acid (5
0/50) P-28) N, N'-dimethylethylenediamine / adipic acid / cyclohexanedicarboxylic acid (50/20 /
30)

P-29) Toluene diisocyanate /
4,4'-diphenylmethane diisocyanate / hexamethylenediamine (30/20/50) P-30) Nonamethylenediamine / urea P-31) Hexamethylenediamine / nonamethylenediamine / urea (25/25/50) P-32 ) Toluene diisocyanate / hexamethylenediamine / 2,2-bis (hydroxymethyl) propionic acid (50/40/10) P-33) 11-aminoundecanoic acid / hexamethylenediamine / urea (33/33/33)

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The molecular weight (Mw) of the polymer of the present invention is usually preferably from 1,000 to 200,000,
More preferably, it is from 0.000 to 50,000. Molecular weight 1
If it is less than 000, it tends to be difficult to obtain a stable colored fine particle dispersion, and if it is more than 200,000, the solubility in an organic solvent becomes poor, or the viscosity of the organic solvent solution increases, making it difficult to disperse. Tend to be.

—Preparation of Colored Particle Dispersion— The colored particle dispersion of the present invention comprises the oil-soluble dye and the polymer of the present invention dispersed in an aqueous medium (a liquid containing at least water) in the form of colored particles. It can be manufactured by doing. Specifically, for example, a method in which a latex of the polymer is prepared in advance and the latex is impregnated with the oil-soluble dye, or a coemulsification dispersion method is used. Among these, the above-mentioned co-emulsification dispersion method is preferable. As the co-emulsification dispersion method, water is added to an organic solvent phase containing the polymer of the present invention and the oil-soluble dye, and the organic solvent phase is added to water. , The organic solvent is preferably emulsified to form fine particles.

First, a method of preparing the polymer latex in advance and impregnating the polymer latex with the oil-soluble dye will be described. The latex means a polymer in which a water-insoluble polymer is dispersed as fine particles in an aqueous medium. As the dispersion state, the polymer of the present invention is emulsified in the aqueous medium, micelle-dispersed, or has a partially hydrophilic structure in the polymer molecule, the molecular chain itself is a molecule Any of those dispersed in a state may be used.

A first example of this method includes a first step of preparing a polymer latex, a second step of preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, and a step of preparing the dye solution and the polymer. Mixing the latex to prepare a colored fine particle dispersion. A second example of this method is a first step of preparing a polymer latex, and preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, and mixing the dye solution with a liquid containing at least water. A second step of preparing a dye fine particle dispersion; and a third step of mixing the polymer latex and the dye fine particle dispersion to prepare a colored fine particle dispersion. As a third example of this method, there is a method described in JP-A-55-139471.

Next, the co-emulsification method will be described. A first example of this method is a first step of preparing a solution in which the oil-soluble dye and the polymer of the present invention are dissolved in an organic solvent, and a solution containing at least water and the solution prepared in the first step. Mixing to prepare a colored fine particle dispersion. A second example of this method includes a first step of preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, and a second step of preparing a polymer solution in which the polymer of the present invention is dissolved in an organic solvent. A third step of preparing a colored fine particle dispersion by mixing the dye solution and the polymer solution with a liquid containing at least water. A third example of this method is a first step of preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, and mixing the dye solution and a liquid containing at least water to prepare a dye fine particle dispersion. And preparing a polymer solution in which the polymer of the present invention is dissolved in an organic solvent,
A second step of mixing the polymer solution and a liquid containing at least water to prepare a polymer fine particle dispersion, and mixing the dye fine particle dispersion and the polymer fine particle dispersion to prepare a colored fine particle dispersion. And a third step.

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

In the colored fine particle dispersion, the amount of the polymer of the present invention is preferably from 10 to 1,000 parts by mass, more preferably from 50 to 1000 parts by mass, per 100 parts by mass of the oil-soluble dye.
600 parts by mass is more preferred. When the use ratio of the polymer is less than 10 parts by mass, fine and stable dispersion of fine particles tends to be difficult, and when it exceeds 1000 parts by mass,
The proportion of the oil-soluble dye in the colored fine particle dispersion is reduced,
When the colored fine particle dispersion is used as an aqueous ink, there is a tendency that there is no room for formulation design.

—Organic Solvent— The organic solvent used for producing the colored fine particle dispersion is not particularly limited, and may be appropriately selected based on the solubility of the oil-soluble dye or the polymer of the present invention. it can.
For example, ketone solvents such as acetone, methyl ethyl ketone and diethyl ketone, methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, te
alcohol solvents such as rt-butanol; chlorine solvents such as chloroform and methylene chloride; aromatic solvents such as benzene and toluene; ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate; diethyl ether; tetrahydrofuran; Ether solvents, ethylene glycol monomethyl ether, glycol ether solvents such as ethylene glycol dimethyl ether,
And the like. Incidentally, one kind of the organic solvent may be used alone, or two or more kinds may be used in combination. A mixed solvent with water may be used depending on the solubility of the dye or the polymer.

The amount of the organic solvent used is not particularly limited as long as the effect of the present invention is not impaired.
10 to 2000 based on 100 parts by mass of the polymer of the present invention
A mass part is preferable, and 100-1000 mass parts is more preferable. When the use amount of the organic solvent is less than 10 parts by mass, the fine and stable dispersion of the colored fine particles tends to be difficult due to the high viscosity of the organic solvent phase, and when the amount exceeds 2000 parts by mass, the organic solvent is removed. There is a tendency that the steps of desolvation and concentration are indispensable and complicated, and that there is no room for blending conditions.

When the solubility of the organic solvent in water is 10% or less, or when the vapor pressure of the organic solvent is higher than water, the organic solvent is removed from the viewpoint of the stability of the colored fine particle dispersion. Preferably. The removal of the organic solvent can be performed at 10 to 100 ° C. under normal pressure or reduced pressure, and is preferably performed at 40 to 100 ° C. under normal pressure or 10 to 50 ° C. under reduced pressure.

—Additives— The colored fine particle dispersion may contain additives appropriately selected according to the purpose within a range that does not impair the effects of the present invention. Examples of the additive include a neutralizer, a dispersant, and a dispersion stabilizer.

When the polymer of the present invention has the unneutralized dissociable group, the neutralizing agent is suitable in terms of pH adjustment of the colored fine particle dispersion, self-emulsification control, and dispersion stability. Can be used for The neutralizing agent may be added at the time of taking out as a polymer before preparing a dispersion, or may be added in any process of performing dispersion or after completion of dispersion. Examples of the neutralizing agent include organic bases and inorganic alkalis for anionic dissociative groups, and organic acids and inorganic acids for cationic dissociative groups.

Among the neutralizing agents for anionic dissociable groups, examples of the organic base include triethanolamine, diethanolamine, N-methyldiethanolamine, dimethylethanolamine and the like. Examples of the inorganic alkali include hydroxides of alkali metals (eg, sodium hydroxide, lithium hydroxide, potassium hydroxide, etc.), carbonates (eg, sodium carbonate, sodium hydrogen carbonate, etc.), and ammonia. Among the neutralizing agents for cationic dissociable groups, examples of the organic acid include acetic acid, propionic acid, trifluoroacetic acid, and alkylsulfonic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid. From the viewpoint of improving the dispersion stability of the colored 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 to 10.0. More preferred.

The dispersant and the dispersion stabilizer may be added to any of a polymer latex, a polymer solution, a dye solution, a solution containing at least water, and the like. Is preferably added to any of a polymer solution, a dye solution, and a solution containing water in the step prior to the preparation of

Examples of the dispersant and dispersion stabilizer include various cationic, anionic and nonionic surfactants, water-soluble or water-dispersible low molecular weight compounds and oligomers. The addition amount of the dispersant and the dispersion stabilizer is 0 to the total amount of the oil-soluble dye and the polymer of the present invention.
It is 100% by mass, preferably 0 to 20% by mass.

In the colored fine particle dispersion, the colored fine particles are preferably contained in an amount of 1 to 45% by mass,
More preferably, the content is 30% by mass. The content can be appropriately adjusted by dilution, evaporation, ultrafiltration and the like.

The particle diameter of the colored fine particles is 1 to 50.
0 nm is preferable, and 3 to 300 nm is more preferable.
~ 200 nm is particularly preferred. The particle size distribution is not particularly limited, and may have a broad particle size distribution or a monodispersed particle size distribution. The particle size, the particle size distribution,
It can also be adjusted by means such as centrifugation and filtration.

The colored fine particle dispersion of the present invention has a maximum absorption wavelength (λmax (nm)) of 580 to 700 n.
m, more preferably 590-690 nm, and particularly preferably 600-650 nm. When the maximum absorption wavelength (λmax (nm)) is within the preferred numerical range, color reproducibility is excellent. When the maximum absorption wavelength (λmax (nm)) is within the preferred numerical range, and particularly within the preferred numerical range, color reproducibility is remarkable. It is advantageous in that it is excellent.

The colored fine particle dispersion of the present invention may have an absorbance at a wavelength (λmax−100 (nm)) of 0.35 or less, where the absorbance at the maximum absorption wavelength (λmax (nm)) is 1. Preferably, it is 0.25 or less, more preferably 0.15 or less. When the absorbance at the wavelength (λmax-100 (nm)) is within the above preferable numerical range, the color reproducibility is excellent, and when the absorbance is within the above more preferable numerical range and the above particularly preferable numerical range, the color reproducibility is excellent. This is advantageous in that it is remarkably excellent.

-Use of Colored Fine Particle Dispersion- The colored fine particle dispersion of the present invention can be used in various fields, and is suitable for aqueous inks for writing, aqueous printing inks, information recording inks, and the like. It can be particularly preferably used for the ink jet recording ink of the present invention.

When the colored fine particle dispersion is used as an ink such as an aqueous ink for writing, an aqueous printing ink, an information recording ink, etc., the recording material of the ink may be plain paper, resin-coated paper, ink jet paper, film And electrophotographic paper, cloth, glass, metal, ceramics and the like.

(Ink for Inkjet Recording) The ink for inkjet recording of the present invention contains the colored fine particle dispersion of the present invention, and further contains other components appropriately selected as necessary. -Other components- The other components are contained within a range that does not impair the effects of the present invention. As the other components, for example, an anti-drying agent, a penetration enhancer, an ultraviolet absorber, an antioxidant,
Known additives such as a viscosity adjuster, a surface tension adjuster, a dispersant, a dispersion stabilizer, a fungicide, a rust preventive, a pH adjuster, an antifoaming agent, a chelating agent and the like can be mentioned.

The above-mentioned anti-drying agent is suitably used for the purpose of preventing clogging due to drying operation of the ink-jet ink at the ink ejection port of a nozzle used in the ink-jet recording system. As the drying inhibitor, a water-soluble organic solvent having a lower vapor pressure than water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, and 2-methyl-1,3. −
Propanediol, 1,2,6-hexanetriol,
Acetylene glycol derivatives, glycerin, polyhydric alcohols represented by trimethylolpropane, etc., ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether,
Lower alkyl ethers of polyhydric alcohols such as triethylene glycol monoethyl (or butyl) ether;
-Pyrrolidone, N-methyl-2-pyrrolidone, 1,3-
Heterocycles such as dimethyl-2-imidazolidinone and N-ethylmorpholine, sulfolane, dimethyl sulfoxide,
Examples thereof include sulfur-containing compounds such as 3-sulfolene, polyfunctional compounds such as diacetone alcohol and diethanolamine, and urea derivatives. Among these, polyhydric alcohols such as glycerin and diethylene glycol are more preferable. These drying inhibitors may be used alone or in combination of two or more.

The content of the anti-drying agent in the ink for ink jet recording is preferably from 10 to 50% by mass.

The penetration enhancer is used for better penetration of the ink for ink jet recording into paper. Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, and 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and a nonionic surfactant. Can be The permeation enhancer is contained within a range that does not cause bleeding of print, paper dropout (print-through), and the like, and usually exhibits a sufficient effect when contained in the ink for inkjet recording at about 5 to 30% by mass.

The ultraviolet absorber is used for the purpose of improving the storability of an image. As the ultraviolet absorber,
For example, JP-A-58-185677 and JP-A-61-19
0537, JP-A-2-782, 5-19
Benzotriazole compounds described in JP-A Nos. 7075, 9-34057 and the like;
JP, JP-A-5-194483, U.S. Pat.
Benzophenone compounds described in JP-A-214463, JP-B-48-30492, JP-B-56-2114.
No. 1, cinnamic acid-based compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, The triazine compounds described in JP-T-8-501291 and the like, Research Disclosure No. Compounds described in No. 24239 and compounds emitting fluorescent light by absorbing ultraviolet rays, represented by stilbene-based and benzoxazole-based compounds, so-called fluorescent whitening agents, and the like.

The antioxidant is used for the purpose of improving the storability of an image. As the antioxidant, for example, various organic and metal complex antifading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles, and the like. Examples of the metal complex anti-fading agent include a nickel complex and a zinc complex. 17643 No.
Nos. VII to VII, VII. 15162; 1
No. 8716, left column, page 650; 527 of 36544
Page, the same No. No. 307105, page 872; 151
Compounds described in the patent cited in No.
Compounds included in the general formulas and examples of the typical compounds described on pages 127 to 137 of JP-A-215272 can be used.

Examples of the fungicide include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. Can be These are contained in the ink
It is preferred to use 1.00% by mass.

Examples of the surface tension modifier include nonionic, cationic and anionic surfactants.

The surface tension of the ink jet recording ink of the present invention is preferably from 25 to 70 mPa · s,
5 to 60 mPa · s is more preferable. Further, the viscosity of the inkjet recording ink of the present invention is 30 mPa
S or less, more preferably 20 mPa · s or less.

As the defoaming agent, a fluorine-based or silicone-based compound, a chelating agent represented by EDTA, or the like can be used as required.

The ink-jet recording ink of the present invention comprises:
Printing or the like can be suitably performed on a known recording material. The recording agent is not particularly limited, but is preferably an inkjet paper. Examples of the inkjet paper include, for example, JP-A-8-169172 and JP-A-8-27693.
Gazette, JP-A-2-276670 and JP-A-7-27678
9, JP-A-9-323475, JP-A-62-2
No. 38783, JP-A-10-153899,
JP-A-10-217473, JP-A-10-235995, JP-A-10-217597, and JP-A-10-3379
No. 47 publication and the like.

Further, in the present invention, the following recording paper and recording film are suitably used as the recording material in addition to the above-mentioned ink jet paper. The recording paper and the recording film are formed by laminating a support and an ink receiving layer, and if necessary, laminating other layers such as a back coat layer. Each layer including the ink receiving layer may be a single layer, or may be two or more layers.

As the support, LBKP, NBKP
Chemical pulp, GP, PGW, RMP, TMP, CT
Examples thereof include mechanical pulp such as MP, CMP, and CGP, and waste paper pulp such as DIP. In the pulp,
If necessary, conventionally known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers and the like may be added and mixed. The support can be manufactured by using various apparatuses such as a fourdrinier paper machine and a round paper machine. The support may be a synthetic paper, a plastic film sheet, or the like.

The thickness of the support is 10 to 250.
It is about μm, and the basis weight is preferably 10 to 250 g / m ² .

The support may be provided directly with the ink receiving layer and, if necessary, a back coat layer.
After providing a size press or an anchor coat layer with starch, polyvinyl alcohol, or the like, the ink receiving layer and the back coat layer may be provided. The support may be subjected to a flattening process using a calender such as a machine calender, a TG calender, and a soft calender.

Among the above supports, both surfaces are polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof).
More preferably, the paper and the plastic film laminated with each other are those in which a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine, neodymium oxide) is added to the polyolefin. preferable.

The ink receiving layer contains a pigment, an aqueous binder, a mordant, a waterproofing agent, a light fastness improving agent, a surfactant and other additives.

The pigment is preferably a white pigment.
Examples of white pigments include calcium carbonate, kaolin,
Talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide,
Examples thereof include inorganic white pigments such as zinc carbonate, and organic pigments such as styrene pigment, acrylic pigment, urea resin, and melamine resin. Among these, porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either silicic anhydride obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but hydrous silicic acid is particularly preferable.

Examples of the aqueous binder include water-soluble binders such as polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. And water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. These may be used alone or in combination of two or more. Among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are preferred from the viewpoints of adhesion to the pigment and peel resistance of the ink receiving layer.

The mordant is preferably immobilized, and for this purpose, a polymer mordant is preferred. Examples of the polymer mordant include JP-A-48-28325.
No., 54-74430, 54-124726,
Nos. 55-22766, 55-142339, 6
0-23850, 60-23851, 60-2
No. 3852, No. 60-23853, No. 60-5783
No. 6, No. 60-60643, No. 60-118834
No. 60-122940, No. 60-122941
No. 60-122942, No. 60-235134
JP-A-1-161236, U.S. Pat.
No. 84430, No. 2548564, No. 3148061
Nos. 3309690, 4115124, 41
24386, 4193800, 4273753
Nos. 4,282,305 and 4,450,224. Among them, the polymer mordants described on pages 212 to 215 of JP-A-1-161236 are preferred. Use of the polymer mordant described in the publication is preferable in that an image with excellent image quality is obtained and the light fastness of the image is improved.

The water-proofing agent is used for the purpose of making an image water-resistant. As the water-proofing agent, a cationic resin is preferable. Examples of the cationic resin include polyamide polyamine epichlorohydrin, polyethylene imine,
Examples thereof include polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferred. The content of the cationic resin is preferably from 1 to 15% by mass, more preferably from 3 to 10% by mass, based on the total solid content of the ink receiving layer.

Examples of the light resistance improver include zinc sulfate, zinc oxide, hinderamine antioxidants, and benzophenone and benzotriazole ultraviolet absorbers. Among these, zinc sulfate is particularly preferred.

The surfactant functions as a coating aid, a release improver, a slipperiness improver, or an antistatic agent. Examples of the surfactant include JP-A-62-17346.
No. 3, No. 62-183457. Note that an organic fluoro compound may be used instead of the surfactant. The organic fluoro compound is preferably hydrophobic. The organic fluoro compound includes, for example, a fluorine-based surfactant, an oily fluorine-based compound (eg, fluorine oil) and a solid fluorine compound resin (eg, tetrafluoroethylene resin), and Japanese Patent Publication No. 57-9053. (Columns 8 to 17), JP-A-61-1
JP-A Nos. 20994 and 62-135826.

Examples of the other additives include a pigment dispersant, a thickener, a defoamer, a dye, a fluorescent brightener, a preservative,
pH adjusters, matting agents, hardeners and the like can be mentioned.

The back coat layer contains a white pigment, an aqueous binder, and other components.

Examples of the white pigment include light calcium carbonate, heavy calcium carbonate, kaolin, talc,
Calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo boehmite, hydroxylated White inorganic pigments such as aluminum, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, and magnesium hydroxide; organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsules, urea resin, and melamine resin. Can be

As the aqueous binder, styrene /
Water-soluble polymers such as maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, and styrene Water-dispersible polymers such as butadiene latex and acrylic emulsion are exemplified.

Examples of the other components include an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, and a waterproofing agent.

Incidentally, a polymer latex may be added to each layer of the recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stability, curl prevention, adhesion prevention, and film crack prevention. As polymer latex, JP-A-62
-245258, 62-136648, 62
And those described in JP-A-110066. When a polymer latex having a low glass transition temperature (40 ° C. or less) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. When a polymer latex having a high glass transition temperature is added to the back layer, curling can be prevented.

(Ink Jet Recording Method) In the ink jet recording method of the present invention, energy is supplied to the ink for ink jet recording of the present invention to discharge droplets of the ink onto an image receiving material, thereby recording an image on the image receiving material. It is characterized by the following. Any inkjet recording method can be applied to the inkjet recording method of the present invention,
For example, a charge control method for discharging ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) using the oscillating pressure of a piezo element, and a radiation pressure by changing an electric signal into an acoustic beam and irradiating the ink. An acoustic ink jet method in which ink is ejected by utilizing the ink, a thermal ink jet (bubble jet) method in which bubbles are formed by heating ink, and the generated pressure is used, and the like can be used.

The ink jet recording method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving the image quality by using a plurality of inks having substantially the same hue and different densities, and the like. A system using colorless and transparent ink is included.

[0163]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples. In the following, “parts” and “%” represent “parts by mass” and “% by mass” unless otherwise specified. <Synthesis Example 1 (Synthesis of oil-soluble dye D-2)> Based on the following reaction formula, Exemplified Compound (D-2) was synthesized. In the following reaction formula, the synthesis of the first compound (a) (the compound on the left side of the arrow in the above reaction formula), which is an intermediate,
It was synthesized according to the method described in JP-A-10-62926.

[0164]

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The first compound (a) was placed in a three-necked flask.
64.5 g, second compound (b) (52.4 g of compound above arrow in the above reaction formula), potassium carbonate 8
2.8 g, ethyl acetate (300 ml) and N, N-dimethylacetamide (100 ml) were added, and the mixture was stirred at room temperature for 5 minutes.
An aqueous solution in which 7.4 g was dissolved in 60 ml of water was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and then extracted by adding 500 ml of ethyl acetate and 500 ml of water, and the obtained ethyl acetate layer was washed with 700 ml of water and 2 ml of water.
The mixture was washed 5 times with a mixed solvent consisting of 00 ml of saturated saline. The ethyl acetate layer thus obtained was dried over anhydrous sodium sulfate and concentrated on a rotary evaporator.
The obtained residue was purified by silica gel column chromatography to give 69.0 g of the desired exemplified compound (D-2).
Was obtained (88% yield).

<Synthesis Example 2 (Synthesis of Oil-soluble Dye D-25)
> Based on the following reaction formula, the exemplary compound (D-25) was synthesized. In the following reaction formula, the synthesis of the first compound (c) as an intermediate (the compound on the left side of the arrow in the above reaction formula) was performed according to the method of Synthesis Example 1 described in JP-A-5-177959. And synthesized.

[0167]

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In a three-necked flask, put the first compound (c)
50.8 g, the second compound (d) (the upper compound indicated by the arrow in the above reaction formula) 40.4 g, potassium carbonate 8
2.8 g, 300 ml of ethyl acetate and 100 ml of N, N-dimethylacetamide were added, and the mixture was stirred at room temperature for 5 minutes.
00 ml was added and the mixture was further stirred for 5 minutes. An aqueous solution obtained by dissolving 27.4 g of ammonium peroxodisulfate in 60 ml of water was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and then extracted by adding 500 ml of ethyl acetate and 500 ml of water. The obtained ethyl acetate layer was washed five times with a mixed solvent consisting of 700 ml of water and 200 ml of saturated saline. did. The ethyl acetate layer thus obtained was dried over anhydrous sodium sulfate, concentrated by a rotary evaporator, and the obtained residue was purified by silica gel column chromatography to obtain the desired exemplary compound (D-25). 8 g was obtained (yield 90%).

<Synthesis Example 3 (Synthesis of Polymer P-5 of the Present Invention)> In a 500 ml three-necked flask equipped with a stirrer and a reflux condenser, 39.1 g of 4,4'-diphenylmethane diisocyanate and hexamethylene diisocyanate were placed. 6.6 g, tetraethylene glycol 1
5.2 g, 4.9 g of ethylene glycol, 5.3 g of 2,2-bis (hydroxymethyl) propionic acid, and 150 ml of N, N-dimethylacetamide were added and dissolved at room temperature with stirring. Here, 0.2 g of di-n-butyltin dilaurate was added, and the mixture was heated to 90 ° C.
After heating and stirring for 6 hours, the mixture was diluted with 50 ml of N, N-dimethylacetamide, cooled to room temperature, and 2.2 g of sodium methoxide was added to 100 ml of methanol.
l was added. The obtained polymer was precipitated by pouring into 5 liters of ethyl acetate / hexane (80/20 by volume), filtered and dried to obtain the title polymer P.
69.5 g of -5 was obtained. The obtained polymer had a dissociable group content of 0.58 mmol / g and a weight average molecular weight of 9,800.

<Synthesis Example 4 (Synthesis of Polymer P-17 of the Present Invention)> Dimethyl terephthalate was placed in a 300 ml three-necked flask equipped with a stirrer and a distillation tube.
6.5 g, dimethyl isophthalate 46.5 g, sodium 5-dimethyl sulfoisophthalate 6.0 g, ethylene glycol 30 g, neopentyl glycol 2
6.0 g, and calcium acetate 0.0 as a condensation catalyst
5 g and 0.05 g of antimony (III) oxide were added, and the mixture was heated and stirred at 150 ° C. for 30 minutes and further at 190 ° C. for 1 hour while distilling off methanol and ethylene glycol generated under a nitrogen stream. Next, the temperature was lowered to about 150 ° C., and the degree of decompression of the reaction system was gradually increased by a pump under stirring, and
The temperature was raised while further distilling off ethylene glycol in the range of 0 to 40 Pa, and the reaction was further carried out at 250 ° C. for 2.5 hours. The reaction product was taken out as it was and cooled to obtain 120 g of the title polymer P-17. The resulting polymer had a dissociable group content of 0.37 mmol / g and a weight average molecular weight of 5,600.

<Production Example 1 (Colored fine particle dispersion (A-1))
Preparation> 20 parts of methyl ethyl ketone, 4 parts of isopropyl alcohol, 4.8 g of the polymer (P-5; sodium salt), 1.2 g of the oil-soluble dye (D-2)
After the mixture was heated to 75 ° C., 60 parts of water was added dropwise with stirring. This solution is concentrated under reduced pressure at 40 ° C.
A colored fine particle dispersion having a solid content of 20% was prepared. The particle diameter of the colored fine particles in the colored fine particle dispersion is 3 by volume average diameter.
It was 9 nm. Hereinafter, this is referred to as a colored fine particle dispersion (A-
Abbreviated as 1).

<Production Example 2 (Colored fine particle dispersion (A-2))
Preparation> A mixture of 10 parts of methyl ethyl ketone, 5 parts of isopropyl alcohol, 3 g of the polymer (P-5; sodium salt) and 1.2 g of the oil-soluble dye (D-25) was heated to 60 ° C. 1 part of a 25% aqueous solution of an activator (manufactured by Kao Corporation; Emal 20C) and 50 parts of water at 60 ° C. are added, and the mixture is treated with a homogenizer for 500 minutes per minute.
The mixture was stirred at a high speed of 0 rotation for 3 minutes. The obtained liquid was concentrated at 40 ° C. under reduced pressure to prepare a colored fine particle dispersion having a solid content of 20%. The particle diameter of the colored fine particles in the colored fine particle dispersion was 55 nm in volume average diameter. Hereinafter, this is referred to as colored fine particle dispersion (A-2).

<Production Example 3 (Colored fine particle dispersion (A-4))
Preparation> 6 parts of tetrahydrofuran, 14 parts of isopropyl alcohol, 4.8 g of the polymer (P-17; sodium salt), 1.2 parts of the oil-soluble dye (D-25) 1.2
g of the mixed solution was heated to 65 ° C., and then, while stirring,
60 parts of water was added dropwise over 30 minutes. This solution is reduced under reduced pressure to 40
The mixture was concentrated at 20 ° C. to prepare a colored fine particle dispersion having a solid content of 20%. The particle diameter of the colored fine particles in the colored fine particle dispersion was 33 nm in volume average diameter. Hereinafter, this is abbreviated as colored fine particle dispersion (A-4).

<Production Examples 4 to 8> Using the same means as described above, the types of the polymer and the oil-soluble dye were changed as shown in Table 1 below, and the colored fine particle dispersions (A-3), (A-3) −
5) to (A-8) were prepared.

<Preparation Example 9 (Preparation of comparative colored fine particle dispersion (B-1))> In Preparation Example 3, except that the oil-soluble dye (D-25) was replaced by the following compound (H-1) Prepared a dispersion of colored fine particles having a solid content of 20% in the same manner as in Production Example 3. The particle diameter of the colored fine particle dispersion was 52 nm in volume average diameter. Abbreviated as (B-1).

[0176]

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Example 1 62 parts of the colored fine particle dispersion (A-1) prepared in Production Example 1 were mixed with 10 parts of diethylene glycol, 8 parts of glycerin, 8 parts of triethylene glycol monobutyl ether, and 25% of a surfactant. An aqueous ink jet recording ink was prepared by mixing 4 parts of an aqueous solution (manufactured by Kao Corporation; Emar 20C) and 8 parts of ion-exchanged water and filtering through a 0.2 μm filter.

(Examples 2 to 8) In Example 1,
Instead of the colored fine particle dispersion (A-1), the colored fine particle dispersions (A-2) to (A-8) were added so that the amount of the oil-soluble dye became constant, and 10 parts of diethylene glycol and 8 parts of glycerin were added. 8 parts of triethylene glycol monobutyl ether and 4 parts of a 25% aqueous solution of a surfactant (manufactured by Kao Corporation; Emar 20C) (in the case where a surfactant was used in advance when the paint was dispersed, the total amount of the surfactant was (The amount was adjusted so as to become the same amount), and ion-exchanged water was added so that the total amount became 100 parts. The mixture was further filtered through a 0.2 μm filter to prepare aqueous ink jet recording inks.

Comparative Example 1 The procedure of Example 1 was repeated, except that the colored fine particle dispersion (A-1) was replaced with the colored fine particle dispersion (B-1) prepared in Production Example 8. An ink-jet ink was prepared as in Example 1.

(Comparative Example 2) Comparative dye (H-2) 4 shown below
In parts, diethylene glycol 10 parts, glycerin 8
Part, tetraethylene glycol monobutyl ether 1
0 parts, 1 part of diethanolamine, and ion-exchanged water
67 parts were mixed and filtered through a 0.2 μm filter to prepare an inkjet recording ink.

[0181]

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(Image Recording and Evaluation) The ink jet recording inks of the above Examples and Comparative Examples were evaluated as follows. The results are shown in Table 1. In Table 1, "absorption of aqueous dispersion" means evaluation of the spectral absorption characteristics of the ink for inkjet recording. The “color tone”, “paper dependence”, “water resistance” and “lightfastness” are defined as follows. Each of the ink jet recording inks is coated on an inkjet printer (manufactured by EPSON Corporation; PM-700C; photo glossy paper). The evaluation was performed after an image was recorded on a photo film (manufactured by Photo Film Co., Ltd .; inkjet paper, photo grade).

<Spectral Absorption Characteristics> Each of the ink jet recording inks was diluted with ion-exchanged water so that the absorbance became 0.8 to 1.2, the visible absorption spectrum was measured, and the maximum absorption wavelength (λmax (nm) Assuming that the absorbance in ()) was 1, the absorbance at a wavelength (λmax-100 (nm)) was measured.

<Color Tone> The recorded image was visually checked for A
(Good) and B (Bad) were evaluated in two stages. <Paper Dependency> The color tone of the image formed on the photo glossy paper and the image formed separately on the plain paper for PPC are compared, and when the difference between the two images is small, A (good) is determined. Was evaluated as B (defective) in two steps. <Water resistance> The photo glossy paper on which the image was formed was dried for 1 hour at room temperature, immersed in water for 30 seconds, allowed to dry naturally at room temperature, and observed for bleeding. A indicates no bleeding, B indicates slight bleeding, and C indicates a large amount of bleeding.
The evaluation was made in three steps. <Light resistance> Xenon light (85,000 lux) was irradiated on the photo glossy paper on which the image was formed using a weather meter (Atlas CI65) for 3 days, and the image density before and after the xenon irradiation was measured using a reflection densitometer (X). -Rite310TR) and evaluated as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0.
A indicates that the dye remaining ratio is 70% or more at any concentration.
B was evaluated when one or two points were less than 70%, and C when less than 70% at all concentrations.

[0185]

[Table 1]

As is evident from the results shown in Table 1, the ink jet recording inks of the examples were excellent in color development and color tone, did not depend on paper, and were excellent in water resistance and light resistance.

[0187]

According to the present invention, the above-mentioned conventional problems can be solved, the dispersion stability of the colored fine particles is excellent, the paper is not dependent on the paper, and the coloring property when printing on an arbitrarily selected paper is achieved. -It is possible to provide a colored fine particle dispersion which is excellent in color tone (particularly cyan color reproduction), excellent in water fastness and light fastness, and suitable for aqueous ink for writing, aqueous printing ink, information recording ink and the like. Also, according to the present invention, thermal,
Suitable for piezoelectric, electric field or acoustic ink jet system, when printing using nozzles etc., without clogging at the nozzle tip, without paper dependence, when printing on arbitrarily selected paper The present invention can provide an ink jet recording ink and an ink jet recording method capable of forming an image having excellent color developability and color tone (especially, color reproducibility of cyan), and also having excellent water fastness and light fastness.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Takahiro Ishizuka 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film F-term (reference) 2C056 EA13 ED07 FC02 2H086 BA02 BA56 BA59 BA60 4J039 AE04 AE06 AE08 BC03 BC52 BC65 BC71 BC72 BC73 BC74 BC75 BC77 BC78 BC79 BD02 BE02 BE07 BE12 CA05 DA02 EA29 EA35 EA38 EA41 EA42 EA44 GA24

Claims (9)

[Claims] 1. Polyurethane, polyester, polyamide
, Polyurea and polycarbonate
At least one kind of polymer is represented by the following general formulas (I), (II),
Oil-soluble dye represented by any of (III) and (IV)
Characterized in that it contains colored fine particles containing
Particle dispersion. Embedded image(In the general formulas (I), (II), (III) and (IV), R¹,
R^Two, R^ThreeAnd R^FourAre each independently a hydrogen atom or a nonmetal
X is -OH or -NR ^FiveR⁶Represents
Then R^FiveAnd R⁶Are each independently a hydrogen atom, an alkyl group,
A reel group or a heterocyclic group;⁷, R⁸And R⁹
Each independently represents a hydrogen atom or a nonmetallic atomic group.
R¹And R^Two, R^TwoAnd R^Five, R^FiveAnd R⁶, R⁶And R^Three, And R^ThreeWhen
R^FourAt least one of which forms a ring structure with each other
May be, R⁷And R⁸Are linked together to form a ring structure
May be formed. ) 2. In the general formulas (I), (II), (III) and (IV), R ⁷ is an acyl group, an acyloxy group, a carbamoyl group having a Hammett substituent constant σ _p value of 0.30 or more; Alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group,
Arylsulfonyl group, sulfamoyl group, halogenated alkyl group, halogenated alkoxy group, halogenated aryloxy group or halogenated alkylthio group, σ _p
The colored fine particle dispersion according to claim 1, wherein the colored fine particle dispersion represents an aryl group or a heterocyclic group substituted with two or more electron-withdrawing groups having a value of 0.15 or more. 3. The sum of Hammett substituent constants of R ⁷ and R ^{8 in} the general formulas (I), (II), (III) and (IV) is 0.70 or more. Item 3. The colored fine particle dispersion according to Item 1 or 2. 4. The method according to claim 1, wherein at least one polymer selected from polyurethane, polyester, polyamide, polyurea and polycarbonate is present in an amount of 0.01 to 3.0 mmol.
The colored fine particle dispersion according to any one of claims 1 to 3, which is a polymer having a dissociable group of / g. 5. The method according to claim 4, wherein the dissociable group is at least one of a carboxyl group and a sulfonic acid group.
3. The colored fine particle dispersion according to item 1. 6. Addition of water to an organic solvent phase containing at least one polymer selected from polyurethane, polyester, polyamide, polyurea and polycarbonate and an oil-soluble dye, and The colored fine particle dispersion according to any one of claims 1 to 5, wherein the dispersion is obtained by emulsifying the organic solvent phase by adding a solvent phase. 7. A maximum absorption wavelength (λmax (nm)) within a wavelength range of 580 to 700 nm, and when the absorbance at the maximum absorption wavelength (λmax (nm)) is 1, the wavelength (λmax−100 (nm) )) Is 0.
The colored fine particle dispersion according to any one of claims 1 to 6, wherein the dispersion is 35 or less. 8. An ink jet recording ink comprising the colored fine particle dispersion according to any one of claims 1 to 7. 9. An ink jet recording method comprising: applying energy to the ink jet recording ink according to claim 8 to discharge droplets of the ink onto an image receiving material, thereby recording an image on the image receiving material. .