JP2971106B2 - Thermal transfer recording material and thermal transfer recording method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a thermal transfer recording material and a thermal transfer recording method, and more particularly, contains a cyan dye excellent in hue, light resistance and heat diffusivity. New thermal transfer recording material
The present invention also relates to a thermal transfer recording method capable of efficiently forming an image using the same.

[Prior Art and Problems to be Solved by the Invention] Conventionally, as a method for obtaining a color hard copy, a color recording technique such as an ink jet method, an electrophotographic method, and a thermal transfer method has been studied. It has advantages such as easy operation and maintenance, downsizing and low cost of the device, and low running cost.

In this heat-sensitive transfer method, a transfer sheet (heat-sensitive transfer recording material) having a heat-meltable ink layer provided on a support is heated by a heat-sensitive head, and ink is transferred from the heat-meltable ink layer to a transfer sheet (image-receiving material). A heat transfer head is used to heat the transfer sheet, which is provided with an ink layer containing a heat-diffusible dye (sublimable dye) on the support, and the heat-diffusible dye is transferred from the ink layer to the transfer-receiving sheet. There are two types of thermal diffusion transfer method (sublimation transfer method), in which the transfer of dye is changed according to the thermal energy of the thermal head. Since the gradation can be controlled, it is advantageous for full-color printing.

By the way, in the conventional thermal diffusion transfer system, the dye used for the thermal transfer recording material is important, and the color tone of the dye greatly affects the speed of thermal transfer recording, image quality, image storage stability, and the like.

It is desired that this type of dye has the following properties.

(B) Easy thermal diffusion under thermal recording conditions (head temperature, heating time).

(B) To have a favorable hue in color reproduction.

(C) Do not thermally decompose at the heating temperature during recording.

(D) Good light resistance, heat resistance, moisture resistance, chemical resistance, etc.

(E) The molar absorption coefficient is large.

(F) Easy addition to thermal transfer recording materials.

(G) Easy synthesis.

(H) Good solubility in solvents.

(I) The obtained image has excellent fixability.

However, a thermal transfer recording material using a dye satisfying the above conditions has not been developed yet.

For example, as cyan dyes for thermal transfer recording materials, JP-A-59-78896, JP-A-59-227948, JP-A-60-24996, and
No. 60-53563, No. 60-130735, No. 60-131292, No. 60
No. 239289, No. 61-19396, No. 61-35994, No. 61-31
No. 292, No. 61-31467, No. 61-35994, No. 61-148269
No. 62-191191, No. 63-91288, No. 63-91287,
JP-A-63-290793 discloses naphthoquinone dyes, anthraquinone dyes, azomethine dyes and the like, but these dyes do not satisfy the aforementioned conditions.

The present invention has been made to improve the above situation.

An object of the present invention is to provide a heat-sensitive transfer recording material and a heat-sensitive transfer recording method using a dye satisfying the above conditions, in particular, a cyan dye excellent in heat diffusion property, hue, and light fastness.

[Means for Solving the Problems] The present invention according to claim 1 for achieving the above object has a layer containing a cyan dye represented by the following general formula [I] on a support. Is a thermal transfer recording material.

Further, the present invention according to claim 2 has the following general formula [I]:
An image receiving material is superimposed on the layer of a thermal transfer recording material having a layer containing a cyan dye represented on a support, and the thermal transfer recording material is heated according to image information, and the cyan dye is applied to the image receiving material side. This is a thermal transfer recording method in which an image is formed on an image receiving material by diffusion transfer.

Wherein R ¹ is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an aryloxy group,
Cyano group, acylamino group, alkylthio group, arylthio group, sulfonylamino group, ureido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfonyl group, acyl group,
Represents an amino group. R ² represents a halogen atom, an alkoxy group or an aryloxy group. R ³ and R ⁴ represent an alkyl group. m represents an integer of 1 to 3. further
R ¹ and R ³ and R ³ and R ⁴ may combine with each other to form a ring. Further, when m is an integer of 2 or more, the groups of R ¹ may be bonded to each other to form a ring. Hereinafter, the general formula [1] will be described in more detail.

R ¹ is a hydrogen atom, a halogen atom (eg, chlorine atom, fluorine atom, etc.), an alkyl group (eg, methyl group, ethyl group, isopropyl group, n-butyl group, etc.), a cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.) , An aryl group (eg, phenyl group), an alkenyl group (eg, 2-propenyl group), an aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), an alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group, n -Butoxy group, etc.), aryloxy group (for example, phenoxy group, etc.), cyano group,
Acylamino group (eg, acetylamino group, propionylamino group, etc.), alkylthio group (eg, methylthio group, ethylthio group, n-butylthio group, etc.), arylthio group (eg, phenylthio group), sulfonylamino group (eg, methanesulfonylamino group, benzene Sulfonylamino group), ureido group (for example, 3-methylureido group, 3,3-dimethylureido group, 1,3-
A carbamoyl group (eg, a methylcarbamoyl group, an ethylcarbamoyl group, a dimethylcarbamoyl group, etc.), a sulfamoyl group (eg, an ethylsulfamoyl group, a dimethylsulfamoyl group, etc.), an alkoxycarbonyl group (eg, a methoxycarbonyl group) , Ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl group (eg, methanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), amino group (For example, a methylamino group, an ethylamino group, a dimethylamino group, etc.).

These groups may have a substituent. Examples of the substituent include an alkyl group (eg, a methyl group, an ethyl group, a trifluoromethyl group), an aryl group (eg, a phenyl group), and an alkoxy group (eg, Methoxy group, ethoxy group, etc.), amino group (for example, methylamino group,
Ethylamino group), acylamino group (eg, acetylamino group), sulfonyl group (eg, methanesulfonyl group), alkoxycarbonyl group (eg, methoxycarbonyl group), cyano group, nitro group, halogen atom (eg, chlorine atom, Fluorine atom).

R ¹ having these substituents R ¹ or which does not have these substituents, is preferably more than 12 carbon atoms, particularly preferred is 8 or less carbon atoms.

Examples of the alkoxy group represented by R ² include a methoxy group, an ethoxy group, an isopropoxy group, and an n-butoxy group, and an alkoxy group having 8 or less carbon atoms is particularly preferable.

Examples of the aryloxy group represented by R ² include a phenoxy group, and the benzene ring may have any substituent.

As the substituent of the benzene ring, a substituent having 8 or less carbon atoms is preferable.

Examples of the halogen atom represented by R ² include a chlorine atom and a bromine atom, and preferably a chlorine atom.

FIG. 1 shows specific representative examples of the cyan dye represented by the general formula [I].

Each of the cyan dyes satisfies the conditions (a) to (li) described above, and is particularly excellent in thermal diffusivity, hue, and light resistance.

The cyan dye represented by the general formula [I], that is, the dye according to the present invention, can be obtained by a known synthesis method, for example, the following general formula [I
A phenol derivative represented by the following general formula [II]
It can be produced by an oxidative coupling reaction with a p-phenylenediamine derivative or a p-aminophenol derivative represented by I].

(In the above formula, R ¹ , R ² , R ³ and R ⁴ have the same meanings as defined in the above general formula [I].) This oxidative coupling reaction proceeds under basic conditions. Preferably, the reaction medium may be any of an organic solvent, an aqueous organic solvent, and an aqueous solution.

The oxidizing agent may be any one having a potential capable of oxidizing a p-phenylenediamine derivative or a p-aminophenol derivative irrespective of organic or inorganic substances. Examples thereof include silver halide, hydrogen peroxide, manganese dioxide, and persulfate. Inorganic oxidants such as potassium and oxygen, and organic oxidants such as N-bromosuccinimide and chloramine T can be used.

Further, the cyan dye according to the present invention, in addition to the above synthesis method,
It can also be produced by an electrode reaction.

When relying on this electrode reaction, it is necessary to appropriately select current, voltage, supporting electrolyte, solvent, electrode and the like.

The heat-sensitive transfer recording material of the present invention is provided with a layer containing a cyan dye represented by the general formula [I] (hereinafter sometimes referred to as a heat-sensitive layer) on a support.

The content of the dye in the thermosensitive layer, the support 1 m ² per
0.05 to 10 g is preferred.

The heat-sensitive layer is prepared by dissolving one or more of the dyes in a solvent together with a binder in a solvent, or dispersing them in the form of fine particles in a solvent, or preparing a heat-sensitive layer-forming coating by a hot melt method. Is coated on a support and dried as appropriate.

The thickness of the heat-sensitive layer is preferably in the range of 0.1 to 5 μm in dry film thickness.

As the binder, cellulose-based, polyacrylic acid-based, polyvinyl alcohol-based, polyvinylpyrrolidone-based water-soluble polymer, acrylic resin, methacrylic resin, polystyrene, polycarbonate, polysulfone,
Examples thereof include polyether sulfone, polyvinyl butyral, polyvinyl acetal, nitrocellulose, and ethyl cellulose.

These binders may be used not only by dissolving one kind or two or more kinds in an organic solvent, but also by dispersing them in latex form.

The amount of the binder, the support 1 m ² per 0.05-3
0 g is preferred.

Examples of the solvent for preparing the paint include water, alcohols (eg, ethanol, propanol), cellosolves (eg, ethyl acetate), aromatics (eg, toluene, xylene, chlorobenzene), ketones (eg, acetone, methyl ethyl ketone), Examples include ethers (eg, tetrahydrofuran, dioxane), chlorinated solvents (eg, chloroform, trichloroethylene), and the like.

The support may be any one that has good dimensional stability and can withstand the heat of the thermal head at the time of recording, but it can be heat-resistant such as condenser paper, thin paper such as glassine paper, polyethylene terephthalate, polyamide, and polycarbonate. Is preferably used.

The thickness of the support is preferably 2 to 30 μm, and the support may have an undercoat layer for the purpose of improving adhesion to a binder, transferring a dye to the support, and preventing dyeing. .

Further, a slipping layer may be provided on the back surface of the support (the side opposite to the heat-sensitive layer) for the purpose of preventing the head from sticking to the support.

The heat-sensitive transfer material of the present invention is provided on the heat-sensitive layer in JP-A-59-1069.
It may have a hot-melt layer containing a hot-melt compound as described in JP-A-97.

As the heat-fusible compound, a colorless or white compound having a melting point of 65 to 130 ° C. is preferably used, for example, carnauba wax, beeswax, waxes such as candeli wax, stearic acid, higher fatty acids such as behenic acid, Examples thereof include alcohols such as xylitol, amides such as acetamide and benzoamide, and ureas such as phenylurea and diethylurea.

In addition, these heat-meltable layers may contain a polymer such as polyvinylpyrrolidone, polyvinylbutyral, and saturated polyester in order to enhance the retention of the dye.

According to the thermal transfer recording material of the present invention, it is possible to obtain a cyan dye image having a gradation with one kind of dye as described later, but when applied to full-color image recording, the cyan dye according to the present invention is used. A total of three layers, that is, a cyan thermosensitive layer, a magenta thermosensitive layer containing a heat-diffusing magenta dye, and a yellow thermosensitive layer containing a heat-diffusing yellow dye, are sequentially and repeatedly coated on the same surface of the support. Is preferred.

Further, a heat-sensitive layer containing a black image-forming substance may be added to the above three layers, and a total of four layers may be sequentially and repeatedly applied on the same surface of the support.

In the heat-sensitive transfer recording method of the present invention, the heat-sensitive layer of the heat-sensitive transfer recording material and the image-receiving material are overlapped, heat corresponding to the image information is applied to the heat-sensitive transfer recording material, and the cyan dye is transferred from the heat-sensitive layer to the image-receiving material and fixed. As a result, an image is formed on the image receiving material.

This image forming method will be described with reference to the drawings.
In the above, when the cyan dye is contained in the heat-sensitive layer 2 of the heat-sensitive transfer recording material 3 composed of the support 1 and the heat-sensitive layer 2, the cyan dye is, for example, a heat-generating resistor of the thermal head 4.
The heat from 4a diffuses and transfers to the image receiving material 5, and is fixed in the image receiving layer 7 on the support 6.

In the case of FIG. 2B using a heat-sensitive transfer recording material in which a heat-meltable layer is laminated on the heat-sensitive layer, the cyan dye is contained in the heat-meltable layer 8 provided on the surface of the heat-sensitive layer 2. In this case, for example, the heat-meltable substance 8a containing the cyan dye undergoes cohesive failure or interfacial peeling due to heat from the heating resistor 4a of the thermal head 4, and moves to the image receiving material 3 side.

The image receiving material used in the present invention is generally a paper, a plastic film, or a paper-plastic film composite as a support, and a polyester resin, a polyvinyl chloride resin, vinyl chloride and other monomers (an image receiving layer) thereon. One or two or more polymer layers of a copolymer resin with, for example, vinyl acetate), polyvinyl butyral, polyvinyl pyrrolidone, polycarbonate and the like are formed.

Further, the support itself may be used as an image receiving material.

The image receiving layer may contain a basic compound and / or a mordant.

The basic compound is not particularly limited, whether inorganic or organic, and examples thereof include calcium carbonate, sodium carbonate, sodium acetate, alkylamine, and arylamine.

Examples of the mordant include compounds having a tertiary amino group, compounds having a nitrogen-containing heterocyclic group, and compounds having these quaternary cation groups.

[Examples] Next, the present invention will be specifically described based on Examples.
The invention is not so limited.

(Example 1)-Preparation of paint-The following raw materials were mixed to obtain a paint of a uniform solution containing a heat-diffusible cyan dye (C-1) having a structure shown in Fig. 1.

Thermal diffusible dye (C-1) 10 g Nitrocellulose 15 g Methyl ethyl ketone 200 ml Thermal transfer recording material Applying and drying a 4.5 μm polyethylene terephthalate film (support) using a wire bar so that the coating amount after drying becomes 1.0 g / m ² , and forming a heat-sensitive layer on the polyethylene terephthalate film A thermal transfer recording material was obtained.

A nitrocellulose layer containing a silicon-modified urethane resin (SP-2105, manufactured by Dainichi Seika) is provided as a sticking prevention layer on the back surface of the polyethylene terephthalate film.

- receiving material - it was laminated with polyethylene on both sides of the paper, including its polyethylene layer on one side [white pigment (TiO ₂₎ and bluing agents. Was coated with a vinyl chloride resin containing 0.15 g / m ² of silicone oil as an image receiving layer so as to have a coating weight of 5 g / m ² to obtain an image receiving material.

The configuration of this image receiving material is illustrated in the drawing as shown in FIG. 3, and polyethylene layers 11a, 11b are provided on both sides of the paper 10.
Are laminated, and a polyvinyl chloride layer 12 is laminated on the polyethylene layer 11a on one side.

-Thermal transfer recording method-The thermal transfer recording material and the image receiving material are overlapped so that the coated surface of the thermal transfer recording material and the image receiving surface of the image receiving material face each other, and a thermal head is placed from the sticking prevention layer side of the thermal transfer recording material. And image recording was performed.

Maximum reflection density and absorption characteristics of the obtained image (2 on the short wave side)
Table 1 shows the measurement results of the secondary absorption) and the image stability (light fastness).

The recording conditions and the measurement method are as shown below.

Line density of main scanning and sub-scanning: 8 dots / mm Recording voltage: 0.6 W / dot Heating time of head: 20 msec (applied energy about 11.2 × 10 ^-3 J) to 2 msec
(Applied energy: about 1.12 × 10 ⁻³ J), the heating time was adjusted stepwise.

Maximum reflection density: Optical densitometer [measured using a PCA-65 type manufactured by Konica Corporation.

Absorption characteristics: Comparative example 1 was regarded as a reference Δ, visually high chroma was evaluated as ○, and low chroma was evaluated as ×.

Image stability: The sample was evaluated by irradiating the sample with a xenon fade meter for 96 hours.

(Examples 2 to 5) The same conditions as in Example 1 except that cyan dyes C-2, C-3, C-10 and C-12 were used instead of cyan dye C-1 in Example 1. To prepare a heat-sensitive transfer recording material and an image receiving material, and an image was formed in the same manner. Table 1 shows the measurement results of the maximum reflection density, absorption characteristics (secondary absorption on the short wavelength side), and image stability (light fastness) of the obtained image.

(Comparative Examples 1 and 2) The following 2 was used in place of the cyan dye C-1 in Example 1.
A thermal transfer recording material and an image receiving material were prepared under the same conditions as in Example 1 except that the comparative dyes A-1 and A-2 were used, and an image was formed in the same manner.

Maximum reflection density and absorption characteristics of the obtained image (2 on the short wave side)
Table 1 shows the measurement results of the secondary absorption) and the image stability (light fastness).

From Table 1, it can be seen that in each of the examples using the cyan dye according to the present invention, a cyan image having a higher density and excellent absorption characteristics and image stability can be obtained as compared with each of the comparative examples using the comparative dye. It turns out that it is possible.

Example 6 A thermosensitive transfer recording material was prepared by sequentially applying a yellow thermosensitive layer, a magenta thermosensitive layer, and a cyan thermosensitive layer on the same support as in Example 1.

However, the cyan thermosensitive layer has the same configuration as in Example 1,
The structures of the yellow thermosensitive layer and the magenta thermosensitive layer are as shown below.

-Yellow heat-sensitive layer-Binder: polyvinyl butyral, coating amount 0.9 g /
m ^2.

Yellow dye: has the following structure. Attached amount 0.6 g / m ² .

- magenta thermosensitive layer - Binder: nitrocellulose, per weight 0.9 g / m ^2.

Magenta dye: has the following structure. Attached amount 0.6 g / m ² .

A video printer (VY-10, manufactured by Hitachi, Ltd.) using the thermal transfer recording material and the same image receiving material as in Example 1.
When the thermal transfer was performed according to 0), a full-color image having good gradation, color reproducibility, and image stability was obtained.

Example 7 100 ml of an aqueous solution containing 5 g of a ball mill dispersion of p-toluamide, 7 g of polyvinylpyrrolidone, and 0.3 g of a hardener having the following composition as an intermediate layer on the cyan ink layer of the thermal transfer recording material of Example 6. Was applied so that the coating amount of p-toluamide was 0.5 g / m ² .

Further, as a heat-fusible layer on the intermediate layer, an ultraviolet ray inhibitor of the following structural formula (with a coating amount of 0.1 g / m ² ), an antioxidant of the following structural formula (with a coating amount of 0.1 g / m ² ), and ethylene-acetic acid vinyl copolymer (vinyl acetate content of 20 wt%, per the amount of 0.2 g / m ²⁾ and a Karubanarou a (per amount 0.2 g / m ²⁾ and coating by hot melt coating, creating a thermal transfer recording material did.

Thermal transfer was performed by a video printer in the same manner as in Example 6 using the thermal transfer recording material and plain white paper as an image receiving material.

As a result, a full-color image having excellent color reproducibility and gradation was obtained.

[Effects of the Invention] The heat-sensitive transfer recording material of the present invention is provided with a layer containing a specific heat-diffusible cyan dye on a support.
An image having excellent heat resistance and light resistance can be obtained.

Further, according to the thermal transfer recording method of the present invention, since the thermal transfer recording material is used, an image having the above-mentioned features can be efficiently formed.

[Brief description of the drawings]

FIG. 1 (part 1), FIG. 1 (part 2), and FIG. 1 (part 3) each show a structural formula of a typical cyan dye according to the present invention. FIGS. 2 (a) and 2 (b) are explanatory views of the principle of the thermal transfer recording method of the present invention. FIG. 3 is a sectional view showing the structure of the image receiving material used in one embodiment of the present invention. DESCRIPTION OF SYMBOLS 1 ... Support, 2 ... Thermal layer, 3 ... Thermal transfer recording material, 4 ... Thermal head, 5 ... Image receiving material, 6 ... Support, 7 ... Image receiving layer, 8 ... Thermal fusibility Layer, 8a: hot-melt substance, 9: thermal transfer material, 10: paper, 11a, 11b ...
Polyethylene layer, 12 ... polyvinyl chloride layer.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-270592 (JP, A) JP-A-61-19396 (JP, A) JP-A-5-17701 (JP, A) JP-A-2- 92686 (JP, A) JP-A-3-124494 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) B41M 5/38 G03C 8/10 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A heat-sensitive transfer recording material having a layer containing a cyan dye represented by the following general formula [I] on a support. Wherein R ¹ is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an aryloxy group,
Cyano group, acylamino group, alkylthio group, arylthio group, sulfonylamino group, ureido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfonyl group, acyl group,
Represents an amino group. R ² represents a halogen atom, an alkoxy group or an aryloxy group. R ³ and R ⁴ represent an alkyl group. m represents an integer of 1 to 3. further
R ¹ and R ³ and R ³ and R ⁴ may combine with each other to form a ring. When m is 2 or more, the groups of R ¹ may be bonded to each other to form a ring. ] 2. An image receiving material is superimposed on the layer of a thermal transfer recording material having a layer containing a cyan dye represented by the general formula [1] according to claim 1 on a support, and the thermal transfer recording material is A thermal transfer recording method, wherein an image is formed on an image receiving material by heating according to image information and diffusing and transferring the cyan dye to the image receiving material side.