JP2893270B2 - Thermal transfer recording material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive transfer material, and more particularly, to a novel heat-sensitive transfer material containing a magenta dye excellent in spectral characteristics, heat resistance and fixability, and the dye. And an image forming method using the same.

[Background of the Invention] As a method for obtaining a color hard copy, a color recording technique using ink jet, electrophotography, thermal transfer, or the like is being studied.

Among them, the thermal transfer method has advantages such as easiness of operation and maintenance, downsizing of the apparatus and cost reduction, and further low running cost.

In this thermal transfer method, a transfer sheet (also referred to as a thermal transfer material) having a fusible ink layer on a support is heated by a thermal head and the ink is transferred onto a transfer-receiving sheet (also referred to as an image receiving material). A heat transfer method in which a transfer sheet having an ink layer containing a heat-diffusible dye (sublimable dye) on a support is heated by a thermal head to transfer the heat-diffusible dye to a transfer-receiving sheet. There are two types of transfer method (sublimation transfer method). In the thermal diffusion transfer method, the tone of the image is controlled by changing the transfer amount of the dye in accordance with the change in the thermal energy of the thermal head. This is advantageous for full-color recording.

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

Therefore, the dye used in the above-mentioned thermal diffusion transfer method needs to have the following properties.

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

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

(3) No thermal decomposition at the heating temperature during recording.

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

(5) The molar absorption coefficient is large.

(6) The addition to the thermal transfer material is easy.

(7) Easy synthesis.

Further, in addition to this, it is required that the fixing property of the image is excellent.

Conventionally, magenta dyes for thermal transfer materials have been disclosed in
Nos. 59-78896, 60-30392, 60-30394, 60-2
No. 53595, No. 61-262190, No. 63-5929, No. 63-20528
No. 8, No. 64-1591, No. 64-63194, etc., anthraquinone dyes, azo dyes, azomethine dyes and the like are disclosed, especially heat diffusion, hue, heat resistance, light resistance A dye satisfying the above conditions and having good fixability has not yet been found.

In view of the above, the present inventors have developed a dye for a thermal transfer material and an image forming method using the same,
As a result of various studies, it was surprisingly found that the dye represented by the general formula [1] satisfies the above-mentioned conditions and is particularly preferable in terms of excellent fixability. It is.

[Object of the Invention] Accordingly, an object of the present invention is to provide a thermal transfer using a magenta dye which satisfies the above-mentioned properties, in particular, heat diffusivity, hue, heat resistance, light resistance and the like, and has greatly improved fixability. An object of the present invention is to provide a material and an image forming method using the dye.

[Constitution of the Invention] The object of the present invention is to provide: 1) a heat-sensitive transfer recording material, characterized by having a heat-sensitive layer containing at least a dye compound represented by the general formula [1] on a support; Wherein R ¹ and R ² are a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group,
Aralkyl, alkoxy, aryloxy, cyano, acylamino, alkylthio, arylthio, sulfonylamino, ureido, carbamoyl, sulfamoyl, alkoxycarbonyl, aryloxycarbonyl, sulfonyl, acyl, Represents an amino group.

X represents an atom group necessary for forming a nitrogen-containing heterocyclic ring.
m represents 1, 2, 3 or 4. 2) A heat-sensitive transfer material having at least a heat-sensitive layer containing a dye compound represented by the following general formula [I] on a support is heated from the back surface of the support according to image information, and a basic image is formed on the image-receiving material. This is achieved by a thermal transfer image forming method, which comprises forming an image with the dye compound in the presence of a compound and / or a mordant.

Wherein R ¹ and R ² are a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group,
Aralkyl, alkoxy, aryloxy, cyano, acylamino, alkylthio, arylthio, sulfonylamino, ureido, carbamoyl, sulfamoyl, alkoxycarbonyl, aryloxycarbonyl, sulfonyl, acyl, Represents an amino group.

X represents an atom group necessary for forming a nitrogen-containing heterocyclic ring.
m represents 1, 2, 3 or 4. Hereinafter, the present invention will be described in more detail.

In the general formula [I], R ¹ and R ² are a hydrogen atom, a halogen atom (eg, a chlorine atom, a fluorine atom, etc.), an alkyl group (eg, a methyl group, an ethyl group, an isopropyl group, an n-butyl group), a cycloalkyl group (Eg, cyclopentyl group, cyclohexyl group, etc.), aryl group (eg, phenyl group, etc.), alkenyl group (eg, 2-propenyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), alkoxy group (eg, methoxy group) Ethoxy, isopropoxy, n-butoxy, etc.), aryloxy (eg, phenoxy), cyano, acylamino (eg, acetylamino, propionylamino), alkylthio (eg, methylthio, ethylthio) Group, n-butylthio group, etc.), arylthio group (for example, phenylthio group), Honiruamino group (e.g. methanesulfonylamino group, Ben diesel sulfonylamino group, etc.), a ureido group (e.g., 3-methylureido group, 3,3
-Dimethylureido group, 1,3-dimethylureido group, etc.), carbamoyl group (for example, methylcarbamoyl group,
Ethylcarbamoyl group, dimethylcarbamoyl group, etc.),
Sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl group (eg, methane Sulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (for example, acetyl group, propanoyl group,
Butyroyl group) and amino group (methylamino group, ethylamino group, dimethylamino group, etc.).

These R ¹ and R ² may be further substituted. 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), an alkoxy group, and the like. Groups (eg, methoxy, ethoxy, etc.), amino groups (eg, methylamino, ethylamino, etc.), acylamino groups (eg, acetyl, etc.), sulfonyl groups (eg, methanesulfonyl, etc.),
Examples include an alkoxycarbonyl group (eg, a methoxycarbonyl group), a cyano group, a nitro group, a halogen atom (eg, a chlorine atom, a fluorine atom, and the like).

Further, the group represented by R ¹ and R ² (including a substituent when it has a substituent) preferably has 12 or less (particularly preferably 8 or less) carbon atoms.

The compound represented by the general formula [I] (hereinafter referred to as the compound used in the present invention) is particularly preferably represented by the following general formulas [II] to [V].

[Wherein, R ¹ , R ² and m have the same meanings as defined in the general formula [I].

R ³ is a hydrogen atom, a halogen atom (eg, a chlorine atom, a fluorine atom, etc.), an alkyl group (eg, a methyl group, an ethyl group,
Isopropyl group, n-butyl group), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aryl group (eg, phenyl group, etc.), alkenyl group (eg, 2-propenyl group, etc.), aralkyl group (eg, benzyl group, -Phenethyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), aryloxy group (for example, phenoxy group, etc.), cyano group, acylamino group (for example, acetylamino group, propionylamino Group), alkylthio group (eg, methylthio group, ethylthio group, n-butylthio group, etc.), arylthio group (eg, phenylthio group), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group ( For example, 3
-Methylureido group, 3,3-dimethylureido group, 1,3-
Dimethylureido group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group) , Ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.) ), Amino group (methylamino group, ethylamino group, dimethylamino group, etc.)
Represents

R ³ may be further substituted. 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, a methoxy group). Ethoxy group), amino group (eg, methylamino group, ethylamino group, etc.), acylamino group (eg, acetyl group, etc.), sulfonyl group (eg, methanesulfonyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group), cyano Group, nitro group, halogen atom (eg, chlorine atom, fluorine atom, etc.).

The group represented by R ³ (including a substituent when it has a substituent) preferably has 12 or less (particularly preferably 8 or less) carbon atoms.

The compound used in the present invention generally has the following general formula [I
I] obtained by oxidative coupling of the coupler represented by formula [I] with a p-aminoenol derivative.

[Wherein, ¹ and X have the same meanings as defined in the general formula [I]. The conventionally known compound is obtained by oxidative coupling of the general formula [VI] with a p-phenylenediamine derivative, whereas the compound used in the present invention is a compound of the general formula [V
I] and a compound obtained by oxidative coupling of a p-aminophenol derivative, and thus having a phenolic hydroxyl group improves fixability.

Next, typical examples of the dye represented by the general formula [I] used in the present invention are shown, but the present invention is not limited thereto.

The compound used in the present invention gives a good hue of magenta under basic conditions, but shifts to a pale color on the acidic side to a red to orange hue. Therefore, although it is possible to transfer the compound used in the present invention alone to form an image alone, a clear magenta image is obtained by forming an image in the presence of a basic compound in the image receiving layer.

Further, the compound used in the present invention gives a good cyan hue regardless of the presence or absence of a basic compound even when the compound is mordant with a mordant. Therefore, it is preferable to form an image in the image receiving layer in the presence of a basic compound and / or a mordant.

In particular, a method of forming an image in the presence of a mordant is more preferable because the dye is morded with the mordant to improve fixability.

In the present invention, the basic compound and / or mordant
It is added to the image receiving material (usually referred to as an image receiving layer). However, when the heat-sensitive transfer material has a two-layer structure as described later, it may be added to the heat melting layer. Further, a basic compound may be added to the ink layer. In those cases, the image receiving layer does not necessarily need to contain a basic compound and / or a mordant.

The basic compound used in the present invention is not particularly limited, but an inorganic or organic basic compound is used, and examples thereof include calcium carbonate, sodium carbonate, sodium acetate, alkylamine, and arylamine.

In the present invention, it is preferable to use a mordant,
It is particularly preferable to add a mordant to the image receiving layer.

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

When a mordant is used in the image receiving layer, the mordant is preferably immobilized, and a polymer mordant is particularly preferred. When a mordant is added to the heat-melted layer of the thermal transfer material, a mordant having a molecular weight of 400 or less is preferable.

The polymer mordant may form the image receiving layer by itself, but is usually used together with another appropriate binder forming the image receiving layer. Examples of the binder include those formed of a heat-resistant organic polymer having a glass transition point of 40 ° C. or more and 250 ° C. or less described in JP-A-57-207250. These polymers are usually carried on a support as an image receiving layer, but may themselves also serve as the support. As this polymer, "Polymer Handbook,
Second Edition ”(J. Brandrup, EHImmergut
Ed.) Synthetic polymers having a glass transition point of 40 ° C. or higher as described in John Wiley & Sons are also useful.

As the polymer mordant, JP-A-48-28325 and JP-A-54-7
No. 4430, No. 54-124726, No. 55-22766, No. 55-14233
No. 9, No. 55-23850, No. 60-23851, No. 60-23852,
No. 60-23853, No. 60-57836, No. 60-60643, No. 60
-118834, 60-122940, 60-1222941, 60-
No. 122942, No. 60-235134, U.S. Pat.No. 2,484,430,
No. 2,548,564, No. 3,148,061, No. 3,148,161, No. 3,3
09,690, 3,756,814, 3,898,088, 3,958,99
No. 5, 4,115,124, 4,124,386, 4,193,800,
JP 4,273,853, JP 4,282,305, JP 4,450,224, British Patent No. 1,594,961, JP 2,056,101, JP 2,093,041, etc. it can.

Hereinafter, specific representative examples of the mordant used in the present invention will be described, but the present invention is not limited to these examples.

(The numbers represent mol%) The nitrogen-containing heterocyclic group is preferably an imidazole group or a pyridyl group, and specific examples of the polymer mordant having the group include the following polymers.

Specific examples of the polymer mordant having a quaternary ammonium group include the following polymers.

The heat-sensitive transfer material of the present invention is prepared by dissolving the dye in a solvent together with a binder or dispersing the dye in fine particles to prepare an ink containing the dye, coating the ink on a support, and drying the ink. A layer or a thermosensitive layer is obtained.

The amount of the dye used in the present invention is per 1 m ² of the support.
0.1 g-20 g is preferred.

The image forming method using the thermal transfer material obtained in this manner prepares an image-receiving material, aligns the heat-sensitive layer and the image-receiving layer surface, and transfers heat from the back surface of the support of the thermal transfer material according to image information. When applied, the dye corresponding to the thermal image diffuses into the image receiving layer, where the dye is fixed and a dye image is obtained.

As the binder, cellulose-based, polyacrylic acid-based, polyvinyl alcohol-based, polyvinylpyrrolidone-based water-soluble polymer, acrylic resin, methacrylic resin, polystyrene, polycarbonate, polysulfone,
There are polymers soluble in organic solvents such as polyether sulfone and ethyl cellulose. When using a polymer soluble in an organic solvent, not only is it used by dissolving it in an organic solvent,
It may be used in the form of a latex dispersion.

The amount of the binder used is 0.1 g / m ² of the support.
50 g is preferred.

The support used in the present invention has good dimensional stability and can withstand heat during recording with a thermal head.
Any material may be used, and heat-resistant plastic films such as thin paper such as condenser paper and glassine paper, polyethylene terephthalate, polyamide and polycarbonate can be used.

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

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

The ink layer, that is, the heat-sensitive layer, used in the present invention is coated on the support or printed on the support by a printing method such as a gravure method. The thickness of the heat sensitive layer is 0.1μ in dry film thickness
m to 5 μm are preferred.

As a solvent for adjusting the ink of the thermosensitive layer, water,
Alcohols (eg, ethanol, propanol), cellosolves (eg, ethyl acetate), aromatics (eg, toluene, xylene, chlorobenzene), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, dioxane), chlorine-based Solvents (for example, chloroform, trichloroethylene) and the like can be mentioned.

The heat-sensitive transfer material of the present invention basically comprises an ink layer comprising the dye and the binder used in the present invention on a support, that is, a heat-sensitive layer. It may have a heat-fusible layer containing a heat-fusible compound as described in JP-A-106997.

Further, when the heat-sensitive transfer material of the present invention is applied to full-color image recording, a cyan ink layer containing a cyan dye, a magenta ink layer containing a heat-diffusible magenta dye, and a heat-diffusible yellow dye are contained on a support. It is preferable that three layers of the yellow ink layer are sequentially and repeatedly applied.

In addition, if necessary, an ink layer containing a black image forming substance is further provided in addition to the yellow, magenta, and cyan layers,
A total of four layers may be sequentially and repeatedly applied.

[Examples] Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to only these Examples.

Example 1 [Ink layer (thermosensitive layer)] A mixture having the following composition was treated using a paint conditioner to obtain an ink in a uniform solution containing a heat-diffusible dye used in the present invention.

Dye compound Dye-2 10g Polyvinyl butyral resin 15g Methyl ethyl ketone 150ml Toluene 150ml [Preparation of transfer sheet] The ink containing the above heat diffusible dye was applied to a thickness of 15 µm.
On a support consisting of a polyimide film, coated as coating amount after drying is 1.0 g / m ² using a wire bar and dried to form a layer containing a thermally diffusible dye, the heat-sensitive transfer material -1 was produced.

Similarly, instead of Dye-2 of the thermal transfer material-1,
Except that the dyes shown in Table 2 were used, thermal transfer materials-2 to 7 were produced in the same manner as thermal transfer material-1.

[Preparation of Image Receiving Material] 10 g of polyvinylpyrrolidone was dissolved in 100 g of a latex dispersion containing 10% of a polymer mordant (P-16), and the amount of polyvinylpyrrolidone (binder) was applied per 1 m ^{2 of the} support.
An image receiving material-A was prepared by applying 10 g on a photographic baryta paper.

Similarly, image receiving materials-B to G having the compositions shown in Table 1 were produced.

[Thermal Transfer Image Forming Method] The thermal transfer sheet (1 to 7) obtained as described above and the image receiving material (A and E) are overlapped so that the ink-coated surface of the thermal transfer sheet and the image receiving surface of the image receiving material face each other. The image was recorded by applying a thermal head from the back of the thermal transfer sheet.
As a result, an image having excellent gradation was obtained.

 Table 2 shows the maximum density of the obtained image.

 The recording conditions at this time are as follows.

Line density of main scanning and sub-scanning 4 dots / mm Recording power 0.8 W / dot Heating time of thermal head Between 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 step by step.

As is apparent from Table 2, a high-density thermal transfer image can be obtained by using the method of the present invention.

Example 2 The image (No. 1 to No. 14) obtained in Example 1 was obtained by laminating high quality paper for dry electrophotography on the image receiving layer side and containing dioctyl phthalate (30%) as a plasticizer. From the top, 30g /
After applying a pressure of ² cm ² and leaving at a temperature of 60 ° C. for 3 days, the high quality paper was peeled off from the image receiving material, and the image density re-transferred onto the high quality paper was measured.

 Table 3 shows the obtained results.

As is apparent from Table 3, an image having excellent fixability can be obtained by the method of the present invention.

Example 3 Thermal transfer material and image receiving materials A to G produced in Example 1
And the same thermal transfer recording as in Example 1 was performed. Table 4 shows the density and hue of the obtained image. Further, a fixing property (non-retransferability) test was performed on these images in the same manner as in Example 2. Table 4 also shows the results.

As is clear from Table 4, the method of the present invention provides an image having high density, good hue, and excellent fixability.
In the case of using a mordant other than the dye D, the effect of the present invention is particularly remarkable.

The absorption spectrum distribution of the obtained image dye (image No. 1) is sharp as shown in FIG. 1, and it has excellent hue as a magenta dye image. I understand.

[Effect of the Invention] The thermal transfer image forming method of the present invention provides good gradation,
Further, a color image having excellent fixability can be obtained.

[Brief description of the drawings]

FIG. 1 is a graph showing the absorption spectrum distribution of the dye used in the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) B41M 5/38-5/40

Claims (2)

(57) [Claims] 1. A heat-sensitive transfer recording material comprising a support having a heat-sensitive layer containing at least a dye compound represented by the general formula [I]. Wherein R ¹ and R ² are 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, a cyano group, an acylamino group, an alkylthio group, an arylthio group. Group, sulfonylamino group, ureido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfonyl group, acyl group, and amino group. X represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. m
Represents 1, 2, 3 or 4. ] 2. On a support, at least the following general formula [I]
A heat-sensitive transfer material having a heat-sensitive layer containing a dye compound represented by is heated from the back surface of the support according to image information, and an image formed by the dye compound is formed on the image receiving material in the presence of a basic compound and / or a mordant. Forming a thermal transfer image. Wherein R ¹ and R ² are 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, a cyano group, an acylamino group, an alkylthio group, an arylthio group. Group, sulfonylamino group, ureido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfonyl group, acyl group, and amino group. X represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. m
Represents 1, 2, 3 or 4. ]