JP2003221518A - Coloring composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide various kinds of coloring compositions such as an ink composition imparting a colored image forming material excellent in hue and fastness, an ink for ink jet printing, etc. <P>SOLUTION: The coloring compositions contains a medium and a compound expressed by following general formula (1). In the formula, R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>and R<SP>5</SP>are each H, a univalent substituent. The arbitrary two in the R<SP>1</SP>to R<SP>5</SP>mean Ra and Rb. A<SP>1</SP>and A<SP>2</SP>are each a (substituted) aryl group or heteroaryl group. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coloring composition used for image formation and the like, more specifically, ink, heat-sensitive recording material,
The present invention relates to a coloring composition used for color toners, color filters and the like.

[0002]

2. Description of the Related Art In recent years, as an image recording material, a material for forming a color image has been mainly used, and specifically, an ink jet recording material, a heat transfer recording material, and an electrophotographic recording material. Materials, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc. are widely used. Further, a color filter is used for recording and reproducing a color image in an image pickup device such as a CCD in a photographing device and in an LCD or a PDP in a display. In order to reproduce or record a full-color image in these color image recording materials and color filters, so-called additive and subtractive colorants of three primary colors are used. It is desired to have a robust dye that has the above properties and can withstand various use conditions and environmental conditions.

The ink jet recording method is rapidly spreading and further developing because of low material cost, high speed recording, low noise during recording, and easy color recording. is there. Ink jet recording methods include a continuous method for continuously ejecting droplets and an on-demand method for ejecting droplets according to an image information signal. The ejection method is a droplet that is applied with pressure by a piezo element. There are a method of ejecting liquid, a method of generating bubbles in the ink by heat to eject a droplet, a method of using ultrasonic waves, or a method of sucking and ejecting a droplet by electrostatic force. As the ink, water-based ink, oil-based ink, or solid (melting type) ink is used.

The dyes used in such inks have good solubility or dispersibility in a solvent, high density recording is possible, good hue, light, heat and environmental conditions. To be robust against the active gas (SOx in addition to oxidizing gas such as NOx and ozone), excellent in toughness against water and chemicals, good in fixing property to the image receiving material and difficult to bleed, It is required that the ink be excellent in storability, have no toxicity, have high purity, and be inexpensively available.
However, it is extremely difficult to search for a dye that meets these requirements at a high level. In particular, there is a strong demand for a dye that has a good hue and that is robust against active gases in the light and the environment, particularly oxidizing gases such as ozone.

In color copiers and color laser printers utilizing the electrophotographic system, toners in which a coloring material is dispersed in resin particles are generally widely used. As the performance required for color toner, absorption characteristics that can realize a preferable color reproduction range, especially Over Head Pr
The high transparency (transparency) which is a problem when used as an injector (hereinafter referred to as OHP), and various robustness under the environmental conditions used. A toner in which a pigment is used as a coloring material and dispersed in particles is disclosed in JP-A-62-157051.
No. 62-255956 and JP-A-6-11871.
As disclosed in No. 5, although these toners have excellent light resistance, they are insoluble and easily aggregate, which causes problems such as a decrease in transparency and a hue change of a transmitted color. On the other hand, a toner using a dye as a coloring material is disclosed in JP-A-3-276161.
Although disclosed in JP-A-7-209912 and JP-A-8-123085, these toners have high transparency and no hue change, but have a problem in light resistance.

The heat-sensitive transfer recording has advantages that the apparatus is small and the cost can be reduced, the operation and maintenance are easy, and the running cost is low. As the performance required for dyes used in thermal transfer recording, absorption characteristics capable of achieving a preferable color reproduction range, compatibility of heat transferability and fixability after transfer, thermal stability, and various robustness of the obtained image are obtained. However, none of the conventionally known dyes satisfy all of these performances. For example, for the purpose of improving fixability and light resistance, a heat-sensitive transfer recording material and an image forming method in which a heat-diffusible dye is chelated by a transition metal ion previously added to an image receiving material are disclosed in JP-A-60-239.
No. 8, etc., the absorption characteristics of the chelate dye formed are unsatisfactory, and there are environmental problems due to the use of transition metals.

Since the color filter is required to have high transparency, a method called a dyeing method for coloring with a dye has been performed. For example, a color filter can be manufactured by sequentially repeating a method of forming a pattern by subjecting a dyeable photoresist to pattern exposure and development, and then dyeing with a filter color dye for all filter colors. In addition to the dyeing method, the color filter can be produced by a method using a positive type resist described in US Pat. No. 4,808,501 and JP-A-6-35182. These methods have a high transmittance due to the use of a dye, and the optical characteristics of the color filter are excellent, but there is a limit to light resistance and heat resistance, and a dye having excellent various resistance and high transparency is desired. Was there. On the other hand, a method of using an organic pigment having excellent light resistance and heat resistance instead of the dye is widely known, but it is difficult to obtain optical characteristics like a dye with a color filter using the pigment.

The dyes used in each of the above-mentioned applications must have the following properties in common. That is, it has favorable absorption characteristics in terms of color reproducibility, fastness under the environmental conditions used, for example, light resistance, heat resistance, moisture resistance, resistance to oxidizing gases such as ozone, and other chemical resistance fastness such as sulfurous acid gas. And the molar absorption coefficient is high.

Conventionally, phenol, naphthol, aniline and the like have been widely used as a coupling component for azo dyes. As an azo dye having a good hue obtained by these coupling components, JP-A-11-209673 can be used.
Although the dyes disclosed in Japanese Patent No. 3020660 and Japanese Patent No. 3020660 are known, they have a problem of poor light fastness. To improve this, a dye having a good hue and improved light fastness has recently been disclosed in Japanese Patent Application No. 2000-220649. However, all of the dyes known in the above patents have extremely insufficient fastness to oxidizing gases such as ozone. The inventor of this patent is to break away from conventional coupling components such as phenol, naphthol and aniline in order to develop a dye that is robust against oxidizing gases such as ozone,
The idea of using a nitrogen-containing heterocyclic compound as a coupling component has been reached. To date, patents relating to azo dyes containing pyridine or pyrazine as a coupling component include JP-A-49-74718, EP23309, and D.
E2513949, DE283202, DE25
No. 25505 and the like are known, but it was not known at that time to use these dyes in ink-jet inks, and in the azo dyes described in these,
The robustness against light, heat, humidity and active gas in the environment was insufficient.

On the other hand, examples of bisazo compounds in which two or more aromatic groups are bonded to one pyridine ring via an azo group are those bonded to the 3- and 5-positions of the pyridine ring, respectively. As US-1680109, US-39
23780, J. Am. Chem. Soc. 19
34, 56, 1711, J. Hete
rocycl. Chem. 1969, Volume 6,
447, J. Pharm. Sci. 1970
Year, 59 volumes, 1031 pages, J. Heteroc
ycl. Chem. 1971, Volume 8, 841
Page, J. Heterocycl. Chem.
1975, Vol. 12, pp. 789, as bound to the 2- and 5-positions, respectively, Tetra
hedron Lett. 1993, Volume 34,
2019 page, Tetrahedron 1994
Year, 50, 4995, etc., but all of them are aryl groups as aromatic groups,
No bisazo compound having a heteroaryl group bonded thereto has been known so far. Further, there is no known example of using these compounds as a coloring component in a coloring composition.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems of the prior art and achieve the following objects. That is, the present invention includes: 1) an ink for printing such as an ink jet, an ink sheet in a thermal recording material, a color toner for electrophotography, which gives a colored image or a coloring material excellent in hue and fastness;
Provided are various colored compositions such as color filters used in displays such as LCDs and PDPs and image pickup devices such as CCDs. 2) Use of the colored compositions has a good hue and active gas in light and environment. Another object of the present invention is to provide an ink capable of forming an image having high fastness to ozone gas and an inkjet recording method suitable for this ink.

[0012]

Means for Solving the Problems The present inventor has studied the azo compound in detail with the aim of providing a colored composition having a good hue and high fastness to light and ozone.
The present invention has been completed by finding that the above-mentioned problems can be solved by a coloring composition containing a bisazo compound represented by the following general formula (1) having a specific dye structure.
Means for solving the above problems are as follows.
That is, 1. A coloring composition comprising a compound represented by the following general formula (1).

[0013]

[Chemical 2]

In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or a monovalent substituent. However, any two of R ^{1 to} R ⁵ represent Ra and Rb. A ¹ and A ² each represent a substituted or unsubstituted aryl group or heteroaryl group. 2. The compound represented by the general formula (1) is represented by the following general formula (1
The coloring composition as described in 1 above, which is represented by a).

[0015]

[Chemical 3]

Wherein R ²³ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹
Represents a hydrogen atom or a monovalent substituent. A ²¹ and A ²²
Represents a substituted or unsubstituted aryl group or heteroaryl group. 3. An ink containing the coloring composition as described in 1 or 2 above. 4. The ink according to item 3, which is for inkjet. 5. An ink jet recording method, wherein an image is formed on an image receiving material having an ink image receiving layer containing white inorganic pigment particles on a support, using the ink described in 4 above. 6. An ink sheet for a heat-sensitive recording material, containing the coloring composition as described in 1 or 2 above. 7. A color toner comprising the coloring composition as described in 1 or 2 above. 8. A color filter comprising the coloring composition as described in 1 or 2 above.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In addition, in this specification, "-" shows the range which includes the numerical value described before and behind that as a minimum value and a maximum value, respectively.

The coloring composition of the present invention is characterized by containing a compound represented by the general formula (1). The compound (1) will be described in detail. In the formula (1), R ¹ , R ² , R ³ ,
R ⁴ and R ⁵ each represent a hydrogen atom or a monovalent substituent. The monovalent substituent is preferably a halogen atom,
Alkyl group (including cycloalkyl group and bicycloalkyl group), alkenyl group (including cycloalkenyl group and bicycloalkenyl group), alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group,
Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, Alkyl and aryl sulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups,
Examples include carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group and silyl group. Among the above substituents, those having a hydrogen atom may be substituted with the above groups after removing the hydrogen atom.

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are preferably hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups, heterocyclic groups and cyano. Group, hydroxyl group, nitro group, carboxyl group (which may be further substituted by an alkyl group having 1 to 3 carbon atoms), alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, amino group, acylamino group, A sulfo group, an alkoxycarbonyl group, and a carbamoyl group. More preferably, it is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an amino group or a carboxyl group. Particularly preferred are hydrogen atom, methyl group, ethyl group, amino group and carboxyl group.

Any two of R ^{1 to} R ⁵ represent Ra and Rb. Ra and Rb may be any of R ^{1 to} R ⁵ , but R ² and R ⁴ are particularly preferable.

In Ra and Rb, A ¹ and A ² each represent a substituted or unsubstituted aryl group or heteroaryl group. A ¹ and A ² may be the same or different. At least one of A ¹ and A ² is preferably a heteroaryl group, and more preferably both are heteroaryl groups.

Specific examples of the aryl group include a phenyl group and a naphthyl group. The aryl group may have a substituent at any position, and the substituents on the aryl group may bond to each other to form a condensed ring.

Specific examples of the heteroaryl group include a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a triazolyl group, a furyl group, an isoxazolyl group, an oxazolyl group,
Examples thereof include thienyl group, isothiazolyl group, thiazolyl group, oxadiazolyl group, thiadiazolyl group, pyridyl group, pyridazinyl group, pyrimidinyl group and pyrazinyl group. The heteroaryl group may have a substituent at any position. Examples of the substituent include the above-mentioned examples of the monovalent substituent. Substituents on the heteroaryl group may combine with each other to form a condensed ring. Further, the nitrogen atom in the heteroaryl group may be quaternized. The heteroaryl group is preferably a pyrazolyl group, an imidazolyl group, a triazolyl group, an oxazolyl group, a thienyl group, a thiazolyl group or a thiadiazolyl group. Particularly preferred is a pyrazolyl group.

The compound (1) is more preferably represented by the compound (1a). That is, it is preferable that the azo group is bonded to the 3 and 5 positions of the pyridine ring and the 2 and 6 positions are amino groups.

R^{twenty three}, A^{twenty one}And A^{twenty two}Respectively above
R³, A¹And A²Is synonymous with. R²⁶, R²⁷,
R²⁸And R²⁹Are hydrogen atom or monovalent substitution, respectively.
Represents a group. Examples of the monovalent substituent include the monovalent substituents described above.
An example is given. R²⁶~ R²⁹As the substitution
Rui or unsubstituted alkyl group, aryl group, heterocyclic group,
An acyl group and a sulfo group. More preferably replacement or
Is an unsubstituted alkyl group, aryl group, or heterocyclic group
It Particularly preferably, R²⁶And R ²⁸Is a hydrogen atom, R²⁷
And R²⁹Is a substituted or unsubstituted aryl group
is there. Also, R²⁶And R²⁷, R²⁸And R²⁹Combined with a pair of
A ring containing a nitrogen atom may be formed.

Examples of the aryl group or heteroaryl group represented by A ¹ and A ^{2 in} the compound (1) and A ²¹ and A ²² in the compound (1a) include the following. The position where the azo group is substituted is marked with *.

[0027]

[Chemical 4]

[0028]

[Chemical 5]

[0029]

[Chemical 6]

Examples of the substituted pyridine ring partial structure excluding the two azo groups in the compound (1) include the following. The substituted pyridine ring partial structure excluding two azo groups is a structure formed by removing two hydrogen atoms on the pyridine ring from the following structures. The position at which the aryl group or the heteroaryl group is bonded via the azo group can be arbitrarily selected except the position having a substituent other than a hydrogen atom.

[0031]

[Chemical 7]

[0032]

[Chemical 8]

[0033]

[Chemical 9]

Specific examples of the compound (1) include specific examples a (1-66) of the substituents on the azo group and specific examples b (101-160) of the substituted pyridine ring partial structure excluding Ra and Rb.
Is a combination of substituents and is described by a combination of a number and a substitution position. For example, at the 3-position of the pyridine ring represented by b101 at the 4-position of the aryl group of the specific example a (2) and at the 5-position of the pyridine ring at the 5-position of the heteroaryl group of the specific example a (11). A compound bonded via a group is represented by "3- (4-2) -5- (5-11) -101". In addition, “4-2” in the above notation (4-2), (5-1
The "5-" in 1) may be deleted, and in that case, the specific example a (2) means that the substitution position to the azo group is not limited. Further, the position numbers of the substituents of the obtained compound (1) shall be in accordance with IUPAC. However, the present invention is not limited to these. In the present specification, Me is a methyl group, Et is an ethyl group, P is
h is a phenyl group, i-Pr is an isopropyl group, n-Bu
Represents a normal butyl group, t-Bu represents a tertiary butyl group, and Ac represents an acetyl group.

The compound (1) may be synthesized by any method. Regarding the azo group in the compound (1), “New Experimental Chemistry Lecture 14 Synthesis and Reaction III of Organic Compounds” edited by The Chemical Society of Japan (1978, Maruzen), 1516-1
534, S.S. R. Sandler, W.M. K
aro "Organic Functional"
Group Preparations Volume
II ”(1971, Academic Pre
ss) Chapter 14, pages 286 to 342, and the like. Among them, a) a primary aniline or a heterocyclic primary amine is reacted with a diazotizing agent to form a diazonium salt, and b) the diazonium salt is reacted with a coupler component to synthesize via a diazo coupling. Is particularly preferred.

Compound (1) has two azo bonds
However, these bonds continuously undergo azo coupling.
Even if it is formed by tracing, one of the azo bonds is formed
Isolated monoazo intermediate and reacted again with diazotizing agent
Alternatively, the other azo bond may be formed. Also isolated
The intermediates used as the diazo component
It may be azo coupled. A place to isolate intermediates
In the case of continuous diazo coupling,
Functional group conversion or the like may be performed before that. A ¹And A²
If they are the same, perform coupling one by one
It is also possible to use two or more equivalents of the diazotizing agent as the coupling agent.
Two azo bonds are formed at once by reacting with each other
You may let me. A¹And A²If different, only one azo binding
The formed monoazo intermediate was isolated to give the next diazocap
Although it is preferable to perform pulling,
After completion of pulling, add the next diazotizing agent.
The reaction may be carried out. In addition, the synthesis of compound (1)
In, even if the final step is diazo coupling,
It may be a functional group conversion reaction other than that.

The step of forming a diazonium salt from a heterocyclic primary amine is described in Chem. Rev. 1975
Year, Vol. 75, page 241 can be referred to. As the diazotizing agent, a dilute hydrochloric acid aqueous solution of sodium nitrite, isopentyl nitrite, nitrosyl sulfuric acid, or the like can be used.

A pyridine derivative which is a coupling component used in the synthesis of the compound (1) is described in JP-A-51-836.
31, JP-A-49-74718, JP-B-52-4623.
It can be synthesized by utilizing the method described in "0."

The azo group in the compound (1) has an azo type (-N = N-) and a hydrazo type (= N) depending on the structure of the compound.
-NH-) can be used, but in the present invention, all are described as the azo type. Even when other tautomers exist in the compound (1), they are described as one of the typical forms in the present specification, but tautomers different from those described in the present specification are also included. Included in the present invention.

The compound (1) also includes a compound with a counter salt due to its synthetic process, isolation method and the like. The counter salt may be any salt, and examples thereof include a halogen ion, a sulfate ion, a nitrate ion, a carbonate ion, a sulfonate ion, a phosphate ion, an acetate ion, a metal ion and an ammonium ion. Depending on the structure, an inner salt may be formed.

Further, the present invention can be applied even if the compound (1) contains an isotope (eg ² H, ³ H, ¹³ C, ¹⁵ N).

Applications of the coloring composition of the present invention containing the compound (1) include image-forming materials for forming images, especially color images. Specifically, there are ink-jet recording materials, heat-sensitive transfer image recording materials, pressure-sensitive recording materials, electrophotographic recording materials, transfer silver halide photosensitive materials, printing inks, recording pens, etc., An inkjet recording material, a heat-sensitive transfer type image recording material and a recording material using an electrophotographic method are preferable, and an inkjet recording material is more preferable. Also, U.S. Pat. No. 4,808,501, JP-A-6-
It can also be applied to color filters used in solid-state imaging devices such as LCDs and CCDs described in No. 35182, and dyeing solutions for dyeing various fibers.

The compound (1) is used after adjusting the substituents according to the required physical properties such as solubility, dispersibility and heat transfer property suitable for its use. Further, the use form of the compound (1) is not particularly limited as long as it is a composition, and dissolution, emulsion dispersion,
Furthermore, it can also be used in solid dispersion. Hereinafter, applications of the coloring composition of the present invention will be individually described in detail.

[Ink] The ink of the present invention can be prepared by dissolving and / or dispersing the compound (1) in a lipophilic medium or an aqueous medium, and preferably an aqueous medium is used. Since the ink of the present invention contains the dye having excellent weather resistance as described above, it can be suitably used as an ink for inkjet recording. If necessary, other additives are contained within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, permeation accelerators, ultraviolet absorbers, preservatives, anti-mold agents, pH.
Known additives such as regulators, surface tension regulators, defoamers, viscosity regulators, dispersants, dispersion stabilizers, rust preventives, chelating agents and the like can be mentioned. In the case of water-soluble ink, these various additives are added directly to the ink liquid. When the oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after preparation of the dye dispersion, but it may be added to the oil phase or the water phase during the preparation. The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the inkjet ink at the ink ejection port of the nozzle used in the inkjet recording system.

The drying inhibitor is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivative, glycerin. , Lower alkyl ethers of polyhydric alcohols such as trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, etc. , 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocycles such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferable. The above-mentioned anti-drying agents may be used alone or in combination of two or more kinds. These drying inhibitors are contained in the ink in an amount of 10 to 50% by mass.
It is preferable to contain.

The penetration enhancer is preferably used for the purpose of allowing the ink jet ink to better penetrate the paper.
As the penetration enhancer, alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants may be used. it can. When these are contained in the ink in an amount of 5 to 30% by mass, a sufficient effect is usually obtained, and it is preferable to use them in an addition amount range that does not cause bleeding of printing and paper drop (print through).

The ultraviolet absorber is used for the purpose of improving the storability of images. Examples of the ultraviolet absorber include JP-A-58-185677 and JP-A-61-190537.
Japanese Patent Laid-Open No. 2-782 and Japanese Patent Laid-Open No. 5-97075.
And benzotriazole compounds described in JP-A-9-34057, JP-A-46-2784,
Japanese Unexamined Patent Publication No. 5-194843, U.S. Pat. No. 32,144
No. 63, etc., benzophenone compounds, JP-B-48-30492, JP-A-56-21141,
Cinnamic acid compounds described in JP-A-10-88106 and the like, JP-A-4-298503 and 8-534.
No. 27, No. 8-239368, No. 10-18.
No. 2621, Japanese Patent Publication No. 8-501291, etc., triazine compounds, Research Disclosure No. Compounds described in JP-A No. 24239, stilbene compounds and benzoxazole compounds, which fluoresce by absorbing ultraviolet rays, so-called fluorescent whitening agents can also be used.

The anti-fading agent is used for the purpose of improving the storability of images. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Hydroquinones as organic anti-fading agents,
Alkoxyphenols, dialkoxyphenols,
There are phenols, anilines, amines, indanes, chromanes, alkoxyanilines, heterocycles and the like, and metal complexes include nickel complexes and zinc complexes. More specifically, Research Disclosure No.
17643, Item VII, I through J, ibid. 1516
2, the same No. 18716, page 650, left column, same No. 36
544, page 527, ibid. 307105, page 872,
Same No. The compounds described in the patent cited in 15162 and pages 127 to 13 of JP-A No. 62-215272.
The compounds included in the general formulas of the representative compounds and the compound examples described on page 7 can be used.

As the antifungal agent, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-
Examples thereof include 1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are 0.02 to 0.02 in the ink.
It is preferable to use 1.00% by mass.

The neutralizer (organic base, inorganic alkali) can be used as the pH adjuster. The pH
The adjusting agent has a pH of 6 to 10 for the purpose of improving the storage stability of the inkjet ink.
It is preferable to add it for summer, and it is more preferable to add it so as to have a pH of 7 to 10.

Examples of the surface tension adjusting agent include nonionic, cationic or anionic surfactants. still,
The surface tension of the inkjet ink containing the coloring composition of the present invention is preferably 20 to 60 mN / m. 25 ~
45 mN / m is preferred. The viscosity of the inkjet ink of the present invention is preferably 30 mPa · s or less. It is more preferable to adjust to 20 mPa · s or less. Examples of the surfactant include fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, dialkylsulfosuccinate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkyl sulfate. Anionic surfactants such as ester salts, 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 Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (AirProdu) which is an acetylene-based polyoxyethylene oxide surfactant is used.
(cts & Chemicals) is also preferably used. Further, amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide are also preferable. In addition, Japanese Patent Laid-Open No. 59-157,636 (3)
7)-(38) pages, Research Disclosure N
o. What was mentioned as a surfactant of 308119 (1989) can also be used.

As the antifoaming agent, a fluorine-based compound, a silicone-based compound, a chelating agent typified by EDTA, or the like can be used if necessary.

When the compound (1) is dispersed in an aqueous medium, it is disclosed in JP-A No. 11-286637 and Japanese Patent Application No. 2000-7.
8491, 2000-80259, 2000-
No. 62370, a colored fine particle containing a compound and an oil-soluble polymer is dispersed in an aqueous medium, or Japanese Patent Application No.
0-78454, 2000-78491, 20
It is preferable to disperse the compound (1) dissolved in a high-boiling point organic solvent in an aqueous medium as described in Nos. 00-203856 and 2000-203857. The specific method for dispersing the compound (1) in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount thereof are preferably those described in the above-mentioned patent. it can. Alternatively, the bisazo compound may be dispersed in a fine particle state as it is as a solid. At the time of dispersion, a dispersant or a surfactant can be used.

As a dispersing device, a simple stirrer or impeller stirring system, in-line stirring system, mill system (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic system, high pressure emulsification dispersion system (High-pressure homogenizer; specific commercially available devices include Gohlin homogenizer, microfluidizer, DeBEE2000, etc.) can be used. Regarding the method for preparing the above ink jet recording ink, in addition to the above-mentioned patent, JP-A-5-1484 is also available.
No. 36, No. 5-295312, No. 7-97541,
7-82515, 7-118584, JP-A-1
The details are described in JP-A Nos. 1-286637 and 2000-87539, and can be used for preparing the ink for inkjet recording of the invention.

As the aqueous medium, a mixture containing water as a main component and, if desired, a water-miscible organic solvent added thereto can be used. Examples of the water-miscible organic solvent include alcohols (for example, methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol,
sec-butanol, t-butanol, pentanol,
Hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (eg ethylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol) Monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amines (e.g., ethanolamine, diethanolamine,
Triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-
Ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2- Pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-
Oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). The water-miscible organic solvent may be used in combination of two or more kinds.

It is preferable that the compound (1) is contained in an amount of 0.2% by mass or more and 20% by mass or less based on 100% by mass of the ink of the present invention. Further, in the inkjet ink of the present invention, other dyes may be used in combination with the compound (1). When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range.

The ink and ink jet recording ink of the present invention can be used not only for forming a single color image but also for forming a full color image. In order to form a full-color image, yellow tone ink, magenta tone ink,
In addition, a cyan color tone ink can be used, and a black color tone ink may be further used to adjust the color tone. In addition to the compound (1), other dyes having a similar color tone may be used in combination.

Any applicable yellow dye can be used. For example, an aryl or heterylazo dye having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, and open chain active methylene compounds as a coupling component (hereinafter referred to as a coupler component); for example, a coupler component Azomethine dyes having open-chain type active methylene compounds and the like; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other dyes Examples of the seed include quinophthalone dye, nitro / nitroso dye, acridine dye, acridinone dye and the like.

Any magenta dye can be used as the applicable magenta dye. For example, aryl or heterylazo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles, etc. as coupler components; for example, arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, Methine dyes such as oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc., quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycycles such as dioxazine dyes, etc. Examples thereof include dyes. Further, two or more kinds of the dyes of the present invention may be used in combination.

Any applicable cyan dye can be used. For example, aryl or heterylazo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having phenols, naphthols, heterocycles such as pyrrolotriazole as coupler components, cyanine dyes, oxonol dyes, Examples thereof include polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes. Each of the above dyes may be one that exhibits yellow, magenta, and cyan colors only after a part of the chromophore is dissociated, in which case the counter cation is an alkali metal or an inorganic cation such as ammonium. It may be an organic cation such as a pyridinium or a quaternary ammonium salt, or a polymer cation having a partial structure of them. Examples of applicable black materials include disazo, trisazo, and tetraazo dyes, and carbon black dispersions.

Next, the ink jet recording method preferably used for the ink of the present invention will be described. [Inkjet recording method] In the inkjet recording method, energy is applied to the inkjet recording ink to obtain a known image receiving material, that is, plain paper, resin-coated paper,
For example, JP-A-8-169172 and JP-A-8-2769.
No. 3, gazette No. 2-276670 gazette, and No. 7-2767.
No. 89, No. 9-323475, and Japanese Patent Laid-Open No. 62-
No. 238,83, JP-A Nos. 10-153989, 10-217473, and 10-23599.
5, gazette 10-337947, gazette 10-21.
Images are formed on inkjet-dedicated paper, film, electrophotographic common paper, cloth, glass, metal, ceramics, etc. described in Japanese Patent Nos. 7597 and 10-337947.

When forming an image, a polymer latex compound may be used together for the purpose of imparting glossiness, water resistance and improving weather resistance. The latex compound may be applied to the image receiving material before, after, or at the same time as the application of the colorant, so that the place of addition is also in the image receiving paper, It may be in the ink or may be used as a liquid substance of the polymer latex alone. Specifically, Japanese Patent Application No. 2000-36
3090, 2000-315231, 2000-3
54380, 2000-343944, 2000-
268952, 2000-299465, 2000
The method described in -297365 can be preferably used.

A recording paper and a recording film for ink jet printing in which the ink of the present invention is used will be described. The support for recording paper and recording film is LBK.
Chemical pulp such as P, NBKP, GP, PGW, RMP,
Mechanical pulp such as TMP, CTMP, CMP, CGP, D
It is made of waste paper pulp such as IP, and if necessary, conventionally known pigments, binders, sizing agents, fixing agents, cationic agents,
It is possible to use those produced by mixing additives such as a paper strength enhancer and produced by various devices such as a Fourdrinier paper machine and a cylinder paper machine.
In addition to these supports, synthetic paper or plastic film sheet may be used, and the thickness of the support is 10 to 2
50 μm, and the basis weight is preferably 10 to 250 g / m ² . The support may be provided with the ink receiving layer and the back coat layer as it is, or may be provided with the ink receiving layer and the back coat layer after the size press or the anchor coat layer is provided with starch, polyvinyl alcohol or the like. Further, the support may be subjected to flattening treatment by a calendar device such as a machine calendar, a TG calendar and a soft calendar. As the support, both surfaces of the polyolefin (for example,
Paper and plastic films laminated with polyethylene, polystyrene, polyethylene terephthalate, polybutene and their copolymers) are more preferably used. It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine blue, neodymium oxide) to the polyolefin.

The ink receiving layer provided on the support is
It contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. As the white pigment contained in the ink receiving layer, a porous inorganic pigment is preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, both silicic acid anhydride obtained by the dry production method and hydrous silicic acid obtained by the wet production method can be used, but it is particularly preferable to use hydrous silicic acid.

As the aqueous binder contained in the ink receiving layer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivative. Water soluble polymer such as styrene butadiene latex,
Examples thereof include water-dispersible polymers such as acrylic emulsion. These aqueous binders can be used alone or in combination of two or more. In the present invention, among them, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peeling resistance of the ink receiving layer. The ink receiving layer may contain a mordant, a water-proofing agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used. Regarding the polymer mordant, JP-A-48-28325 and JP-A-54-74430 are used.
No. 54-124726, No. 55-22766,
No. 55-142339, No. 60-23850, No. 6
0-23851, 60-2852, 60-2
3853, 60-57836, 60-6064.
No. 3, No. 60-118834, No. 60-122940
No. 60-122941, No. 60-122942
No. 60-235134, JP-A-1-161236.
Publications, US Pat. Nos. 2,484,430 and 25,485.
No. 64, No. 3148061, No. 3309690, No. 4115124, No. 4124386, No. 41938.
No. 00, No. 4273853, No. 4282305, and No. 4450224. JP-A-1-
An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A-161236 is particularly preferable. When the polymer mordant described in the publication is used, an image with excellent image quality can be obtained and the light resistance of the image can be improved.

The water-proofing agent is effective for making the image water-proof, and as these water-proofing agents, cationic resins are particularly desirable. As such a cationic resin, polyamide polyamine epichlorohydrin, polyethyleneimine,
Examples thereof include polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. The content of these cationic resins is preferably 1 to 15% by mass based on the total solid content of the ink receiving layer, and particularly 3
It is preferably from 10 to 10% by mass.

Examples of the light resistance improver include zinc sulfate, zinc oxide, hindered amine antioxidants, and benzophenone or benzotriazole ultraviolet absorbers. Of these, zinc sulfate is particularly preferable.

The above-mentioned surfactant functions as a coating aid, a peeling property improving agent, a sliding property improving agent or an antistatic agent. For the surfactant, see JP-A-62-173463.
No. 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 (for example, fluorine oil) and a solid fluorine compound resin (for example, tetrafluoroethylene resin). Regarding organic fluoro compounds, JP-B-57-9053 (columns 8 to 17), JP-A-61-2
It is described in each publication of 0994 and 62-135826. Other additives added to the ink receiving layer include pigment dispersants, thickeners, defoamers, dyes, optical brighteners,
Preservatives, pH adjusters, matting agents, hardeners and the like can be mentioned. The ink receiving layer may be one layer or two layers.

A back coat layer may be provided on the recording paper and the recording film, and components that can be added to this layer include a white pigment, an aqueous binder, and other components. 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, satin white, and aluminum silicate. , Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite,
Examples thereof include white inorganic pigments such as hydrolyzed halloysite, magnesium carbonate and magnesium hydroxide, organic pigments such as styrene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, urea resins and melamine resins.

The aqueous binder contained in the back coat layer includes styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin. , Water-soluble polymers such as carboxymethyl cellulose, hydroxyethyl cellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the back coat layer include a defoaming agent, a defoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water resistance agent.

Polymer latex may be added to the constituent layers (including the back coat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, and film crack prevention. Regarding the polymer latex, JP-A Nos. 62-245258 and 62-1
It is described in each publication of 316648 and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking or curling of the layer can be prevented. Curling can also be prevented by adding a polymer latex having a high glass transition temperature to the back coat layer.

The ink jet recording method to which the ink of the present invention is applied is not limited, and known methods such as a charge control method for ejecting ink by utilizing electrostatic attraction, and a drop utilizing vibration pressure of a piezo element are used. On-demand method (pressure pulse method), acoustic ink jet method in which electric signals are converted into acoustic beams to irradiate ink, and ink is ejected using radiation pressure; and pressure generated by heating ink to form bubbles It is used for a thermal ink jet system and the like. The inkjet recording method uses a method of ejecting a large number of low density inks called photo ink in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue but different densities, and a colorless transparent ink. Method is included.

[Color Toner] As the binder used for the present invention, that is, the binder resin for the color toner into which the compound (1) is introduced, all commonly used binders can be used. For example, styrene resin, acrylic resin, styrene / acrylic resin, polyester resin, etc. may be mentioned. Inorganic fine powder or organic fine particles may be externally added to the toner for the purpose of improving fluidity and controlling charging. Silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. In addition,
These preferably have a number average primary particle diameter of 10 to 500 nm, and more preferably 0.1 to 20% by mass in the toner.

As the release agent, all the release agents which have been conventionally used can be used. Specific examples thereof include olefins such as low molecular weight polypropylene / low molecular weight polyethylene / ethylene-propylene copolymer, and microcrystalline wax / carnauba wax / sazol wax / paraffin wax. The addition amount of these is preferably 1 to 5% by mass in the toner.

The charge control agent may be added if necessary, but a colorless one is preferable from the viewpoint of color developability. Examples thereof include those having a quaternary ammonium salt structure and those having a calixarene structure.

As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron and ferrite, or a resin coated carrier in which the surface of the magnetic material particles is coated with a resin may be used. The volume average particle diameter of the carrier is preferably 30 to 150 μm.

The image forming method to which the color toner of the present invention is applied is not particularly limited. For example, a method of repeatedly forming a color image on a photoconductor and then transferring the image, or a method of forming an image Examples include a method in which images formed on the body are sequentially transferred to an intermediate transfer member or the like, a color image is formed on the intermediate transfer member or the like, and then transferred to an image forming member such as paper to form a color image.

[Heat-sensitive transfer material] The heat-sensitive recording material has moved in accordance with the ink sheet in which the compound (1) is coated on the support together with the binder, and the heat energy applied from the thermal head according to the image recording signal. It consists of an image-receiving sheet that fixes the dye. Ink sheet,
It is formed by dissolving the compound (1) in a solvent together with a binder or by dispersing the compound (1) into fine particles in the solvent to prepare an ink liquid, coating the ink on a support and appropriately drying. be able to. A preferred binder resin, ink solvent that can be used,
Regarding the support and further the image receiving sheet, see JP-A-7-13.
What was described in 7466 can be used preferably.

In order to apply the heat-sensitive recording material to a heat-sensitive recording material capable of full-color image recording, a cyan ink sheet containing a heat-diffusible cyan dye capable of forming a cyan image and a magenta image can be formed. It is preferable that a magenta ink sheet containing a heat-diffusible magenta dye and a yellow ink sheet containing a heat-diffusible yellow dye capable of forming a yellow image are successively applied on a support to form a yellow image. In addition, an ink sheet containing a black image forming substance may be further formed, if necessary.

[Color Filter] As a method for forming a color filter, a method of first forming a pattern with a photoresist and then dyeing it, or JP-A-4-1-1.
63552, JP-A-4-128703, JP-A-4-128703
As disclosed in Japanese Patent No. 175753, there is a method of forming a pattern with a photoresist to which a dye is added. As a method used when introducing the compound (1) into a color filter, any of these methods may be used, but a preferable method is JP-A-4-175.
No. 753 and JP-A-6-35182, a positive resist composition containing a thermosetting resin, a quinonediazide compound, a crosslinking agent, a dye and a solvent, and after coating it on a substrate. Exposing through a mask and developing the exposed portion to form a positive resist pattern,
There can be mentioned a method for forming a color filter, which comprises exposing the whole positive resist pattern to light and then curing the exposed positive resist pattern. or,
A black matrix is formed according to a conventional method, and the RGB primary color system or Y, M. A C-complementary color filter can be obtained.

Regarding the thermosetting resin, the quinonediazide compound, the crosslinking agent, and the solvent used in this case, and the amounts used thereof, those described in the above patent can be preferably used.

[0083]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to these. <Example 1> (Preparation of water-based ink) Deionized water was added to the following components to prepare 1
After setting to L, it stirred for 1 hour, heating at 30-40 degreeC. Thereafter, pH was adjusted to 9 with KOH 10 mol / L, and vacuum filtration was performed using a microfilter having an average pore size of 0.25 μm to prepare a magenta ink liquid A. Magenta dye of Compound (1) 8.5 g / L (Specific Example 3- (65) -5- (65) -154) Diethylene glycol 150 g / L Urea 37 g / L Glycerin 130 g / L Triethylene glycol monobutyl ether 130 g / L Tri Ethanolamine 6.9 g / L Benzotriazole 0.08 g / L Surfynol 465 10 g / L PROXEL XL2 3.5 g / L

Ink liquids B to K were prepared in the same manner as the ink liquid A, except that the compound (1) was changed as shown in Table 1 below.

(Image recording and evaluation) The ink liquids A to L were packed in a cartridge of an ink jet printer (PM-670C, manufactured by Seiko Epson Corp.), and the same machine was used to eject ink jet paper photo gloss paper EX (Fuji Photo Film Co., Ltd.). Image). The obtained image was evaluated for hue, paper dependence, water resistance, light fastness, ozone gas resistance, and paper dependence. <Hue> The hue was visually evaluated on the basis of three grades: best, good and bad. The evaluation results are shown in Table 11 below. In Table 1 below, ◯ indicates the best hue; Δ indicates that the hue is good, and x indicates that the hue is poor. <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 images is small, A (good), and between the both images are compared. When the difference was large, it was evaluated as B (poor) in two stages.

<Water resistance> A sample having a reflection density of about 1.0 on which an image was formed on the photo glossy paper was dried at room temperature for 1 hour, immersed in ion-exchanged water for 3 minutes, and naturally dried at room temperature. It was evaluated based on the change in the concentration. Evaluation was made in three stages, with A showing almost no change, B showing a decrease in concentration and C showing a large decrease in concentration.

<Light resistance> The photo glossy paper on which the above image was formed was irradiated with xenon light (85000 lux) for 5 days using a weather meter (Atlas CI65).
Image densities before and after xenon irradiation were measured using a reflection densitometer (X-Rit
e310TR) and measured as the dye residual rate. The reflection density is 1, 1.5 and 2.0.
Measured at points. At any concentration, the dye residual rate was 80% or more, A, 1 or 2 points was less than 80% as B, and all the concentrations were less than 80% as C.

<Ozone resistance> The photo glossy paper on which the image is formed is left in a box in which the ozone gas concentration is set to 0.5 ppm for 5 days, and the image density before and after being left under ozone gas is measured by a reflection densitometer (X- Rite 310TR), and evaluated as the residual dye rate. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor manufactured by APPLICS (model: OZG-EM-01). A at 1% or less than 80% of the dye residual rate is 80% or more at all concentrations, B is 70% at all concentrations
The case of less than was set as C, and evaluated in three stages.

[0089]

[Table 1]

[0090]

[Chemical 10]

As shown in Table 1, the images obtained from the ink liquids A to G were clearer than the images obtained from the ink liquids H to K. In addition, the images obtained using the ink liquids A to G were excellent in light fastness and ozone gas resistance.

<Example 2> Further, using the ink liquids A to G, an PM printer paper (PM-670C, manufactured by Seiko Epson Corp.) was used for PM photo paper <Gloss>.
Images were recorded on (KA420PSK, Seiko Epson Corporation). When the hue, paper dependence, water resistance, light fastness, and ozone gas resistance of the obtained images were evaluated, the same results as in Table 1 were obtained.

<Example 3> The same ink prepared in Example 1 was used as an ink jet printer BJ-F850 (CA).
Example 1
When the same evaluation as described in (1) was performed, the same results as in Examples 1 and 2 were obtained.

Example 4 (Emulsion Dispersion Ink) Preparation of Sample 101 Azo Compound (Specific Example 3- (66) -5- (66) -15)
4) 5.63 g, and sodium dioctylsulfosuccinate 7.04 g were used in the following high boiling point organic solvent (S-2) 4.22.
g, the following high-boiling organic solvent (S-11) (5.63 g) and ethyl acetate (50 ml) were dissolved at 70 ° C. To this solution, 500 ml of deionized water was added while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion. Next, this coarse particle dispersion is treated with a microfluidizer (MICROFLUIDEX INC) at 60 MPa.
The particles were made into fine particles by passing it 5 times at the pressure of. The resulting emulsion was desolvated with a rotary evaporator until the odor of ethyl acetate disappeared. To the fine emulsion of the hydrophobic dye thus obtained, 140 g of diethylene glycol, 50 g of glycerin, SURFYNOL
465 (Air Products & Chemicals
7 g) and 900 ml of deionized water were added to prepare an ink.

[0095]

[Chemical 11]

Preparation of Samples 102 to 107 The azo compound of Sample 101 (Specific Example 3- (65) -5-
Samples 102 to 105 were prepared in the same manner as Sample 101, except that (65) -154) was changed to the azo compounds shown in Table 2 below. Samples 10 and 10 were also used for Comparative Dyes 5 and 6 below.
Samples 106 and 107 were prepared in the same manner as in 1.

[0097]

[Chemical 12]

[0098]

[Table 2]

(Image recording and evaluation) Ink samples 101 to
The following evaluations were performed on 107 and the comparative sample. "Paper dependency", "Water resistance" and "Light resistance" are the same as those for ink jet printers (EPSON
It is evaluated after recording an image on a photo gloss paper (manufactured by Fuji Photo Film Co., Ltd .; inkjet paper, photo grade) with PM-700C manufactured by Co., Ltd.

<Paper Dependency> The hues of the image formed on the photo glossy paper and the image separately formed on the PPC plain paper are compared, and when the difference between the images is small, A (good), both When the difference between the images was large, it was evaluated as B (defective) in two stages.

<Water resistance> The photo-glossy paper on which the above image was formed was dried at room temperature for 1 hour, then immersed in water for 30 seconds and naturally dried at room temperature, and bleeding was observed. The case without bleeding was evaluated as A, the case with slight bleeding as B, and the case with large bleeding as C.

<Light resistance> The photo glossy paper on which the above image was formed was irradiated with xenon light (85000 lx) for 3 days using a weather meter (Atlas CI65), and the image density before and after the xenon irradiation was measured by a reflection densitometer. (X-Rite
310TR), and evaluated as the residual dye rate. The reflection density was measured at three points of 1, 1.5 and 2.0. At any concentration, the case where the residual dye ratio was 70% or more was evaluated as A, 1 or 2 points was less than 70% as B, and the case where all the concentrations were less than 70% was evaluated as C.

<Ozone Resistance> The photo glossy paper on which the above image was formed was subjected to the same measurement and evaluation as in the aqueous ink of Example 1.

As is clear from Table 2, the ink-jet ink of the present invention has little paper dependency and is excellent in water resistance, light resistance and ozone gas resistance.

<Example 5> The same ink prepared in Example 4 was used as an ink jet printer BJ-F850 (CA).
Example 4 in which the image is printed on the photo glossy paper GP-301 of the same company by packing in a cartridge (made by NON).
When the same evaluation as in Example 4 was performed, the same results as in Example 4 were obtained.

Example 6 Compound (1) (3- (66)
-5- (66) -154) 3 parts by mass and a resin for toner [styrene-acrylic acid ester copolymer; trade name Heimer TB-1000F (manufactured by Sanyo Kasei)] 100 parts by mass were mixed and pulverized with a ball mill, and then 150 ° C. After heating, the mixture was melted and mixed, cooled, coarsely pulverized using a hammer mill, and then finely pulverized by an air jet type fine pulverizer. Further classification was carried out to select 1 to 20 micro to prepare a toner. To 10 parts of this toner, carrier iron powder (trade name EFV2
900 parts of 50/400; manufactured by Nippon Iron and Powder Co., Ltd. were uniformly mixed to obtain a developer. Similarly, samples were prepared in the same manner except that the coloring agents shown in Table 3 were used in an amount of 3 parts by mass for the dye (the present invention and Comparative Examples 1 and 2) and 6 parts by mass for the pigment (Comparative Examples 3 and 4). A dry plain paper electrophotographic copying machine [trade name NP-5000; manufactured by Canon Inc.] using these developers.
I made a copy at.

The evaluation test was carried out by using the developer using the color toner of the present invention and the paper and O by the image forming method.
A reflection image (image on paper) and a transmission image (OHP image) were prepared on the HP, respectively, and were carried out by the method described below. The toner adhesion amount is 0.7 ± 0.05 (mg / c
It was evaluated in the range of m ² ).

The hue and light fastness of the obtained image were evaluated. The hue was visually evaluated on the basis of 3 grades: best, good and bad. The evaluation results are shown in Table 3 below. In Table 3 below, ◯ indicates that the hue is the best; Δ indicates that the hue is good, and x indicates that the hue is poor. Regarding light fastness, after measuring the image density Ci immediately after recording, after irradiating the image with xenon light (85,000 lux) for 5 days using a weather meter (Atlas C.165),
The image density Cf was measured again, and the dye residual ratio ({(Ci-Cf) / Ci} ×) was calculated from the difference in image density before and after the irradiation with xenon light.
100%) was calculated and evaluated. The image density was measured using a reflection densitometer (X-Rite 310TR). The evaluation results are shown in Table 3 below. In Table 3 below, the dye residual rate is 90%
The above cases are shown as ◯, 90 to 80% as Δ, and less than 80% as x.

The transparency of the OHP image was evaluated by the following method. "330 type self-recording spectrophotometer" made by Hitachi Ltd.
The visible spectral transmittance of the image is measured by using the OHP sheet on which the toner is not carried as a reference by 650
The spectral transmittance in nm was obtained and used as a measure of the transparency of the OHP image. A spectral transmittance of 80% or more was evaluated as ◯, 70 to 80% was evaluated as Δ, and 70% or less was evaluated as x. The above results are shown in Table 3.

[0110]

[Table 3]

[0111]

[Chemical 13]

As is clear from Table 3, the use of the color toner of the present invention shows high OHP quality.
The color toner of the present invention is suitable for use as a full color toner. Further, since it has good light resistance, it is possible to provide an image that can be stored for a long period of time.

<Example 7><Preparation of thermal transfer dye-donor material> A polyethylene terephthalate film (manufactured by Teijin) having a thickness of 6 μm and having a heat resistant slip treatment on the back surface was used as a support, and the following was formed on the surface of the film. The coating composition for a thermal transfer dye-donating layer having the composition was applied by wire bar coating so as to have a dry thickness of 1.5 μm to prepare a thermal transfer dye-donating material (5-1). Coating composition for thermal transfer dye-donating layer: Compound (1) (3- (48) -5- (48) -128) 10 mmol Polyvinyl butyral resin (Denka Butyral 5000-A manufactured by Electrochemical Co., Ltd.) 3 g Toluene 40 ml Methyl ethyl ketone 40 ml Polyisocyanate 0.2 ml (Takenate D110N manufactured by Takeda Pharmaceutical Co., Ltd.) Next, the above compound (1) (3- (48) -5- (48)-
128) was replaced with the other compounds listed in Table 4, and the thermal transfer dye-donor material of the present invention and the comparative thermal transfer dye-donor materials (5-2) to (5-5) were respectively prepared in the same manner as above. Created.

(Preparation of Thermal Transfer Image Receiving Material) A synthetic paper having a thickness of 150 μm (YUPO-FPG-manufactured by Oji Yuka)
150) was used to apply the following composition to the surface by wire bar coating so that the thickness when dried was 8 μm, to prepare a thermal transfer image-receiving material. Drying was performed for 30 minutes in an oven at a temperature of 100 ° C. after temporary drying with a dryer. Coating composition for image-receiving layer: Polyester resin 22 g (Voyron-280 manufactured by Toyobo) Polyisocyanate 4 g (KP-90 manufactured by Dainippon Ink and Chemicals) Amino-modified silicone oil (KF-857 manufactured by Shin-Etsu Silicone) 0.5 g Methyl ethyl ketone 85 ml Toluene 85 ml Cyclohexanone 15 ml

The thermal transfer dye-donating materials (5-1) to (5-5) obtained as described above and the thermal transfer image-receiving material are superposed so that the thermal transfer dye-donating layer and the image-receiving layer are in contact with each other, and thermal transfer is carried out. A thermal head is used from the support side of the dye-donor element, and the output of the thermal head is 0.25 W / dot.
Pulse width 0.15 to 15 ms, dot density 6 dots /
When printing was carried out under the condition of mm, and a dye was dyed imagewise on the image receiving layer of the image receiving material, clear image recording without transfer unevenness was obtained. Next, each of the recorded thermal transfer image-receiving materials obtained as described above was irradiated with Xe light (17,000 lux) for 5 days, and the light stability of the color image was examined. The status A reflection density after irradiation of the portion showing the status A reflection density of 1.0 was measured, and its stability was evaluated by the residual rate (percentage) with respect to the reflection density of 1.0 before irradiation. The results are shown in Table 4.

[0116]

[Table 4]

[0117]

[Chemical 14]

As described above, the compound (1) was superior in light fastness to the dye for comparison. The hue was also fresh

<Example 8> As for the method for producing a color filter, a silicon wafer was spin-coated with a positive resist composition containing a thermosetting resin, a quinonediazide compound, a crosslinking agent, a dye and a solvent, and the solvent was evaporated by heating. After that, exposure was performed through a mask to decompose the quinonediazide compound. If necessary, after heating, development was carried out to obtain a mosaic pattern. Exposure is Hitachi's i-line exposure stepper HITACHI LD-5010-i
(NA = 0.40). As the developing solution, SOPD or SOPD-B manufactured by Sumitomo Chemical Co., Ltd. was used.

<Preparation of Positive Resist Composition> Cresol novolac resin (polystyrene-equivalent weight average molecular weight 430) obtained from a mixture of m-cresol / p-cresol / formaldehyde (reaction molar ratio = 5/5 / 7.5).
0) 3.4 parts by mass, the following formula

[0121]

[Chemical 15]

O-Naphthoquinonediazide-5-sulfonic acid ester prepared by using the phenol compound represented by (1) (on average, two hydroxyl groups are esterified)
8 parts by mass, hexamethoxymethylolated melamine 0.8
Parts by mass, 20 parts by mass of ethyl lactate and compound 1 shown in Table 5
A positive resist composition was obtained by mixing parts by mass.

<Preparation of Color Filter> A silicon wafer was spin-coated with the obtained positive resist composition, and then the solvent was evaporated. After exposing the silicon wafer,
After heating at 100 ° C., the exposed portion was removed by alkali development to obtain a positive colored pattern having a resolution of 0.8 μm. This was exposed on the entire surface and then heated at 150 ° C. for 15 minutes to obtain a magenta complementary color filter.

Comparative Example A positive resist composition was obtained by mixing 1 part by mass of Orazole Pink (magenta dye) manufactured by Ciba-Geigy Co., Ltd. in place of the magenta dye of the compound (1) used in the above examples. A silicon wafer was spin-coated with this positive resist composition, and then the solvent was evaporated. After exposing a silicon wafer, alkali develop it to 1
A positive colored pattern with a resolution of μm was obtained. This was exposed on the entire surface and then heated at 150 ° C. for 10 minutes to obtain a magenta color filter.

<Evaluation> The transmission spectrum of the obtained magenta color filter was measured, and the breakage on the short wave side and the long wave side of the spectrum important for color reproduction was relatively evaluated. ○ is good,
△ represents an acceptable level, and × represents an unacceptable level. In addition, a weather meter (Atlas C.I6
Using 5), xenon light (85000 lx) was irradiated for 7 days, the image density before and after irradiation with xenon was measured, and evaluated as the dye residual rate.

[0126]

[Table 5]

It can be seen that the dye of the compound (1) is superior in color reproducibility as compared with the comparative example. Further, it was found that the light fastness was superior to that of the comparative compound.

INDUSTRIAL APPLICABILITY According to the present invention, an ink for printing such as an ink jet, an ink sheet for a thermal recording material, a color toner for electrophotography, an LCD, which gives a colored image or a coloring material excellent in hue and fastness, Provided are various coloring compositions such as color filters used in displays such as PDPs and image pickup devices such as CCDs, and dyeing solutions for dyeing various fibers. Further, it is possible to provide an ink and an inkjet recording method capable of forming an image having high fastness to an active gas in the environment, particularly ozone gas.

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Claims (2)

[Claims] 1. A coloring composition comprising a medium and a compound represented by the following general formula (1). [Chemical 1] In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or a monovalent substituent. However, any two of R ^{1 to} R ⁵ represent Ra and Rb. A ¹ and A ² each represent a substituted or unsubstituted aryl group or heteroaryl group. 2. An ink jet characterized in that an image is formed using an ink containing the coloring composition according to claim 1 on an image receiving material having an ink image receiving layer containing white inorganic pigment particles on a support. Recording method.