JP2002020657A - Ink jet recording method, and manufacturing method of ink for thermal ink jet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet thermal recording method not suffering from deterioration of a heating unit or occurrence of clogging of a nozzle caused by an adhesion of an ink component to the surface of the heating unit element, scorching (kogation), deposition and the like, free from dependency on paper, excellent in color-developing properties when printed on an arbitrarily selected paper and in ink permeability through a photographic quality paper, settling the trouble of stains by rubbing just after printed, excellent in water resistance after recording and capable of high-speed, high-quality recording. SOLUTION: The ink jet recording method adopts a thermal ink jet printing system and makes a record on an image-receiving material using an ink composition comprising a dye dispersion obtained by emulsifying and dispersing in an aqueous medium an oil-soluble dye dissolved in a high-boiling point organic solvent having a boiling point of at least 150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording method capable of high-speed recording and maintaining excellent recording quality for a long time.

[0002]

2. Description of the Related Art With the spread of computers in recent years, ink jet printers are widely used not only in offices but also at home for printing on paper, film, cloth and the like. The ink jet recording system is roughly classified into a continuous system and an on-demand system. The on-demand system is widely used at present for office and home use. Among the on-demand systems, there are electro-mechanical conversion systems,
Although a heat conversion method, an electrostatic suction method, and the like are known, it is well known that the electric-mechanical conversion method and the electric-heat conversion method divide the market into two at present.

[0003] Among them, the electric-heat conversion method is also called a thermal method, which utilizes a boiling phenomenon of a liquid (usually water) on a fine heater surface. It is said that this thermal method is suitable for high-speed recording and high image quality by increasing the number of nozzles in the future because the processing of the head is easier than the electro-mechanical conversion method.

[0004] The print head of a thermal ink jet printer has a heating element in a plenum, which is an ink chamber having an outlet connected to a discharge nozzle. This plenum is connected to an ink cartridge that stores ink. Such heating elements are arranged in a specific pattern by the number of discharge nozzles, and the whole of them constitutes a print head. Each heating element is connected to the microprocessor by a conductive trace, and the heating of each element is controlled by energizing each heating element in response to a signal from the microprocessor. Bubbles are generated on the surface of the heated heating element, and the bubbles eject ink from the nozzles toward the print medium. In this way, characters and images are formed by instantaneously heating the plurality of heating elements. A thermal ink jet printer has features such as lower cost and less noise than conventional printers. Furthermore, rapid progress in head processing technology in recent years has made it possible to increase the number of nozzles, and merits have been recognized in terms of high-speed printing and print quality.

[0005] Oil-based, water-based, and solid inks are known as ink-jet inks. However, for thermal ink-jet inks, water is used in terms of head structure and handling, odor and safety. An aqueous ink as a main component is used. Among water-based inks, a water-soluble dye ink using a water-soluble dye that dissolves in a molecular state is mainly used. Aqueous inks have the advantage of high transparency and color density, but have poor water resistance, and when printed on so-called plain paper, cause bleeding (bleeding), resulting in a remarkable decrease in print quality and poor light resistance. There is. Further, a method of adding various additives has been proposed for the purpose of improving the above-mentioned drawbacks. However, in the thermal method, non-discharge caused by sticking of these components to the heater surface, so-called kogation There is a problem that is easy to cause.

[0006] Further, an ink described as an ink-jet ink is often used without distinction for a thermal printer and other non-heating (non-thermal type). A typical example of the non-thermal method here is a piezoelectric ink jet method. However, non-thermal inks tend to cause various chemical and physical changes in the ink composition due to the influence of heat, and cannot be used for thermal printers in many cases. In particular, in an ink jet printer using a thermal method, in order to guarantee repetitive heating of 10 million times or more, deterioration of the heating element due to adhesion, burning, and deposition of the ink composition on the surface of the heating element becomes a serious problem.

As a method for improving the above problem, for example,
JP-A-56-157468, JP-A-4-1846
No. 8, JP-A-10-110126, JP-A-1
Japanese Patent Application No. 0-195355 proposes various water-based inks for a thermal system using pigments and disperse dyes. According to these methods, the water resistance is certainly improved to some extent but is not perfect, and particularly in the case of a pigment ink, the coloring property is inferior to the dye ink, and the dispersion of the pigment ink or the dye ink Lacks storage stability,
In addition, there is a problem that the storage stability of the dispersion is apt to cause clogging at the ink discharge port due to lack of storage stability. Further, recording paper provided with an ink receiving layer containing a porous inorganic pigment on the surface thereof (hereinafter, may be referred to as “photo-quality paper”) has been used due to the recent trend toward higher image quality of inkjet technology. )), There is a problem that the aqueous ink using the pigment or the dye has poor penetrability, and the dye or the pigment easily peels off from the surface when rubbed by hand.

Japanese Patent Application Laid-Open No. 58-45272 proposes a method of enclosing a dye in urethane polymer latex particles. However, encapsulating a dye to a desired concentration by this method has a problem that it is difficult to obtain colored particles having excellent dispersion stability, and also has a problem of peeling of the dye as described above.

Furthermore, Japanese Patent Application Laid-Open No. 10-279873 discloses a method in which an acrylic polymer and an oil-soluble dye are dissolved in an organic solvent, and after dispersion, the organic solvent is removed to obtain colored polymer fine particles. However, there is a problem in the quality of the recorded image, particularly in the quality when recorded on a paper medium for photographic quality and stability in continuous recording, and there is also a problem that the temporal stability of the dispersion is not sufficient. . In addition, it has been found that the polymer latex itself easily adheres to the heater surface and easily causes kogation.

On the other hand, Japanese Patent Publication No. 5-76977 discloses that
There is disclosed an ink composition in which an oil-soluble dye is dissolved and dispersed in an organic solvent having a low solubility in water and a specific gravity close to that of water. However, since the organic solvent used here generally has insufficient compatibility with the oil-soluble dye, not only the recording density is low, but also when the heating of the heater is repeated, the precipitation of the dye is promoted, and as described above. This may cause kogation and nozzle clogging. There are also problems of color reproducibility due to insufficient color tone of the disclosed oil-soluble dyes, and problems of insufficient storage stability of the obtained image.

[0011] As described above, in the ink jet printer using the thermal method, which is easy to operate at high speed and has high image quality by reducing the number of nozzles, has a handleability, odor, and safety, and has a heating element surface. There is no deterioration of the heating element due to the adhesion of the ink composition to the surface, burning (kogation), deposition, etc., and no clogging of the nozzle occurs, and it is excellent in color developability (color density) and hardly causes abrasion stain immediately after printing. At present, an ink jet recording method which is excellent in water resistance and capable of high quality recording has not yet been provided. In addition, in order to stably perform high-quality recording, it is required that the ink has excellent long-term stability. In particular, in the case of ink containing emulsified dispersed particles, high dispersion stability over time is essential. It is.

[0012]

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, in the present invention, there is no deterioration of the heating element due to adhesion of ink components to the surface of the heating element, burning (kogation), sedimentation, etc., no clogging of nozzles, no dependence on paper, and any selection. Excellent color development when printed on paper,
It is an object of the present invention to provide a thermal ink jet recording method which is excellent in ink permeability to photographic quality paper, eliminates scratches and dirt immediately after printing, has excellent water resistance after recording, and is capable of high-speed high-quality recording. Aim. The present invention is easy to handle,
It is excellent in odor and safety, and has no precipitation of dyes. The deterioration of the heating element due to adhesion of ink components to the surface of the heating element, burning (kogation), deposition, etc. No clogging at the nozzle tip, excellent ejection stability, no dependence on paper, excellent ink permeability during recording, eliminating stains immediately after printing, and excellent color development and water resistance, high image quality at high density It is an object of the present invention to provide a method for producing a thermal inkjet ink which can be recorded on a recording medium.

[0013]

Means for solving the above problems are as follows. <1> An ink-jet recording method using a thermal ink-jet printing method, wherein an ink containing a dye dispersion obtained by emulsifying and dispersing an oil-soluble dye dissolved in a high-boiling organic solvent having a boiling point of 150 ° C. or higher in an aqueous medium. An ink jet recording method characterized in that recording is performed on an image receiving material using a composition.

<2> The high-boiling organic solvent contained in the dye dispersion has a relative dielectric constant of 3 to 12 at 25 ° C.
1>.

<3> The above <1> or <1>, wherein the average particle size of the dispersed particles in the dye dispersion is 100 nm or less.
2>.

<4> The ink jet recording method according to any one of <1> to <3>, wherein the image receiving material has an image receiving layer containing a white pigment on a support.

<5> A method for producing a thermal ink-jet ink in which an oil-soluble dye dissolved in a high-boiling organic solvent is emulsified and dispersed in an aqueous medium.
A method for producing a thermal ink-jet ink, comprising adding a low-boiling organic solvent having a temperature of 50 ° C. or lower and substantially removing the low-boiling organic solvent from the dye dispersion after emulsification and dispersion.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an ink-jet recording method and a method for producing a thermal ink-jet ink of the present invention will be described.

In the ink-jet recording method of the present invention, a thermal ink-jet method is adopted and the boiling point is 15
Recording is performed on an image receiving material using an ink composition containing a dye dispersion obtained by emulsifying and dispersing an oil-soluble dye dissolved in a high boiling organic solvent having a temperature of 0 ° C. or higher in an aqueous medium. In particular, in the thermal ink jet system, a heat-generating portion in contact with the ink is provided, and the above-described problems associated with kogation are caused, and the high-speed recording performance, which is a characteristic thereof, is easily impaired.However, in the present invention, if kogation can be avoided. At the same time, it is possible to improve the rubbing stain and the water resistance of the image, particularly after printing, and to stably form a clear, high-quality ink image without bleeding.
In addition, the ink permeability and color development characteristic of the aqueous ink are not impaired.

(Ink Composition) The following can be used as the ink composition. The ink composition comprises a dye dispersion obtained by emulsifying and dispersing an oil-soluble dye dissolved in a high-boiling organic solvent having a boiling point of 150 ° C. or higher in an aqueous medium. Boiling point 1 in advance
It is used by dissolving it in a high boiling point organic solvent of 50 ° C. or higher. In addition, other components such as a low-boiling organic solvent, a surfactant, and an anti-drying agent are included as necessary. The dye dispersion,
At least one of an oil-soluble dye and a high-boiling organic solvent having a boiling point of 150 ° C. or higher is dispersed in an aqueous medium. That is, the dye dispersion is a so-called emulsified dispersion in which an oil-soluble dye and a high-boiling organic solvent are dispersed as fine oil droplets in an aqueous medium. Incidentally, the "aqueous medium" in the present invention is water, or a mixture of water and a small amount of a water-miscible organic solvent, if necessary, a surfactant,
It means those to which additives such as a wetting agent, a stabilizer and a preservative are added.

—Oil-Soluble Dye— Examples of the oil-soluble dye include a yellow dye, a magenta dye, and a cyan dye, and those having an arbitrary solubility in water can be used.

The yellow dye is not particularly limited and can be appropriately selected from known dyes. Examples of the coupling component include phenols, naphthols, anilines, pyrazolones, pyridones, open-chain actives. Aryl or hetenylazo dyes having methylene compounds; azomethine dyes having open-chain active methylene compounds as coupling components; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; And quinophthalone dyes, nitro / nitroso dyes, acridine dyes, acridinone dyes, and the like. These yellow dyes may exhibit a yellow color only when a part of the chromophore dissociates, and in this case, the counter cation may be an alkali metal or an inorganic cation such as ammonium. And organic cations such as pyridinium and quaternary ammonium salts, and polymer cations having these in their partial structures.

The magenta dye is not particularly limited and may be appropriately selected from known dyes. For example, aryl or hetenylazo dyes having phenols, naphthols, and anilines as coupling components; coupling components Azomethine dyes having pyrazolones or pyrazolotriazoles; methine dyes such as arylidene dyes, styryl dyes, merocyanine dyes, and oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, and xanthene dyes;
Quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; condensed polycyclic dyes such as dioxazine dye;
And the like. These magenta dyes may exhibit magenta only when a part of the chromophore dissociates, and in that case, as a counter cation,
An alkali metal or an inorganic cation such as ammonium, an organic cation such as pyridinium or a quaternary ammonium salt, or a polymer cation having such a partial structure may be used. Good.

The cyan dye is not particularly limited and may be appropriately selected from known dyes. Examples thereof include azomethine dyes such as indoaniline dyes and indophenol dyes; and cyanine dyes, oxonol dyes, and merocyanine dyes. Polymethine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; phthalocyanine dyes; anthraquinone dyes; aryl or hetenylazo dyes having phenols, naphthols and anilines as coupling components; indigo / thioindigo dyes; No.
These cyan dyes may exhibit cyan only after a part of the chromophore dissociates, and in this case, the counter cation may be an alkali metal or an inorganic cation such as ammonium. And organic cations such as pyridinium and quaternary ammonium salts, and polymer cations having these in their partial structures.

Among the above-mentioned oil-soluble dyes, dyes which are used in color photographic materials and are formed from a developing agent and a coupler by oxidation are preferable. Among them, the following general formula (I)
Is preferred. In addition, the following formula (I)
The compound represented by the following formula (I) is preferably a compound in which at least one of the groups of the following general formula (I) is in the following preferable range, and a compound in which more groups are in the preferable range is more preferable. Compounds in which the group is in the preferred range are most preferred.

Formula (I)

Embedded image

In the general formula (I), X represents a residue of a color coupler. A represents -NR ⁴ R ⁵ or a hydroxyl group. R ⁴ and R ⁵ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. As A,
—NR ⁴ R ⁵ is preferred. R ⁴ and R ⁵ are each independently preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom, an alkyl group or a substituted alkyl group, and more preferably a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or 1 carbon atom.
~ 18 substituted alkyl groups are most preferred.

B ¹ represents ＝ C (R ⁶ )-or ＮN-.
B ² is, -C (R ⁷⁾ = or an -N =. Is preferably B ¹ and B ² are not -N = at the same time, B ¹ is = C
(R ⁶ ) — and B ² is more preferably —C (R ⁷ ) =.

In the general formula (I), R^Two, R^Three, R
⁶, R⁷Are independently a hydrogen atom, a halogen atom,
Aliphatic group, aromatic group, heterocyclic group, cyano group, -OR⁵¹, −
SR ⁵², -CO_TwoR⁵³, -OCOR⁵⁴, -NR⁵⁵R⁵⁶,
-CONR⁵⁷R⁵⁸, -SO_TwoR ⁵⁹, -SO_TwoNR⁶⁰R⁶¹,
-NR⁶²CONR⁶³R⁶⁴, -NR⁶⁵CO_TwoR⁶⁶, -CO
R⁶⁷, -NR⁶⁸COR⁶⁹Or -NR⁷⁰SO_TwoR⁷¹The table
You. The R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷,
R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R
⁶⁶, R⁶⁷, R⁶⁸, R⁶⁹, R⁷⁰, R⁷¹Are independent of each other
Represents a hydrogen atom, an aliphatic group or an aromatic group.

Among them, R ² and R ⁷ each independently represent a hydrogen atom, a halogen atom, an aliphatic group, —OR
⁵¹ , -NR ⁶² CONR ⁶³ R ⁶⁴ , -NR ⁶⁵ CO ₂ R ⁶⁶ ,-
Preferably NR ^{6 8} COR ⁶⁹ and -NR ⁷⁰ SO ₂ R ^71, a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group, a substituted alkyl group, -NR ⁶² CONR ⁶³ R ⁶⁴ and -NR ⁶⁸ COR ⁶⁹
Are more preferable, a hydrogen atom, a chlorine atom, and a carbon atom number of 1
Particularly preferred are a 10 alkyl group and a substituted alkyl group having 1 to 10 carbon atoms, and most preferred are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and a substituted alkyl group having 1 to 4 carbon atoms.

Among them, R ³ and R ⁶ are each independently preferably a hydrogen atom, a halogen atom and an aliphatic group, more preferably a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group and a substituted alkyl group. Particularly preferred are a hydrogen atom, a chlorine atom, an alkyl group having 1 to 10 carbon atoms and a substituted alkyl group having 1 to 10 carbon atoms, and a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and 1 to carbon atoms.
Four substituted alkyl groups are most preferred.

In the general formula (I), R ² and R ³ are:
R ³ and R ^4, R ⁴ and R ^5, R ⁵ and R ^6, and, R ⁶ and R ⁷
And may combine with each other to form a ring. Examples of the combination forming the ring include R ³ and R ⁴ , R ⁴ and R ^5, and R ⁵
And a combination of R ⁶ is preferred.

The ring formed by combining R ² and R ³ or R ⁶ and R ⁷ with each other is preferably a 5- or 6-membered ring. As the ring, an aromatic ring (for example, a benzene ring or the like)
Alternatively, an unsaturated heterocyclic ring (for example, a pyridine ring, an imidazole ring, a thiazole ring, a pyrimidine ring, a pyrrole ring, a furan ring, and the like) is preferable. R ³ and R ⁴ or R ⁵ and R ⁶ are
The ring formed by bonding to each other is preferably a 5-membered ring or a 6-membered ring. As the ring, a tetrahydroquinoline ring and a dihydroindole ring are preferable. The ring formed by combining R ⁴ and R ⁵ with each other is preferably a 5- or 6-membered ring. As the ring, a pyrrolidine ring, a piperidine ring and a morpholine ring are preferred.

In the present specification, the aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group and a substituted aralkyl group.

The alkyl group may be branched or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 20, and more preferably 1 to 18. The alkyl part of the substituted alkyl group is the same as the above-mentioned alkyl group. The alkenyl group may be branched or cyclic. The number of carbon atoms of the alkenyl group is preferably 2 to 20, and more preferably 2 to 18. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group.

The alkynyl group may be branched or cyclic. The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 18 carbon atoms. The alkynyl part of the substituted alkynyl group is the same as the alkynyl group. The alkyl part of the aralkyl group and the substituted aralkyl group is the same as the above-mentioned alkyl group. The aryl part of the aralkyl group and the substituted aralkyl group is the same as the following aryl group.

Examples of the substituent of the alkyl moiety in the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group and the substituted aralkyl group include, for example, a halogen atom, a cyano group, a nitro group, a heterocyclic group, -OR ¹¹¹ ,
-SR ¹¹² , -CO ₂ R ¹¹³ , -NR ¹¹⁴ R ¹¹⁵ , -CON
R ¹¹⁶ R ¹¹⁷ , —SO ₂ R ¹¹⁸ and —SO ₂ NR ¹¹⁹ R ¹²⁰ . R ¹¹¹ , R ¹¹² , R ¹¹³ , R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ and R ¹²⁰ each independently represent a hydrogen atom, an aliphatic group or an aromatic group. Examples of the substituent of the aryl moiety in the substituted aralkyl group include the same substituents as those described below for the substituted aryl group.

The aromatic group means an aryl group and a substituted aryl group. As the aryl group, a phenyl group or a naphthyl group is preferable, and a phenyl group is particularly preferable. The aryl part of the substituted aryl group is the same as the above-mentioned aryl group. Examples of the substituent of the substituted aryl group, a halogen atom, a cyano group, a nitro group, an aliphatic group, a heterocyclic ^{group, -OR 121, -SR 122, -CO} 2 R 123, -NR
¹²⁴ R ¹²⁵ , -CONR ¹²⁶ R ¹²⁷ , -SO ₂ R ¹²⁸ and -S
O ₂ NR ¹²⁹ R ¹³⁰ is mentioned. R ¹²¹ , R ¹²² , R
¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ and R ¹³⁰ each independently represent a hydrogen atom, an aliphatic group or an aromatic group.

The heterocyclic group includes a group having a saturated heterocyclic ring or an unsaturated heterocyclic ring. The heterocyclic ring in the heterocyclic group is preferably a 5- or 6-membered ring. In addition, an aliphatic ring, an aromatic ring, or another hetero ring may be condensed with the hetero ring. As a hetero atom in the heterocyclic ring,
B, N, O, S, Se and Te are included. Among these, N, O and S are preferable as the hetero atom.
Of the atoms constituting the heterocyclic ring, a heterocyclic group in which a carbon atom has a free valence (monovalent) (a heterocyclic group is bonded at a carbon atom) is preferable. Examples of the saturated heterocyclic ring include a pyrrolidine ring, a morpholine ring,
It includes a 1,3-dioxolane ring and a 1,3-thiazolidine ring. Examples of the unsaturated heterocyclic ring include an imidazole ring, a thiazole ring, a benzothiazole ring, a benzoxazole ring, a benzotriazole ring, a benzoselenazole ring, a pyridine ring, a pyrimidine ring, and a quinoline ring.

The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an aliphatic group, an aromatic group, a heterocyclic group, -OR ¹³¹ ,-
SR ^{1 32} , -CO ₂ R ¹³³ , -NR ¹³⁴ R ¹³⁵ , -CONR
¹³⁶ R ¹³⁷ , -SO ₂ R ¹³⁸ and SO ₂ NR ¹³⁹ R ¹⁴⁰ . R ¹³¹ , R ¹³² , R ¹³³ , R ¹³⁴ , R ¹³⁵ , R
¹³⁶ , R ¹³⁷ , R ¹³⁸ , R ¹³⁹ and R ¹⁴⁰ are each independently
Represents a hydrogen atom, an aliphatic group or an aromatic group.

In the general formula (I), X represents a residue of a color coupler. The dye represented by the general formula (I) is
X is generated by the reaction between the oxidized form of the developing agent and the coupler, and X represents a group derived from the coupler. Here, a coupler refers to a compound capable of performing a coupling reaction with an oxidized form of a color developing agent. For a more specific explanation, see "Basics of Photonic Engineering-Silver Halide Photography-" edited by The Photographic Society of Japan (1979,
20 of “3.6 Couplers and Related Substances” by Corona
It is described on pages 4 to 222. Here, the developing agent refers to a compound capable of forming a cyan, magenta or yellow azomethine dye, an indoaniline dye or the like by a coupling reaction of an oxidized product thereof with a coupler. For example, p
-Phenylenediamine derivatives, p-aminophenol derivatives and the like (preferably p-phenylenediamine derivatives)
Can be mentioned. For a more specific explanation, see “Basics of Photographic Engineering-Silver halide photography-” edited by The Photographic Society of Japan (1979
"Corona Publishing Co., Ltd.", "4.3 Color Photographic Processing"
345-354.

The yellow coupler is described in US Pat. Nos. 3,933,501 and 4,022,620.
Nos. 4,326,024 and 4,401,752
No. 4,248,961, JP-B-58-10739
No., British Patent Nos. 1,425,020 and 1,476,7
No. 60, U.S. Pat. Nos. 3,973,968 and 4,31
4,023, 4,511,649, European Patent 24
9,473A and 502,424A, formula (I),
Couplers represented by the formulas (1) and (2) of JP-A-513,496A (particularly Y on page 18).
-28), a coupler represented by the formula (I) in claim 1 of U.S. Pat. No. 5,066,57.
A coupler represented by general formula (I) on line 45-55 of column 1 of No. 6, paragraph 0008 of JP-A-4-274425.
A coupler represented by the general formula (I), EP 498,
No. 381A1, page 40, claim 1 (especially D-35 on page 18), and couplers represented by formula (Y) on page 4 of 447,969 A1 (especially Y-1 (1
7), Y-54 (page 41)), U.S. Pat.
Formulas (II) to (IV) on lines 36 to 58 of column 7 of No. 219
(Particularly II-17, 19 (column 1)
7), II-24 (column 19)).

Examples of the magenta coupler include US Pat. Nos. 4,310,619 and 4,351,897, EP 73,636, US Pat. No. 3,061,432,
No. 3,725,067, Research Disclosure No. No. 24220 (June 1984); 24
230 (June 1984), JP-A-60-33552
No. 60-43659, No. 61-72238, No. 60-35730, No. 55-118034, No. 60
No. 185951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, WO 88/04795, and JP-A-3-39737 (L-57 (right of page 11)). Bottom), L-68 (page 12, lower right),
L-77 (page 13, lower right), European Patent 456,257 [A-4] -63 (page 134), [A-4] -73,-
75 (p. 139) and M-4, -6 of JP-A-486-965.
(P. 26), M-7 (p. 27), M-45 (p. 19) of JP-A-571-959A, (M-1) (p. 6) of JP-A-5-204106, and JP-A-4-362633. Paragraph 02
37 M-22 and U.S. Pat. Nos. 3,061,432 and 3,725,067.

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

In addition, JP-A-62-215272 (9)
1), JP-A-2-33144 (pages 3 and 30), E
Couplers described in P355, 660A (pages 4, 5, 45, 47) are also useful.

Among the compounds represented by the general formula (I), a compound represented by the following general formula (II) is particularly preferably used as the magenta dye.

General formula (II)

Embedded image

In the general formula (II), R¹Is hydrogen field
Child, aliphatic group, aromatic group, heterocyclic group, cyano group, -OR
¹¹, -SR¹², -CO_TwoR¹³, -OCOR¹⁴, -NR^Fifteen
R¹⁶, -CONR¹⁷R¹⁸, -SO_TwoR¹⁹, -SO_TwoNR²⁰
R^{twenty one}, -NR^{twenty two}CONR^{twenty three}R ^{twenty four}, -NR^{twenty five}CO_TwoR²⁶,
-COR²⁷, -NR²⁸COR²⁹Or -NR³⁰SO_TwoR³¹
Represents The R¹¹, R¹², R¹³, R¹⁴, R^Fifteen, R¹⁶, R
¹⁷, R¹⁸, R¹⁹, R²⁰, R^{twenty one}, R^{twenty two}, R^{twenty three}, R^{twenty four},
R^{twenty five}, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰And R³¹Are each
Independently represents a hydrogen atom, an aliphatic group or an aromatic group. Ma
R^Two, R^Three, A, B¹, And B^TwoIs represented by the general formula (I)
And the preferred range is also the same.
You.

In the general formula (II), D is a 5-membered or
Represents an atomic group forming a 6-membered nitrogen-containing heterocyclic ring,
May be substituted with one substituent. In addition,
The heterocyclic ring may form a condensed ring with another ring. D
Atom forming a 5- or 6-membered nitrogen-containing heterocyclic ring represented by
In the group, at least one substituent is an aliphatic
Group, aromatic group, heterocyclic group, cyano group, -OR ⁸¹, -SR
⁸², -CO_TwoR⁸³, -OCOR⁸⁴, -NR⁸⁵R⁸⁶, -C
ONR⁸⁷R⁸⁸, -SO_TwoR⁸⁹, -SO_TwoNR⁹⁰R⁹¹, -N
R⁹²CONR⁹³R⁹⁴, -NR⁹⁵CO_TwoR⁹⁶, -CO
R⁹⁷, -NR⁹⁸COR⁹⁹And -NR¹⁰⁰SO_TwoR¹⁰¹Is raised
I can do it. The R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶,
R⁸⁷, R⁸⁸, R⁸⁹, R⁹⁰, R⁹¹, R⁹², R⁹³, R⁹⁴, R
⁹⁵, R⁹⁶, R⁹⁷, R⁹⁸, R⁹⁹, R¹⁰⁰And R¹⁰¹Is it
Each independently represents a hydrogen atom, an aliphatic group or an aromatic group.

In the general formula (II), R ¹ represents a hydrogen atom, an aliphatic group, an aromatic group, —OR ¹¹ , —SR
^{12, -NR 15 R 16, -SO} 2 R 19, -NR 22 CONR 23
_{^{R 24, -NR 25 CO 2 R}} 26, -NR 28 COR 29 and -N
R ³⁰ SO ₂ R ³¹ is preferred, and a hydrogen atom, an aliphatic group, an aromatic group, —OR ¹¹ and —NR ¹⁵ R ¹⁶ are more preferred, and a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, Alkoxy groups, substituted alkoxy groups, phenoxy groups, substituted phenoxy groups, dialkylamino groups, and substituted dialkylamino groups are more preferred, a hydrogen atom,
Alkyl group having 1 to 10 carbon atoms, 1 to 10 carbon atoms
Particularly preferred are a substituted alkyl group, an aryl group having 6 to 10 carbon atoms and a substituted aryl group having 6 to 10 carbon atoms, and a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and substitution having 1 to 6 carbon atoms. Alkyl groups are most preferred.

In the general formula (II), A is
—NR ⁴ R ⁵ is preferred. As D, it is preferable to form a 5-membered nitrogen-containing heterocyclic ring, and as the 5-membered nitrogen-containing heterocyclic ring, for example, an imidazole ring, a triazole ring,
A tetrazole ring is more preferred.

Among the compounds represented by the general formula (II), an oil-soluble pyrazolotriazole azomethine compound represented by the following general formula (III) is particularly preferred.

Formula (III)

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In the general formula (III), R ¹ , R ² ,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the same meanings as in the case of the general formula (II). Also, X and Y are each independently -C (R ⁸⁾ = or an -N =. R ⁸ represents a hydrogen atom, an aliphatic group or an aromatic group. One of X and Y must be -N
=, And X and Y are not -N = at the same time.

In the formula (III), R ⁸ is preferably a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.
A substituted alkyl group having 1 to 150 carbon atoms and a substituted aryl group having 6 to 150 carbon atoms are more preferable, and a substituted alkyl group having 1 to 100 carbon atoms and a substituted aryl group having 6 to 100 carbon atoms are particularly preferable. Further, when X and Y are -C (R ⁸⁾ = the same time, each of R ⁸ may be bonded to each other to form a ring, the ring 6 membered ring. As the ring, an aromatic ring (for example, a benzene ring or the like) is more preferable.

Among the compounds represented by the general formula (III), pyrazolotriazole azomethine dyes in which X is -N = and Y is -C (R ⁸ ) = are preferable.

Next, examples of the pyrazolotriazole azomethine dye represented by the general formula (II) (M-1 to M-1)
16) is shown below, but the present invention is not limited to these.

[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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Examples of the compounds usable in the present invention include the compounds described in Japanese Patent Application No. 11-365189, but the present invention is not limited thereto.

The dye represented by the general formula (II) is described, for example, in JP-A-4-126772, JP-B-7-94180.
The compound can be synthesized with reference to the methods described in Japanese Patent Application Laid-Open No. 11-365187 and Japanese Patent Application No. 11-365187.

As the cyan dye, pyrrolotriazole azomethine compounds represented by the following formulas (IV-1) to (IV-4) are particularly preferably used.

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In the above formulas (IV-1) to (IV-4),
A, R ² , R ³ , B ¹ and B ² have the same meanings as those in the formula (I), and their preferred ranges are also the same. R
²⁰¹ , R ²⁰² and R ²⁰³ are each independently the above-mentioned general formula (I
It is the same as R ¹ in I). R ²⁰¹ and R ²⁰² may combine with each other to form a ring structure.

Further, in the pyrrolotriazoleazomethine compounds represented by the formulas (IV-1) to (IV-4), ^R201 is an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.30 or more. Has sharp absorption and is more preferable. Then, the sum of Hammett substituent constant σ _p values of R ²⁰¹ and R ²⁰² in pyrrolotriazole azomethine is
Those having 0.70 or more exhibit an excellent hue as a cyan color, and are particularly preferable.

Here, the above formulas (IV-1) to (IV-4)
The hue of the pyrrolotriazole azomethine compound represented by the formula will be described. The pyrrolotriazole azomethine compounds represented by the formulas (IV-1) to (IV-4) include:
^{R 201, R 202, R 203} , and R ^2, R ^3, A, the combination of B ^1, B ^2, can have a variety of colors. The pyrrolotriazole azomethine compounds represented by the above formulas (IV-1) to (IV-4) are preferable when R ²⁰¹ is an electron-withdrawing substituent, because the absorption waveform becomes sharper than in the case where R ²⁰¹ is not. The absorption waveform becomes sharper as the degree of electron attraction increases. From this viewpoint, R ²⁰¹ is preferably an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.30 or more, more preferably 0.45 or more than an alkyl group or an aryl group. .
Particularly preferred are 60 or more electron-withdrawing groups.

The pyrrolotriazoleazomethine compound can be used as a magenta dye or a cyan dye, but is more preferably used as a cyan dye. The pyrrolotriazole azomethine compounds represented by the formulas (IV-1) to (IV-4) can also be used as a magenta dye. Formulas (IV-1) to
In order to make the pyrrolotriazole azomethine compound represented by (IV-4) a cyan compound, the sum of Hammett substituent constant σ _p values of R ²⁰¹ and R ²⁰² is preferably 0.70 or more. If the sum of the σ _p values is less than 0.70, the absorption maximum wavelength becomes a short wavelength for the cyan dye, and looks blue to human eyes, which is not preferable. Among them, Hammett substituent constant sigma _p value is more preferably one having 0.30 or more R ^202, the sum of the Hammett substituent constant sigma _p value of R ²⁰¹ and R ²⁰² is particularly preferably from 2.0 or less.

The Hammett substituent constant σ _p value is 0.3
Examples of the zero or more electron-withdrawing group 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, an arylsulfinyl group, an alkylsulfonyl group, and an arylsulfonyl group. group, a sulfamoyl group, a halogenated alkyl group, halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylthio group, two or more sigma _p value is an aryl group substituted with 0.15 or more electron-withdrawing group, And a heterocyclic group.

More specifically, an acyl group (eg, acetyl, 3-phenylpropanoyl, etc.), an acyloxy group (eg, acetoxy, etc.), a carbamoyl group [eg,
N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl,
N-methyl-N-dodecylcarbamoyl, etc.], an alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl, etc.), a cyano group,
Nitro group, alkylsulfinyl group (eg, 3-phenoxypropylsulfinyl, etc.), arylsulfinyl group (eg, 3-pentadecylphenylsulfinyl, etc.), alkylsulfonyl group (eg, methanesulfonyl, octanesulfonyl, etc.), arylsulfonyl group ( For example, benzenesulfonyl, etc.), sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, etc.), alkyl halide group (eg, trifluoromethyl, heptafluoropropyl, etc.), halogenated alkoxy Group (eg, trifluoromethyloxy), a halogenated aryloxy group (eg, pentafluorophenyloxy), a halogenated alkylthio group (eg, difluoromethylthio), two or more σ _p values of 0.15 Above other An aryl group substituted with an electron-withdrawing group (for example, 2,4-dinitrophenyl, 2,4,6
-Trichlorophenyl, pentachlorophenyl, etc.), a heterocyclic group (for example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl,
5-chloro-1-tetrazolyl, 1-pyrrolyl, etc.).

As the electron-withdrawing group having a Hammett σ _p value of 0.45 or more, an acyl group (eg, acetyl, 3-
Phenylpropanoyl, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl), an aryloxycarbonyl group (eg, m-chlorophenoxycarbonyl), a cyano group, a nitro group, an alkylsulfinyl group (eg, n-propylsulfinyl) An arylsulfonyl group (for example, phenylsulfinyl and the like), an alkylsulfonyl group (for example, methanesulfonyl, n-octanesulfonyl and the like), an arylsulfonyl group (for example, benzenesulfonyl and the like), a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dimethylsulfamoyl and the like, a halogenated alkyl group (for example, trifluoromethyl and the like) and the like.

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.

As a combination in which the sum of the Hammett substituent constants σ _p values of R ²⁰¹ and R ²⁰² is 0.70 or more, R ²⁰¹ is a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group and an alkyl halide. A combination wherein R ²⁰² is 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. preferable.

The preferred structure of the pyrrolotriazoleazomethine compound in the present invention is represented by the following general formula (IV-
1a) a compound represented by the formula: wherein R ² is a hydrogen atom,
An alkyl group having 1 to 4 carbon atoms, a substituted alkyl group having 1 to 4 carbon atoms, a halogen atom (fluorine, chlorine, bromine), 1 carbon atom
5 acylamino group, an aminocarbonylamino group having 1 to 5 carbon atoms, or an alkoxycarbonylamino group having 1 to 5 carbon atoms, R ⁴ and R ⁵ are each independently a hydrogen atom, C1-18 R ²⁰¹ and R ²⁰² are each independently an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.30 or more, wherein R ²⁰¹ and R ²⁰² are each independently ²⁰³ is an alkyl group having 1 to 18 carbon atoms, a substituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

When the pyrrolotriazole azomethine compound is used as a cyan dye, a compound having a sum of Hammett substituent constant σ _p values of R ²⁰¹ and R ²⁰² of 0.70 or more is preferable among the preferable structures, More preferably, the sum of Hammett substituent constant σ _p values is 1.00 or more. Among the pyrrolotriazole azomethine compounds in the present invention, a structure represented by the following general formula (IV-1a), wherein R ² is a hydrogen atom or a methyl group, and R ⁴ and R ⁵ are each independently: An alkyl group having 1 to 5 carbon atoms, R ²⁰¹ is a cyano group, R ²⁰² is an alkoxycarbonyl group, and R ²⁰³ is an aryl group;
Most preferred.

[0079]

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Here, the Hammett substituent constant used in this specification is described in Japanese Patent Application No. 11-365188, and the σ _p value and σ _m value of the present invention are also described in the description. It is synonymous with what is specified.

Here, the exemplary compounds (C-1 to 9) of the pyrrolotriazole azomethine compound will be listed, but the present invention is not limited thereto.

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[0084]

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The compounds usable in the present invention include, but are not limited to, the exemplified compounds described in Japanese Patent Application No. 11-365188.

The pyrrolotriazole azomethine dyes represented by the formulas (IV-1) to (IV-4) are disclosed in
No. 7959, No. 9-292679, No. 10-6292
The compound can be synthesized with reference to the method described in Japanese Patent Application Laid-Open No. 6-63, and Japanese Patent Application No. 11-365188.

-High-boiling organic solvent- The high-boiling organic solvent is an organic solvent having a boiling point of 150 ° C or higher. Among them, those having a boiling point of 170 ° C. or higher are preferred. The high-boiling organic solvent has a dielectric constant of 3 to
12 is preferable and 4 to 10 are more preferable. Here, the dielectric constant represents a relative dielectric constant at 25 ° C. in a vacuum.

The high boiling organic solvent is not particularly limited and may be appropriately selected depending on the purpose.
Compounds described in U.S. Pat. No. 2,322,027 are exemplified, and high-boiling organic solvents such as phosphoric acid esters, fatty acid esters, phthalic acid esters, benzoic acid esters, phenols, and amides are preferable. .

As the high boiling organic solvent, the following formula [S
Compounds represented by [-1] to [S-9] are particularly preferred.

[0090]

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In the formula [S-1], R ³⁰ , R ³¹ and R ³² each independently represent an aliphatic group or an aryl group. A, b and c each independently represent 0 or 1.

In the above formula [S-2], R ³³ and R ³⁴
Each independently represents an aliphatic group or an aryl group. R
³⁵ is a halogen atom (F, Cl, Br, I, the same applies hereinafter), an alkyl group, an alkoxy group, an aryloxy group,
Represents an alkoxycarbonyl group or an aryloxycarbonyl group. d represents an integer of 0 to 3. When d is plural, plural R ³⁵ may be the same or different.

In the above formula [S-3], Ar represents an aryl group. e represents an integer of 1 to 6. R ³⁶ represents an e-valent hydrocarbon group or a hydrocarbon group bonded to each other by an ether bond.

In the formula [S-4], R ³⁷ represents an aliphatic group. f represents an integer of 1 to 6. R ³⁸ represents a f-valent hydrocarbon group or a hydrocarbon group bonded to each other by an ether bond.

In the formula [S-5], g represents an integer of 2 to 6. R ³⁹ represents a g-valent hydrocarbon group (excluding an aryl group). R ⁴⁰ represents an aliphatic group or an aryl group.

In the formula [S-6], R ⁴¹ , R ⁴² and R ⁴³ each independently represent a hydrogen atom, an aliphatic group or an aryl group. X is, -CO- or SO ₂ - represents a. R
⁴¹ and R ⁴² or R ⁴² and R ⁴³ may be bonded to each other to form a ring.

In the formula [S-7], R ⁴⁴ represents an aliphatic group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group or a cyano group. R ⁴⁵ represents a halogen atom, an aliphatic group, an aryl group, an alkoxy group or an aryloxy group. h represents an integer of 0 to 3, and when h is plural, plural R ⁴⁵ may be the same or different.

In the above formula [S-8], R ⁴⁶ and R ⁴⁷
Each independently represents an aliphatic group or an aryl group. R
⁴⁸ represents a halogen atom, an aliphatic group, an aryl group, an alkoxy group or an aryloxy group. i represents an integer of 0 to 4, when i is two or more, plural R ⁴⁸ may be the same or may be different.

In the above formula [S-9], R ⁴⁹ and R ⁵⁰
Represents an aliphatic group or an aryl group. j represents 1 or 2.

In the above formulas [S-1] to [S-9],
When R ^{30 to} R ³⁵ , R ³⁷ , and R ^{40 to} R ⁵⁰ are an aliphatic group or a group containing an aliphatic group, the aliphatic group may be linear, branched, or cyclic. And may contain an unsaturated bond, and may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a hydroxyl group, an acyloxy group, an epoxy group and the like.

In the formulas [S-1] to [S-9],
When R ^{30 to} R ³⁵ , R ³⁷ , and R ^{40 to} R ⁵⁰ are a cyclic aliphatic group, that is, a cycloalkyl group or a group containing a cycloalkyl group, the cycloalkyl group has 3 to 8 members. The ring may contain an unsaturated bond, and may have a substituent or a crosslinking group. Examples of the substituent include a halogen atom,
Examples thereof include an aliphatic group, a hydroxyl group, an acyl group, an aryl group, an alkoxy group, an epoxy group, and an alkyl group. Examples of the cross-linking group include a methylene group, an ethylene group, and an isopropylidene group.

In the formulas [S-1] to [S-9],
When R ^{30 to} R ³⁵ , R ³⁷ , and R ^{40 to} R ⁵⁰ are an aryl group or a group containing an aryl group, the aryl group may be a halogen atom, an aliphatic group, an aryl group, an alkoxy group, an aryloxy group, an alkoxy group. It may be substituted with a substituent such as a carbonyl group.

In the above formulas [S-3], [S-4] and [S-5], when R ³⁶ , R ³⁸ or R ³⁹ is a hydrocarbon group, the hydrocarbon group is It may contain a cyclic structure (for example, a benzene ring, a cyclopentane ring, or a cyclohexane ring) or an unsaturated bond, and may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an acyloxy group, an aryl group, an alkoxy group, an aryloxy group, an epoxy group, and the like.

Next, a particularly preferred high-boiling organic solvent in the present invention will be described.

In the above formula [S-1], R ³⁰ , R ³¹ and R ^{32 each} represent 3 to 24 carbon atoms (hereinafter abbreviated as C number).
(Preferably 4 to 18) aliphatic groups (for example, n-butyl, 2-ethylhexyl, 3,3,5-trimethylhexyl, n-dodecyl, n-octadecyl, benzyl, oleyl, 2-chloroethyl, 2,3- Dichloropropyl, 2-butoxyethyl, 2-phenoxyethyl, cyclopentyl, cyclohexyl, 4-t-butylcyclohexyl, 4-methylcyclohexyl) or a C number of 6 to 24
(Preferably 6 to 18) aryl groups (for example, phenyl, cresyl, p-nonylphenyl, xycle, cumenyl, p-methoxyphenyl, p-methoxycarbonylphenyl). a, b, and c are each independently 0 or 1, and preferably all 1.

In the above formula [S-2], R ³³ and R ³⁴
Is an aliphatic group having 4 to 24 (preferably 4 to 18) C atoms (for example, the same group as the alkyl group mentioned for R ³⁰ above)
Ethoxycarbonylmethyl, 1,1-diethylpropyl, 2-ethyl-1-methylhexyl, cyclohexylmethyl, 1-ethyl-1,5-dimethylhexyl, 3,
5,5-trimethylcyclohexyl, 1-methylcyclohexyl) or an aryl group having a C number of 6 to 24 (preferably 6 to 18) (for example, the aryl group described for R ³⁰ , 4-t-butylphenyl, 4-t-) Octylphenyl, 1,3,5-trimethylphenyl, 2,4, -di-
t-butylphenyl, 2,4, -di-t-pentylphenyl). R ³⁵ is a halogen atom (preferably C
l), an alkyl group having 1 to 18 C atoms (for example, methyl, isopropyl, t-butyl, n-dodecyl);
(E.g., methoxy, n-butoxy, n-
Octyloxy, methoxyethoxy, benzyloxy), an aryloxy group having 6 to 18 carbon atoms (for example, phenoxy, p-tolyloxy, 4-methoxyphenoxy,
-T-butylphenoxy) or an alkoxycarbonyl group having 2 to 19 carbon atoms (for example, methoxycarbonyl, n-butoxycarbonyl, 2-ethylhexyloxycarbonyl) or an aryloxycarbonyl group having 6 to 25 carbon atoms. d is 0 or 1.

In the above formula [S-3], Ar represents an aryl group having a C number of 6 to 24 (preferably 6 to 18) (for example, phenyl, 4-chlorophenyl, 4-methoxyphenyl, 1-naphthyl, 4-n -Butoxyphenyl, 1,
3,5-trimethylphenyl), e is an integer of 1 to 4 (preferably 1 to 3), and R ³⁶ is an e-valent C number of 2
24 (preferably 2 to 18) of the hydrocarbon group [for example, alkyl groups as described as R ^33, a cycloalkyl group,
An aryl group,-(CH ₂ ) _2- , and the following groups,

[0108]

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Or a hydrocarbon group bonded to each other by an e-valent ether bond having 4 to 24 (preferably 4 to 18) carbon atoms [for example, -CH ₂ CH ₂ OCH ₂ CH _2- , -CH ₂
CH ₂ (OCH ₂ CH ₂ ) ₃ —, —CH ₂ CH ₂ CH ₂ OCH ₂ C
H ₂ CH ₂ — and further the following groups.

[0110]

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In the formula [S-4], R ³⁷ represents an aliphatic group having 3 to 24 (preferably 3 to 17) C atoms (for example, n
-Propyl, 1-hydroxyethyl, 1-ethylpentyl, n-undecyl, pentadecyl, 8,9-epoxyheptadecyl, cyclopropyl, cyclohexyl, 4-
Methyl is a cyclohexyl), f is an integer of 1 to 4 (preferably 1 to 3), and R ³⁸ is an f-valent C number of 2 to 2
4 (preferably 2 to 18) of the hydrocarbon group or f-valent carbon atoms from 4 to 24 (preferably 4 to 18) carbon atoms linked together by an ether bond therein (for example, the same as described as R ³⁶ groups) is there.

In the formula [S-5], g is 2 to 4
(Preferably 2 or 3) and R ³⁹Is a g-valent hydrocarbon
Element group [for example, -CH_Two-,-(CH_Two)_Two-,-(CH_Two)_Four
-,-(CH_Two)₇-, And the following groups.

[0113]

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R ⁴⁰ has a C number of 4 to 24 (preferably 4 to 1).
8) an aliphatic group or a C number of 6 to 24 (preferably 6 to 1);
Aryl groups of 8) (e.g., an aliphatic group as described as R ^33, an aryl group).

In the formula [S-6], R ⁴¹ represents an aliphatic group having 3 to 20 carbon atoms [eg, n-propyl, 1-ethylpentyl, n-undecyl, n-pentadecyl, 2,4
-Di-t-pentylphenoxymethyl, 4-t-octylphenoxymethyl, 3- (2,4-di-t-butylphenoxy) propyl, 1- (2,4-di-t-butylphenoxy) propyl, cyclohexyl, 4-methylcyclohexyl) or an aryl group having 6 to 24 (preferably 6 to 18) C atoms (for example, the aryl groups mentioned above for Ar). R ⁴² and R ⁴³ are an aliphatic group having 3 to 24 (preferably 3 to 18) C atoms (eg, isopropyl, n-butyl, n-hexyl, 2-ethylhexyl, n-dodecyl, cyclopentyl, cyclopropyl) or C Number 6-1
8 (preferably 6 to 15) aryl groups (for example, phenyl, 1-naphthyl, p-tolyl). R ⁴² and R ⁴³ may be bonded to each other to form a pyrrolidine ring, piperidine ring, or morpholine ring together with N, or R ⁴¹ and R ⁴² may be bonded to each other to form a pyrrolidone ring. X is-
CO- or -SO ₂ - represents, -CO- are preferable.

In the above formula [S-7], R ⁴⁴ is an aliphatic group having 3 to 24 (preferably 3 to 18) C atoms (eg, isopropyl, t-butyl, t-pentyl, t-hexyl, t-hexyl). Octyl, 2-butyl, 2-hexyl, 2-octyl, 2-dodecyl, 2-hexadecyl, t-pentadecyl, cyclopentyl, cyclohexyl), C number 5
24 (preferably 5 to 17) alkoxycarbonyl groups (for example, n-butoxycarbonyl, 2-ethylhexyloxycarbonyl, n-dodecyloxycarbonyl) C
An alkylsulfonyl group having a number of 3 to 24 (preferably 3 to 18) (for example, n-butylsulfonyl or n-dodecylsulfonyl), or an arylsulfonyl group having a C number of 6 to 30 (preferably 6 to 24) (for example, p-tolylsulfonyl) , P-
Dodecylphenylsulfonyl, p-hexadecyloxyphenylsulfonyl), a C number of 6 to 32 (preferably 6 to 32)
24) aryl groups (for example, phenyl, p-tolyl) or cyano groups.

R ⁴⁵ is a halogen atom (preferably C
l) alkyl group (e.g., alkyl groups as described as R ⁴⁴ a C number of 3 to 24 (preferably 3 to 18)), cycloalkyl group having a C number of 5 to 17 (e.g. cyclopentyl,
Cyclohexyl), C number of 6 to 32 (preferably 6 to 2)
4) aryl group (e.g., phenyl, p-tolyl) and C1-24 (preferably 1-18) alkoxy group (e.g., methoxy, n-butoxy, 2-ethylhexyloxy, benzyloxy, n-dodecyloxy, n -Hexadecyloxy) or a C number of 6 to 32 (preferably 6 to 2)
4) aryloxy group (for example, phenoxy, pt-
Butylphenoxy, pt-octylphenoxy, m-
Pentadecylphenoxy, p-dodecyloxyphenoxy), and h is an integer of 1-2.

In the above formula [S-8], R ⁴⁶ and R ⁴⁷
, Which are the same as R ⁴² and R ^43, R ⁴⁸ are as defined above R ^45. i represents 0 to 4, and preferably 1 to 3.

In the above formula [S-9], R ⁴⁹ and R ⁵⁰
Is the same as the R ^30, R ³¹ and R ^32. j represents 1 or 2, and 1 is preferable.

The following are specific examples of the high boiling organic solvent (S-101 to S-101 as the compound represented by the above [S-1]).
23, S-2 as a compound represented by the above [S-2]
01 to 216, S-301 to S-305 as the compound represented by the above [S-3], S-401 to 406 as the compound represented by the above [S-4], and S-401 to the above [S-5] S-501 to 508 as the compound to be prepared,
S-601 to 609 as the compound represented by 6] and S-701 to 7 as the compound represented by the above [S-7]
08, S-8 as a compound represented by the above [S-8]
01 to 804, and S-901 to 902) as the compound represented by the above [S-9].

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In the present invention, the high boiling point organic solvent may be used alone or in combination of two or more.
For example, a combination use of tricresyl phosphate and dibutyl phthalate, a combination use of trioctyl phosphate and di (2-ethylhexyl) sebacate, and the like can be given.

Examples of compounds other than the above-mentioned high-boiling organic solvents and / or methods for synthesizing these high-boiling organic solvents include, for example, US Pat. Nos. 2,322,027 and
No. 2,533,514, No. 2,772,163, No. 2,835,579,
No. 3,594,171, No. 3,676,137, No. 3,689,271
No. 3,700,454, No. 3,748,141, No. 3,764,
No. 336, No. 3,765,897, No. 3,912,515, No. 3,
936,303, 4,004,928, 4,080,209, 4,127,413, 4,193,802, 4,207,393
No. 4,220,711, No. 4,239,851, No. 4,278,
No. 757, No. 4,353,979, No. 4,363,873, No. 4,
430,421, 4,430,422, 4,464,464, 4,483,918, 4,540,657, 4,684,606
No. 4,728,599, No. 4,745,049, No. 4,935,
Nos. 321 and 5,013,639, EP 276,319A, 286,253A, 289,820A, 309,158A,
309,159A, 309,160A, 509,311A, 51
No. 0,576A, East German Patent No. 147,009, No. 157,147, No. 159,573, No. 225,240A, British Patent No. 2,091,124A
No., JP-A-48-47335, JP-A-50-26530, JP-A-51-25133,
No. 51-26036, No. 51-27921, No. 51-27922, No. 51-149
028, 52-46816, 53-1520, 53-1521,
53-15127, 53-146622, 54-91325, 54-1
06228, 54-118246, 55-59464, 56-64333
No. 56-81836, No. 59-204041, No. 61-84641, No.
62-118345, 62-247364, 63-167357, 63
-214744, 63-301941, 64-9452, 64-945
No. 4, No. 64-68745, JP-A No. 1-101543, No. 1-102454
No. 2-792, No. 2-4239, No. 2-43541, No. 4-2923
No. 7, No. 4-30165, No. 4-232946, No. 4-346338, etc.

-Production of thermal ink-jet ink- A thermal ink-jet ink is produced by including an ink composition containing a dye dispersion, and the dye dispersion comprises at least the above-mentioned oil-soluble dye and a high boiling organic solvent. It is obtained by emulsifying and dispersing in an aqueous medium. (Emulsification Dispersion) Emulsification dispersion involves dispersing an oil phase obtained by dissolving an oil-soluble dye in a mixed solvent with a high-boiling organic solvent and, in some cases, a low-boiling organic solvent, in an aqueous phase mainly composed of water. This is done to make micro oil droplets. At this time, an additive such as a surfactant, a wetting agent, a dye stabilizer, an emulsion stabilizer, a preservative, and a fungicide described below is added to one or both of the aqueous phase and the oil phase as necessary. be able to. Specific examples of the dispersion method include a method of co-emulsifying and dispersing the oil-soluble dye and the high boiling point organic solvent (co-emulsification dispersion method). As the co-emulsification dispersion method, a method of adding an organic solvent phase (oil phase) containing an oil-soluble dye and a high-boiling organic solvent to an aqueous medium (aqueous phase) to make the oil phase finer is generally used. However, a so-called phase inversion emulsification method in which an aqueous phase is added to an organic solvent phase (oil phase) can also be suitably used.

Examples of the surfactant include fatty acid salts, alkyl sulfate salts, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonic acid formalin condensates, Anionic surfactants such as oxyethylene alkyl sulfates,
Nonionics such as polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, and oxyethylene oxypropylene block copolymer Surfactants and SURFYNOLS (Ai) which are acetylene-based polyoxyethylene oxide surfactants
rProducts & Chemicals)
Amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide,
No. 9-157,636, pages (37) to (38), Research Disclosure No. 308119 (1989) is also preferable.

For the purpose of stabilization immediately after emulsification, a water-soluble polymer can be added in combination with the surfactant. Examples of the water-soluble polymer include, for example, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polyacrylic acid, polyacrylamide and copolymers thereof, and polysaccharides, casein, natural water-soluble polymers such as gelatin, and the like. No.

In the case where the oil-soluble dye is dispersed into an aqueous ink by the emulsification dispersion, it is particularly important to control the particle size. In order to increase the color purity and density when an image is formed by an inkjet recording method, it is essential to reduce the average particle size of the dispersed particles in the dye dispersion, and the volume average particle size is preferably 100 nm or less, -50 nm is more preferable.

It was also found that the presence of coarse particles plays a very important role in printing performance. That is, it has been found that the coarse particles clog the nozzles of the head, or form dirt even if they are not clogged, causing non-ejection of the inkjet ink and / or the ejection to be disturbed, which has a significant effect on the printing performance. In order to prevent this, it is preferable to suppress the number of particles having a size of 5 μm or more to 10 or less and the number of particles having a size of 1 μm or more to 1000 or less in 1 μl of the ink.

As a method for removing these coarse particles, a known centrifugation method, microfiltration method, or the like can be used. These separation means may be performed immediately after emulsification and dispersion, or may be performed immediately after filling the ink cartridge after adding various additives such as a wetting agent and a surfactant to the emulsified dispersion. As an effective means for reducing the average particle size of the dispersed particles in the dye dispersion, and eliminating coarse particles,
An emulsifying and dispersing apparatus that performs mechanical stirring can be suitably used.

As the emulsifying and dispersing device used in the co-emulsifying and dispersing method, known devices such as a simple stirrer, an impeller stirring method, an in-line stirring method, a mill method such as a colloid mill, and an ultrasonic method can be used. In the present invention, a high-pressure emulsification dispersion device is preferable,
Among them, a high-pressure homogenizer is particularly preferable.

The high-pressure homogenizer is US-453.
No. 3,254, JP-A-6-47264, etc., a detailed mechanism is described, but as a commercially available device, a Gaulin homogenizer (APV GAULIN INC.),
Microfluidizer (MICROFLUIDEX
INC. ), Ultimateizer (Sugino Machine Co., Ltd.) and the like.

In recent years, US Pat.
The high-pressure homogenizer having a mechanism for atomization in an ultra-high-pressure jet stream as described in the above item is particularly effective for the emulsification and dispersion of the present invention. As an example of an emulsifying and dispersing apparatus using this ultrahigh-pressure jet stream, DeBEE2000 (BE
E INTERNATIONAL LTD. ).

The pressure at the time of emulsifying and dispersing using the high-pressure emulsifying and dispersing apparatus is preferably 50 MPa or more (500 bar or more), and 60 MPa or more (600 bar or more).
Is more preferable, and 180 MPa or more (1800 bar or more) is still more preferable. In the present invention, it is particularly preferable to use two or more emulsifiers in combination during the emulsification and dispersion, for example, by emulsifying with a stirring emulsifier and then passing through a high-pressure homogenizer. Further, it is also preferable that the emulsion is once emulsified and dispersed by these emulsifying apparatuses, and then an additive such as a wetting agent or a surfactant is added. Then, the ink is passed through a high-pressure homogenizer again while the ink-jet ink is filled in the cartridge.

In the present invention, an organic solvent phase (oil phase) containing an oil-soluble dye and a high boiling point organic solvent and an aqueous medium (aqueous phase) are used.
Before emulsifying and dispersing, the organic solvent phase has a boiling point of 150 ° C.
It is preferable that the following low-boiling organic solvent is added, and after the addition, the dispersion is emulsified and dispersed to obtain a dye dispersion, and then the low-boiling organic solvent is substantially removed from the dye dispersion. Removal of the low-boiling organic solvent is preferable from the viewpoint of stability of the dye dispersion (emulsion) and safety and health.

As a method for substantially removing the low-boiling organic solvent, various known methods, for example, an evaporation method, a vacuum evaporation method, an ultrafiltration method and the like are employed according to the kind of the low-boiling organic solvent. can do. The step of removing the low-boiling organic solvent is preferably performed as soon as possible immediately after emulsification.

The low boiling organic solvent has a boiling point of about 30 at normal pressure.
An organic solvent having a temperature of not less than 150 ° C. and not more than 150 ° C., for example, esters (eg, ethyl acetate, butyl acetate, ethyl propionate, β-ethoxyethyl acetate,
Methylcellosolve acetate), alcohols (eg, isopropyl alcohol, n-butyl alcohol, secondary butyl alcohol), ketones (eg, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone), amides (eg, dimethylformamide, N-
Preferred are methylpyrrolidone), ethers (eg, tetrahydrofuran, dioxane) and the like.

The aqueous medium was appropriately selected as necessary, based on water or a mixture of water and a small amount of a water-miscible organic solvent.
Additives such as surfactants, wetting agents, stabilizers and preservatives are added.

When the above-mentioned dye dispersion (dye dispersion) is used as a thermal inkjet ink, a drying inhibitor is used for the purpose of preventing clogging due to the drying operation at the ejection port (nozzle) of the inkjet ink. Penetration enhancer, UV absorber,
Additives such as antioxidants, fungicides, pH adjusters, surface tension adjusters, dispersants, dispersion stabilizers, defoamers, viscosity adjusters, rust preventives, chelating agents, etc. are appropriately selected and added in suitable amounts. Can be added.

As the anti-drying agent, 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. Polyhydric alcohols represented by -1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, trimethylolpropane, etc., ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ) Lower alkyl ethers of polyhydric alcohols such as ether, triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazoly Non, heterocyclic compounds such as N- ethylmorpholine, sulfolane, dimethyl sulfoxide, sulfur-containing compounds such as 3-sulfolene, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Among these, polyhydric alcohols such as glycerin and diethylene glycol are more preferable. They are,
One type may be used alone, or two or more types may be used in combination. These anti-drying agents are preferably added in an amount of 10 to 50% by weight in the inkjet ink.

Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and 1,2-hexanediol; sodium lauryl sulfate; sodium oleate; Nonionic surfactants listed as surfactants for use. These have a sufficient effect if added to the ink for ink jet in an amount of 10 to 30% by weight, and are added within a range that does not cause bleeding of a print and paper missing (print-through).

The above-mentioned ultraviolet absorbers are used for the purpose of improving the storability of an image.
Nos. 77, 61-90537 and JP-A-2-
No. 782, No. 5-1970075, No. 9-34
Benzotriazole compounds described in JP-A-557 / 057, JP-A-46-2784, JP-A-5-1944
No. 83, U.S. Pat. No. 3,214,463, benzophenone-based compounds described in JP-B-48-30492, JP-B-56-21141, and JP-A-10-881.
No. 06, etc., cinnamic acid-based compounds,
298503, 8-53427 and 8-
Nos. 339368, 10-182621, and JP-A-8-501291, and the like. 2423
Compounds described in No. 9 and compounds emitting fluorescent light by absorbing ultraviolet light represented by stilbene-based and benzoxazole-based compounds, so-called fluorescent whitening agents, and the like are also included.

The antioxidant is used for the purpose of improving the storability of an image, and examples thereof include various organic and metal complex antifading agents. 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-based anti-fading agent include a nickel complex, a zinc complex, and the like. No. 17643, Sections VII I through J; 15162; 18716 of 65
Page 0, left column, same No. No. 36544, page 527; 3
No. 07105, page 872; The compounds described in the patent cited in US Pat.
Preferred examples include compounds included in the general formulas and compound examples of typical compounds described on pages 127 to 137 of JP-A No. 195/1992.

Examples of the fungicide include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. Is mentioned. These are contained in the ink at 0.0
It is preferable to use 2 to 1.00% by weight.

Examples of the pH adjusting agent include hydroxides of alkali metals such as lithium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and sodium hydrogen carbonate, and the like.
Inorganic bases such as potassium acetate, sodium silicate and disodium phosphate, and organic bases such as N-methyldiethanolamine and triethanolamine are exemplified. From the viewpoint of improving the storage stability of the ink, the pH is preferably from 6 to 10, and more preferably from 7 to 10.

The surface tension of the ink is 20 to 60 m.
N / m is preferable, and 25 to 45 mN / m is more preferable. Examples of the surface tension adjusting agent that can be used for adjusting the surface tension include nonionic, cationic and anionic surfactants. For example, the surfactant used for the above emulsification and dispersion can be used. The surfactant used here has a solubility in water at 25 ° C. of 0.5%.
The above are preferred. In addition, as viscosity of the ink,
It is preferably at most 30 mPa · s, more preferably at most 20 mPa · s.

As the dispersant and the dispersion stabilizer,
Preferable examples include the above-mentioned cations, anions, and various nonionic surfactants. Examples of the antifoaming agent include chelating agents represented by fluorine-based and silicone-based compounds and EDTA. Various additives such as the above anti-drying agent are generally added to the emulsified dispersion after emulsification of the oil-soluble dye. Is also good.

-Image-Receiving Material- The image-receiving material is not particularly limited, and is a known recording material, that is, plain paper, resin-coated paper, for example, JP-A-8-1
Nos. 69172, 8-27693 and 2-2
Nos. 76670, 7-276789, 9-
323475, JP-A-62-28783, JP-A-10-153899, and 10-217
Nos. 473 and 10-235995 and 10-
JP-A-337947, JP-A-10-217597, and JP-A-10-337947, etc., include paper for exclusive use of ink jet, film, electrophotographic common paper, cloth, glass, metal, ceramics, and the like.

In the present invention, among the above-mentioned image receiving materials, recording paper and recording film having an image receiving layer on a support are particularly preferable.

As the support, LBKP, NBKP
Chemical pulp, GP, PGW, RMP, TMP, CT
It consists of mechanical pulp such as MP, CMP and CGP, waste paper pulp such as DIP, etc., and if necessary, mixes known additives such as pigments, binders, sizing agents, fixing agents, cationic agents, and paper strength enhancers. However, those manufactured by various apparatuses such as a fourdrinier paper machine and a round paper machine can be used, and in addition to these, synthetic paper, plastic film sheets and the like may be used. As the thickness of the support, 10 to 250
μm, and its basis weight is 10 to 250 g /
m ² is preferred.

On the support, the image receiving layer may be provided as it is, or a back coat layer may be further provided. Also, after providing a size press or an anchor coat layer with starch, polyvinyl alcohol or the like, An image receiving layer and a 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-mentioned supports, paper and plastic films laminated on both sides with a polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. In polyolefin polyolefin,
It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine, neodymium oxide).

The image receiving layer is provided on the support and contains a pigment and an aqueous binder. As the pigment,
Preferred are white pigments, such as calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina,
Inorganic pigments such as lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, zinc carbonate,
Organic pigments such as styrene-based pigments, acrylic-based pigments, urea resins, and melamine resins are preferably used. Among these white pigments, inorganic pigments are preferred,
Porous inorganic pigments are more preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, any of silicic anhydride obtained by a dry production method and hydrous silicic acid obtained by a wet production method can be used, but it is particularly preferable to use hydrous silicic acid.

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. Polymers, water-dispersible polymers such as styrene-butadiene latex, acrylic emulsions, and the like are included. These aqueous binders may be used alone or in combination of two or more. Among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are preferable in terms of adhesion to the pigment and peel resistance of the image receiving layer.

The image receiving layer may contain, in addition to the pigment and the aqueous binder, a mordant, a waterproofing agent, a light resistance improving agent, a surfactant and other additives.

It is preferable that the mordant is immobilized. For this purpose, a polymer mordant is preferably used. The polymer mordant is described in
No. 28325, No. 54-74430, No. 54-124
No. 726, No. 55-22766, No. 55-14233
No. 9, No. 60-23850, No. 60-23851,
No. 60-23852, No. 60-23853, No. 60
No.-57836, No. 60-60643, No. 60-11
No. 8834, No. 60-122940, No. 60-122
No. 941, No. 60-122942, No. 60-2351
No. 34, JP-A-1-161236, U.S. Pat. Nos. 2,484,430, 2,548,564 and 31,480.
No. 61, No. 3309690, No. 4115124, No. 4124386, No. 4193800, No. 42738
No. 53, No. 4,282,305, and No. 4,450,224. An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A-1-161236 is particularly preferred. By using the polymer mordant described in the publication, an image with excellent image quality is obtained, and the light fastness of the image is improved.

The water-proofing agent is effective for making the image water-resistant, and cationic resins are particularly preferred. Examples of the cationic resin, for example, polyamide polyamine epichlorohydrin, polyethylene imine, polyamine sulfone, dimethyl diallyl ammonium chloride polymer,
Examples thereof include cationic polyacrylamide and colloidal silica, and among these, polyamide polyamine epichlorohydrin is particularly preferable. The content of these cationic resins is 1 to 15 with respect to the total solid content of the image receiving layer.
% By weight, and particularly preferably 3 to 10% by weight.

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

The surfactant functions as a coating aid, a releasability improver, a slipperiness improver or an antistatic agent. The surfactant is described in JP-A-62-1734.
Nos. 63 and 62-183457. An organic fluoro compound may be used instead of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (eg, fluorine oil), and a solid fluorine compound resin (eg, ethylene tetrafluoride resin). The above-mentioned organic fluoro compounds are described in JP-B-57-9053 (Nos. 8 to 17).
Column), JP-A-61-20994 and JP-A-62-13582.
No. 6 describes each.

Examples of the other additives include a pigment dispersant, a thickener, a defoamer, a dye, a fluorescent brightener, a preservative, a pH adjuster, a matting agent, and a hardener. .
The image receiving layer may be a single layer or two or more layers.

The thickness of the image receiving layer is 10 to 50 μm.
m is preferable and 20 to 40 μm is more preferable.

The image receiving material may be provided with a back coat layer. Examples of components that can be added to the back coat layer include white pigments, aqueous binders, and other additives.

Examples of the white pigment contained in the back coat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, and the like.
Satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite,
White inorganic pigments such as aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, magnesium hydroxide, etc., organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsules, urea resin, melamine resin, etc. Is mentioned.

As the aqueous binder contained in the back coat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch,
Examples include water-soluble polymers such as cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, and polyvinylpyrrolidone, and water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion.

Other components contained in the back coat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a waterproofing agent.

A polymer latex may be added to the constituent layers (including the back coat layer) in the image receiving material. 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. The polymer latex is described in JP-A Nos. 62-245258 and 62-13166.
Nos. 48 and 62-11066. 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 coat layer, the back coat layer can be prevented from curling.

The ink jet recording method of the present invention is a thermal ink jet recording method, and the recording method includes:
Examples include a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different densities, and a method of using colorless and transparent ink.

[0180]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 <Preparation of Sample 101> 8 g of the magenta dye (exemplary compound M-6, oil-soluble dye) and 5 g of sodium dioctylsulfosuccinate described above were mixed with an organic solvent (exemplary compound S- 102) 7 g in 6 g, 10 g of the exemplified high boiling organic solvent (exemplified compound S-111) and 50 ml of ethyl acetate.
Dissolved at 0 ° C. 500 ml of deionized water is added to the solution while stirring with a magnetic stirrer,
An oil-in-water type coarse particle dispersion was prepared. Next, this coarse particle dispersion was subjected to a high-pressure emulsifier Microfluidizer (MICRO).
FLUIDEX INC) at 60MPa (600ba)
The particles were pulverized by passing them 5 times under the pressure of r).
Further, the resulting emulsion was desolvated by a rotary evaporator until the odor of ethyl acetate disappeared.
140 g of diethylene glycol, 50 g of glycerin and SURFY were added to the fine emulsion of the oil-soluble dye thus obtained.
NOL465 (Air Products & Chemic
(Als) and 900 ml of deionized water were added to prepare a light magenta ink (sample 101).

<Preparation of Sample 102> Exemplary high-boiling organic solvents (S-102, S-11) contained in the preparation of Sample 101
A sample 102 was prepared in the same manner as the sample 101, except that 1) was not used.

<Preparation of Sample 103> Instead of 6 g of the exemplified high-boiling organic solvent (S-102) and 10 g of the exemplified high-boiling organic solvent (S-111) contained in the preparation of Sample 101,
Sample 103 was prepared in the same manner as Sample 101, except that 16 g of the following comparative compound r-1 (acrylic polymer) was used.

(Preparation of Sample 104) Instead of 6 g of the exemplified high-boiling organic solvent (S-102) and 10 g of the exemplified high-boiling organic solvent (S-111) contained in the preparation of Sample 101,
A sample 104 was made in the same manner as the sample 101 except that 16 g of toluene was used.

(Preparation of Sample 105) In place of 6 g of the exemplified high-boiling organic solvent (S-102) and 10 g of the exemplified high-boiling organic solvent (S-111) contained in the preparation of Sample 101,
Sample 105 was prepared in the same manner as Sample 101, except that 16 g of cyclohexylbenzene was used.

(Preparation of Sample 106) Instead of 6 g of the exemplified high-boiling organic solvent (S-102) and 10 g of the exemplified high-boiling organic solvent (S-111) contained in the preparation of Sample 101,
Sample 1 was obtained except that 16 g of the following comparative compound r-2 was used.
Sample 106 was manufactured in the same manner as in Sample No. 01.

[0187]

Embedded image

(Preparation of Sample 107) Instead of the microfluidizer used for preparing Sample 101, a Gaulin homogenizer (APV GAULIN INC) was used and emulsified at 45 MPa (450 bar).
A sample 107 was manufactured in the same manner as the sample 101.

(Preparation of Sample 108) A high-speed impeller type homogenizer (manufactured by Nippon Seiki Co., Ltd.) was used in place of the microfluidizer (high-pressure emulsifier) used for preparing sample 101, and the rotation was performed at 10,000 rpm. Sample 1 was prepared in the same manner as Sample 101 except that the mixture was stirred and emulsified for one minute.
08 was produced.

(Preparation of Sample 109) Instead of the microfluidizer used for preparing Sample 101, DeBEE2
000 (BEE INTERNATIONAL LT
Sample 109 was prepared in the same manner as Sample 101 except that emulsification was performed using D) at a pressure of 210 MPa (2100 bar).
Was prepared.

(Preparation of Sample 110) Sample 110 was prepared in the same manner as Sample 101, except that in the preparation of Sample 101, ethyl acetate was not contained, and the step of removing the solvent with a rotary evaporator was not performed.

(Preparation of Sample 111) In place of the microfluidizer used for preparing Sample 110, DeBEE2
000 and emulsified at a pressure of 210 MPa (2100 bar) in the same manner as sample 101, except that
0 was produced.

Samples 101 to 1 obtained as described above
The light-magenta ink of No. 11 has a volume average particle size of
It was measured using Microtrac UPA (manufactured by Nikkiso Co., Ltd.). The measured results are shown in Table 1 below.

<Evaluation> Samples 101 to 111 were packed in cartridges of an ink jet printer BJ-F850 (manufactured by Canon Inc.), which is a thermal ink jet printing method, and an image was printed on the company's photo print paper using the same machine. Was evaluated. The results of the measurement and evaluation are shown in Table 2 below. -Printing performance- Continuous printing is performed, and (1) the ink ejection amount until the streak is generated and (2) the ink ejection amount until the ink becomes non-ejection are measured. A comparison was made with the case where genuine light magenta ink was used.

-Printing Performance- Each cartridge filled with the samples 101 to 111 was allowed to stand for one week in an environment of 60 ° C., and the same evaluation as the printing performance was performed using the ink state after standing and the cartridge after standing. The amount of each ink ejected when the test was performed was measured and compared in the same manner.

-Drying property- The drying property was evaluated by visually observing stains (rubbing stains) when touched with a finger immediately after printing. —Water Resistance— The water resistance was evaluated from this value by measuring the rate of decrease (%) in image density after immersing the printed image in water for 1 minute. It can be said that the range of the concentration reduction within 10% is a practical range.

(Example 2) Instead of the magenta dye M-6 (oil-soluble dye) used for producing the sample 101 of Example 1,
A sample was prepared in the same manner as in Example 1 except that the above-described cyan dye (exemplary compound C-1, oil-soluble dye) was used, and the same evaluation as in Example 1 was performed using the sample.
The same evaluation as in Example 1 was obtained by the above evaluation.

(Example 3) Instead of the magenta dye M-6 (oil-soluble dye) used for producing the sample 101 of Example 1,
A sample was prepared in the same manner as in Example 1 except that the following yellow dye Y-1 (oil-soluble dye) was used, and the same evaluation as in Example 1 was performed using the sample. The same evaluation as in Example 1 was obtained by the above evaluation.

[0199]

Embedded image

[0200]

[Table 1]

[0201]

[Table 2]

The cause of the discharge failure (streak, non-discharge) shown in Table 1 above was mainly due to kogation.
From the results in Table 1 above, in the samples containing the high-boiling organic solvents (samples 101 and 107 to 111 of each color), the generation of streaks and non-ejection due to kogation were suppressed, and the dispersion of the ink during storage over time was stable. Thus, a large number of images could be formed stably with high image quality. Further, it was excellent in water resistance after printing and also excellent in drying property, and generation of abrasion stain immediately after printing was not recognized. Above all, the ink finely dispersed by using a high-pressure emulsifying machine was particularly excellent in both printing stability and stability over time of the ink. On the other hand, samples without using high-boiling organic solvents (samples 102 to 106 of each color)
In this case, streaks and non-ejections due to kogation were likely to occur, and a large amount of continuous processing could not be performed. Further, the dispersion stability of the ink during storage over time was poor, and the dispersed particles were coarsened in the ink or the precipitation of the dye was recognized, so that sufficient ink performance could not be obtained. In the conventional product, although the ejection failure caused by kogation did not occur, the drying property and the water resistance were extremely low, and the image stability after printing was poor.

Example 4 An ink jet printer BJ-F850 (Canon Inc.) used in Example 1 and the like was used.
), A sample 101, a sample 102, and light magenta ink (conventional product; genuine for BJ-F850, Can)
on (manufactured by On Co., Ltd.), and an image was printed on PM photo paper manufactured by Epson Co., Ltd. using the same machine, and the same measurements and evaluations as in Example 1 were performed. The results of the measurement and evaluation are shown in Table 3 below.

[0204]

[Table 3]

Sample 101 containing a high boiling point organic solvent has a remarkable water resistance characteristic as compared with a commercially available water-soluble dye ink (conventional product: Canon light magenta ink), but has a similar property to the oil-soluble dye. In comparison with the sample 102 which did not use the high boiling point organic solvent, the non-thermal method has less usefulness in comparison with the use of the high boiling point organic solvent in the thermal method in which ejection failure due to kogation occurs. The result was obtained. Therefore, in the ink jet recording method of the present invention, the characteristics are remarkably exhibited by the thermal method.

[0206]

According to the present invention, there is no deterioration of the heating element due to adhesion of ink components to the surface of the heating element, burning (kogation), deposition, etc., and no clogging of nozzles, and there is no paper dependence. Excellent color development when printing on arbitrarily selected paper, excellent ink penetration into photographic quality paper, eliminating rubbing stains immediately after printing, and excellent water resistance after recording, high speed and high quality The present invention can provide a thermal inkjet recording method capable of recording an image. In addition to being excellent in handling, odor, and safety, there is no precipitation of dye, and the deterioration of the heating element due to adhesion of ink components to the surface of the heating element, burning (kogation), deposition, etc., and printing through a nozzle, etc. In the case of performing, there is no clogging of the nozzle tip and excellent ejection stability, there is no dependence on paper, excellent ink permeability at the time of recording, eliminating stains immediately after printing, and excellent color development, water resistance, It is possible to provide a method for producing a thermal inkjet ink capable of recording at high density and high image quality.

Claims (5)

[Claims] 1. An ink jet recording method using a thermal ink jet printing method, comprising: an ink containing a dye dispersion obtained by emulsifying and dispersing an oil-soluble dye dissolved in a high boiling organic solvent having a boiling point of 150 ° C. or higher in an aqueous medium. An ink jet recording method comprising recording on an image receiving material using a composition. 2. The ink jet recording method according to claim 1, wherein the high-boiling organic solvent contained in the dye dispersion has a relative dielectric constant of 3 to 12 at 25 ° C. 3. The ink jet recording method according to claim 1, wherein the average particle size of the dispersed particles in the dye dispersion is 100 nm or less. 4. The ink jet recording method according to claim 1, wherein the image receiving material has an image receiving layer containing a white pigment on a support. 5. A method for producing an ink for thermal inkjet, comprising emulsifying and dispersing an oil-soluble dye dissolved in a high-boiling organic solvent in an aqueous medium, wherein a low-boiling organic solvent having a boiling point of 150 ° C. or lower is added before emulsifying and dispersing. Wherein the low-boiling organic solvent is substantially removed from the dye dispersion after emulsification and dispersion.