JPH11151865A - Heat-sensitive transfer material, and ink jet recording liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-sensitive transfer material which is excellent in fastness, especially in light-resistance by forming a layer containing at least a coloring matter of a specified structure on a supporting body. SOLUTION: For this heat-sensitive transfer material, a layer which contains at least a coloring matter represented by a formula is formed on a supporting body. In the formula, A indicates an atomic group which constitutes a six- membered heterocycle having -NRR as a substitutional group, and bonds with D by carbon atom in the ring represented by A. B indicates a coupler component, and bonds with D by an active site of the coupler component. D indicates nitrogen atom or CH. R1 , R2 respectively independently indicate hydrogen atom, an alkyl group which may have a substitutional group, an aryl group which may have a substitutional group, and a hetero ring group which may have a substitutional group. R1 , R2 may form a ring by bonding with each other. G indicates hydrogen atom or an alkyl group which may have a substitutional group, and an aryl group which may have a substitutional group. By this method, the heat-sensitive transfer material becomes excellent in fastness, especially in light-resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to thermal transfer recording and ink jet recording, and more particularly to a thermal transfer material and an ink jet recording liquid using a dye having excellent fastness.

[0002]

2. Description of the Related Art Conventionally, a method using a heat-sensitive transfer material has been known as a method for obtaining a high-quality full-color image with a simple apparatus. In this method, a dye for forming a color image is very important, and greatly affects various properties such as color reproducibility, various fastnesses, maximum density, and thermal sensitivity of the color image. Until now, various dyes such as styryl type, pyridone azo type, pyrazole azo type, anthraquinone type, naphthoquinone type, and indoaniline type have been studied. Not found.

In recent years, azomethine dyes and indoaniline dyes in which the aniline structure of the aniline structure is replaced with a heterocyclic group have been studied to improve the light fastness. For example, pyridine-based dyes are described in JP-A-4-89287 and JP-A-5-239367.
Nos. 6-73009, 6-80638, 7-
No. 232482 is known. Examples of the thiazole dyes include JP-A-3-93862 and JP-A-4-234460.
No. 4,338,592, No. 5-309954, and No. 8-283591. Examples of thiophene dyes include JP-A-6-143838 and JP-A-6-143.
No. 839 is known. Also, Japanese Patent Application Laid-Open No. Hei 6-21905
No. 7 discloses furan dyes, oxazole dyes, pyrrole dyes, and the like. However, dyes having satisfactory light fastness have not yet been found among the dyes studied so far, and further improvement in light fastness is eagerly desired.

In ink jet recording, conventionally used azo dyes, xanthene dyes, triphenylmethane dyes and the like do not have satisfactory fastness, especially light fastness. Among azomethine dyes, particularly those in which the aniline structure is replaced with a heterocyclic ring have been studied in recent years, and light resistance has been improved. For example, Japanese Unexamined Patent Publication (Kokai) No. 9-150572 is known as a pyridine dye, but a dye having satisfactory light fastness has not yet been found, and further improvement in light fastness is desired.

Japanese Patent Application Laid-Open No. 6-148845 discloses a pyrimidine skeleton diamine compound as a silver halide color photographic developing agent. There is no specific description. There is no description about using the dye for image formation other than silver halide color photography.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-sensitive transfer material and an ink jet recording liquid using a dye excellent in fastness, especially light fastness.

[0007]

The above objects of the present invention are as follows. A heat-sensitive transfer material comprising at least a layer containing a dye represented by the following general formula (1) on a support:

[0008]

Embedded image In the formula, A represents an atomic group constituting a 6-membered heterocyclic ring having —NR ₁ R ₂ as a substituent, and is bonded to D by a carbon atom in the ring represented by A. B represents a coupler component and is bonded to D at the active site of the coupler component. D represents a nitrogen atom or CH. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent; ₁ and R ₂ may combine with each other to form a ring. G represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.

[0009] 2. This is achieved by each of the inkjet recording liquids characterized by containing at least the dye represented by the general formula (1).

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below. First, the dye represented by the following general formula (1) will be described.

[0011]

Embedded image A represents an atomic group constituting a 6-membered hetero ring having —NR ₁ R ₂ as a substituent, wherein R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group which may have a substituent, Represents an aryl group which may have a group or a heterocyclic group which may have a substituent, and R ₁ and R ₂ may be bonded to each other to form a ring, but R ₁ and R ₂ are both alkyl Preferably, R ₁ and R ₂ may be bonded to each other to form a ring. D represents a nitrogen atom or CH, and is more preferably a nitrogen atom. G represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and an alkyl group is preferable.

Among the dyes represented by the general formula (1), the following general formulas (2) to (6) are preferable, and the general formulas (2) and (3) are particularly preferable.

[0013]

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In the general formulas (2) to (6), R ₃ , R
₄ independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent; R ₃ , R ₄ May combine with each other to form a ring. R ₅ represents a substituent that can be substituted on the pyrimidine ring, n represents 0 to 2, and when n = 2, R ₅ may be the same substituent or different substituents. B represents a coupler component, which is bonded to a nitrogen atom at the active site of the coupler component. G represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.

R ₃ and R _{4 in} formulas (2) to (6) each independently represent a hydrogen atom, an alkyl group which may have a substituent,
Represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, and examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, an n-propyl group, and a hydroxy group. Ethyl group, methanesulfonylaminoethyl group,
Specific examples include a cyanoethyl group and the like, and an aryl group which may have a substituent includes a phenyl group which may have a substituent.Examples of the substituent in this case include an alkyl group and an alkoxy group. Group, a halogen atom, an acylamino group, an acyloxy group, a carbamoyl group, an oxycarbonyl group, and the like.Examples of the heterocyclic group which may have a substituent include a pyridyl group, a thienyl group, a furyl group,
Oxazolyl, imidazolyl groups and the like are mentioned as specific examples.

In the general formulas (1) to (6), B represents a coupler component. The term "coupler component" as used herein means a coupler component which is oxidatively coupled with a p-phenylenediamine compound, and is an active methylene compound. , Compounds having active hydrogen, phenols, naphthols and the like. Preferred B includes the following general formulas (7) to (13).

[0017]

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In the general formula (7), R ₆ represents a carbamoyl group or a cyano group, and R ₇ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. Represents a hetero ring which may be substituted. The carbon atom marked with * is the active site.

In the general formula (8), R ₈ has the same meaning as R ₇ , and R ₉ has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a group which has a substituent. And a heterocycle, an acylamino group, an anilino group, an amino group, an alkyloxy group, a cyano group, a carbamoyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group which may be substituted. The carbon atom marked with * is the active site.

In the general formula (9), R ₁₀ and R ₁₁ have the same meaning as R ₉ . The carbon atom marked with * is the active site.

In the general formula (10), R ₁₂ and R ₁₃ are R ₉
Is synonymous with The carbon atom marked with * is the active site.

In the general formula (11), R ₁₄ represents an alkyl group which may have a substituent, an acylamino group, a halogen atom,
Represents a ureido group, an alkoxycarbonylamino group, or an aryloxycarbonylamino group. p represents 1 to 4, and when p is 2, 3, or 4, R ₁₄ may be the same or different. The carbon atom marked with * is the active site.

In the general formula (12), R ₁₅ represents an acylamino group, a sulfonylamino group, a ureido group, a carbamoyl group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an amino group or an alkyl group;
Represents 1 to 3, and when q is 2, 3, or 4, R ₁₄ may be the same or different. The carbon atom marked with * is the active site.

In the general formula (13), R ₁₆ and R ₁₇ are R ₇
Is synonymous with The carbon atom marked with * is the active site.
Preferred specific examples of A in the general formula (1) are shown below.

[0025]

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[0026]

Embedded image Preferred examples of B = D- in the general formula (1) are shown below.

[0027]

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[0028]

Embedded image

[0029]

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Specific examples of the dye represented by formula (1) of the present invention are shown below, but the present invention is not limited thereto.

[0031]

[Table 1]

The compound represented by the general formula (1) of the present invention can be synthesized by a conventional method from a compound synthesized with reference to JP-A-6-14845 and a coupler component.

Specific examples of the synthesis of the compound represented by formula (1) are shown below. Synthesis Example 22.6 g of compound S1 (synthesized with reference to JP-A-6-14845), 25.4 g of compound S2, and methanol 4
Then, the mixture was stirred at room temperature. Further, a solution in which 41.4 g of potassium carbonate was dissolved in 120 ml of water was added. Here, sodium peroxosulfate (Mw228)
A solution of 50.1 g dissolved in 300 ml of water was added dropwise.
After the addition, the mixture was further stirred at room temperature for 1 hour, and the produced dye was extracted with ethyl acetate. After the ethyl acetate solution was washed with a saturated saline solution, ethyl acetate was distilled off to obtain a dye residue. The residue was recrystallized from acetonitrile to obtain 22.0 g of the desired compound. The synthesized compound is NMR,
It was confirmed by mass spectrometry that the substance was the target substance.

[0034]

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Next, the heat-sensitive transfer material containing the dye of the present invention will be described. The thermal transfer material containing the dye of the present invention preferably has a dye-containing layer comprising at least a dye and a binder on a support. The content of the dye is preferably the support 1 m ² per 0.05 to 10 g.

The binder is preferably a solvent-soluble polymer such as an acrylic resin, a methacrylic resin, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyvinyl butyral, polyvinyl acetal, nitrocellulose and ethyl cellulose. These binders may be used in the form of a latex dispersion, as well as one or more of them dissolved in a solvent. The amount of the binder used is preferably 0.1 to 20 g. The binder amount to the support 1 m ² per dye amount is preferably 2 times 0.5 times.

The dye-containing layer is prepared by dissolving the dye of the present invention together with a binder or dispersing it in fine particles in a solvent to prepare an ink liquid for forming a heat-sensitive transfer layer, and coating the ink on a support. And dried as appropriate. The thickness of the dye-containing layer is preferably from 0.1 to 10 μm in dry film thickness.

The heat-sensitive transfer material containing the dye of the present invention may be any material as long as it has good dimensional stability and can withstand heating of a heat-sensitive head or the like at the time of recording, and thin paper such as condenser paper or glassine paper. A heat-resistant plastic film such as polyethylene terephthalate, polyamide and polycarbonate is preferably used. The thickness of the support is preferably from 2 to 30 μm, and the support has an undercoat layer made of a polymer selected for the purpose of improving the adhesiveness with a binder, and preventing the transfer and dyeing of the dye to the support. It is preferable to have Further, a slipping layer may be provided on the back surface of the support (the side opposite to the dye-containing layer) for the purpose of preventing the head from sticking to the support.

To apply the heat-sensitive transfer material containing the dye of the present invention to a heat-sensitive transfer material capable of full-color image recording, a yellow heat-sensitive transfer layer containing a yellow dye, a magenta heat-sensitive transfer layer containing a magenta dye, and cyan It is preferred that at least a total of three cyan thermal transfer layers containing a dye are repeatedly and sequentially coated on the same surface on the support. Further, if necessary, a total of four heat-sensitive transfer layers containing a black image-forming substance may be sequentially and repeatedly coated on the same surface.

As a recording method using the heat-sensitive transfer material containing a dye of the present invention, for example, a heat-sensitive material according to image information is formed after a dye-containing layer of the heat-sensitive transfer material and an image receiving material described later are superposed. The image can be formed on the image receiving material by applying the dye to the thermal transfer material.

As the image receiving material, those having an image receiving layer on a support are used. As the support of the image receiving material, paper, plastic film, paper-plastic film composite, or the like can be used. Specifically, examples of the support include those described in JP-A-3-54556, page 5, line 17 from the upper right to line 11 from the upper left. The image receiving layer is composed of a polymer binder.

The polymer binder is preferably a thermoplastic polymer, for example, a polyester resin, a polyvinyl chloride resin, a copolymer resin of vinyl chloride and another monomer (for example, vinyl acetate, etc.), polyvinyl butyral, polyvinyl pyrrolidone, polycarbonate and the like. One or two of
More than one kind of polymer layer is formed.

Next, the ink jet recording liquid containing the dye of the present invention will be described. As the inkjet recording liquid containing the dye of the present invention, an aqueous inkjet recording liquid, an oil-based inkjet recording liquid, a solid (phase change) inkjet recording liquid and the like can be preferably used. 10 per weight
A water-based inkjet recording liquid containing water in an amount of at least% by weight) can be particularly preferably used.

The aqueous ink jet recording liquid preferably uses water and a water-soluble organic solvent as a solvent in addition to the dye of the present invention.

Examples of the water-soluble organic solvent include alcohols (eg, methanol, ethanol, propanol,
Isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc., and polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene) Propylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, ethylene glycol monophenyl ether, Propylene glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylene Pentamine, Liethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocycles (eg, 2-pyrrolidone, N-methyl) -2-pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2
-Imidazolidinone), sulfoxides (eg, dimethylsulfoxide), sulfones (eg, sulfolane), urea, acetonitrile, acetone and the like. Preferred water-soluble organic solvents include polyhydric alcohols. The water-soluble organic solvents may be used alone or in combination of two or more. The total amount of the water-soluble organic solvent in the ink is 5 to 60% by weight, preferably 1 to 60% by weight.
0 to 30% by weight.

In the aqueous ink jet recording liquid described above, the dye can be used as it is if it is soluble in the solvent system. On the other hand, in the case of a solid which is insoluble as it is, various kinds of dispersers (for example, ball mill, sand mill, attritor, roll mill, agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, jet mill, ong mill, etc.) Or after dissolving the dye in a soluble organic solvent, it can be dispersed in a solvent system together with a polymer dispersant and a surfactant. Furthermore, when the liquid or semi-molten substance is insoluble as it is, it can be dissolved as it is or dissolved in a soluble organic solvent, and can be dispersed in the solvent system together with the polymer dispersant and the surfactant. For a specific method for preparing such an aqueous inkjet recording liquid, see, for example,
No. 148436, No. 5-295121, No. 7-975
Nos. 41, 7-82515, and 7-118584 can be referred to.

The aqueous, oil-based, and solid ink-jet recording liquids described above have a viscosity of 40 cp during flight.
s or less, and more preferably 30 cps or less.

The surface tension of the ink jet recording liquid of the present invention during flight is preferably 20 dyn / cm or more, more preferably 40 to 60 dyn / cm.

The dye concentration is preferably used in the range of 0.1 to 25% by weight, more preferably in the range of 0.5 to 10% by weight, based on the total amount of the ink jet recording liquid.

In the ink jet recording liquid, a viscosity adjusting agent, a surface tension adjusting agent, A resistance adjusting agent, a film-forming agent, a dispersant, a surfactant, an ultraviolet absorber, an antioxidant, an anti-fading agent, a sunscreen, and a rust preventive can also be added.

The ink jet recording liquid is not particularly limited with respect to the recording method used, and can be preferably used as an ink jet recording liquid for a continuous type and an on-demand type ink jet printer. Examples of the on-demand method include an electric-mechanical conversion method (for example, a single-cavity type, a double-cavity type, a bender type, a piston type, a shared mode type, a shared wall type, and the like), and an electro-thermal conversion method (for example, thermal inkjet). Mold, bubble jet type, etc., electrostatic suction type (eg, electric field control type, slit jet type, etc.), discharge type (eg, spark jet type, etc.) and the like.

[0052]

EXAMPLES The present invention will be described more specifically with reference to examples, but the present invention is not limited to the embodiments in the examples. Example 1 Production of Thermal Transfer Material and Evaluation of Image [Ink Preparation] The following materials were mixed to obtain an ink containing a dye according to the present invention. Dye No. 15 g polyvinyl butyral resin (BL-1, manufactured by Sekisui Chemical Co., Ltd.) 5 g methyl ethyl ketone 200 ml

[Preparation of Thermal Transfer Material] The ink was applied on a 4.5 μm-thick polyethylene terephthalate base using a wire bar so that the applied amount after drying was 0.8 g / m ² , and dried. A thermal transfer material 1 having a thermal transfer layer formed on a polyethylene terephthalate base was produced. A nitrocellulose layer containing a silicon-modified urethane resin (SP-2105, manufactured by Dainichi Seika) is provided on the back surface of the polyethylene terephthalate base as a sticking prevention layer.

[Preparation of Image-Receiving Material] On a support in which polyethylene is laminated on both sides of paper (a polyethylene layer on one side contains a white pigment (TiO ₂ ) and a bluing agent), an ester-modified silicon (image-receiving layer) is formed as an image-receiving layer. An amount of 0.15 g / m ² ) of a methyl ethyl ketone solution containing a polyester resin was applied so that the weight of the polyester resin was 5 g / m ² , to obtain an image receiving material 1.

[Formation of Thermal Transfer Image] The thermal transfer material 1 and the image receiving material 1 were overlaid, and a thermal head was applied from the back side of the thermal transfer material to perform image recording under the following recording conditions. A yellow image (image 1) was obtained.

(Recording conditions) Recording density in main scanning and sub-scanning: 8 dots / mm Power consumption: 0.6 W / dot Heating time: Heating time is adjusted stepwise from 20 msec to 0.2 msec. In the same manner as the method for obtaining the image 1, the thermal transfer materials 1 to 25 were prepared using the dyes shown in Table 2, and corresponding images were obtained. In addition, the thing of the following structures was used as a comparative dye.

[0057]

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[Evaluation of Thermal Transfer Image] (Evaluation of light fastness) A sample having a reflection density of about 1.0 obtained by the above method was irradiated with a Xe fade meter (70000 L).
x, 50 hours) The reflection density change rate was determined as follows. Reflection density change rate = (reflection density after Xe irradiation) / (reflection density before Xe irradiation) × 100 Table 2 shows relative values when the reflection density change rate of the comparative compound is set to 100.

[0059]

[Table 2] From the results in Table 2, it was found that the image formed from the thermal transfer material containing the dye of the present invention had high light fastness.

Example 2 [Preparation of ink] 3% by weight of the dyes shown in Table 3, 19% by weight of diethylene glycol, 9% by weight of triethylene glycol monobutyl ether, 0.6% by weight of Surfynol 465 as a surfactant, and the balance Was used as ion-exchanged water to prepare an ink. In addition, the thing of the following structures was used as a comparative dye.

[0061]

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[Formation of Inkjet Image] The ink was recorded on plain paper (Xerox 4024) by an inkjet printer MJ-5000C (manufactured by Seiko Epson Corporation, electro-mechanical conversion system) to obtain an image sample.

[0063]

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[Evaluation of Inkjet Image] (Evaluation of Lightfastness) The sample having a reflection density of about 1.0 obtained by the above method was irradiated with a Xe fade meter (70000 L).
x, 50 hours) The reflection density change rate was determined as follows. Reflection density change rate = (reflection density after Xe irradiation) / (reflection density before Xe irradiation) × 100 Table 3 shows relative values when the reflection density change rate of the comparative compound is 100.

[0065]

[Table 3] From the results in Table 3, it was found that the image formed from the inkjet recording liquid containing the dye of the present invention had high light fastness.

[0066]

According to the present invention, it is possible to provide a heat-sensitive transfer material and an ink jet recording liquid using a dye having excellent fastness, particularly light fastness.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 11/00 C09D 11/00

Claims (2)

[Claims] 1. A heat-sensitive transfer material comprising at least a layer containing a dye represented by the following general formula (1) on a support. Embedded image In the formula, A represents an atomic group constituting a 6-membered heterocyclic ring having —NR ₁ R ₂ as a substituent, and is bonded to D by a carbon atom in the ring represented by A. B represents a coupler component and is bonded to D at the active site of the coupler component. D represents a nitrogen atom or CH. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent; ₁ and R ₂ may combine with each other to form a ring. G represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. 2. An ink jet recording liquid comprising at least a dye represented by the following general formula (1). Embedded image In the formula, A represents an atomic group constituting a 6-membered heterocyclic ring having —NR ₁ R ₂ as a substituent, and is bonded to D by a carbon atom in the ring represented by A. B represents a coupler component and is bonded to D at the active site of the coupler component. D represents a nitrogen atom or CH. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent; ₁ and R ₂ may combine with each other to form a ring. G represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.