JPH0491988A - Thermal transfer recording material and thermal transfer recording method - Google Patents

Abstract

PURPOSE:To improve thermal diffusibility, hue, and light fastness by a method wherein a layer containing cyan coloring matter is established on a base material. CONSTITUTION:A thermal transfer recording material is formed by establishing a layer containing cyan coloring matter expressed by the formula I on a base material [where, in the formula, R<1> represents a hydrogen atom, a halogen atom, an alkoxy radical, etc., R<2> a halogen atom, an alkoxy radical, etc., R<3> and R<4> an alkyl radical, (m) an integer of 1-3, R<1> and R<3>, and R<3> and R<4> may form a ring by combining with each other, and, in the case where (m) is an integer of 2 or more, R<1> radicals may be combined with each other to form a ring.] An image receiving material is superimposed on a layer containing the cyan coloring matter, and the thermal transfer recording material is heated according to image information. An image is formed on the image receiving material by transfer by diffusion of the cyan coloring matter to the image receiving material side.

Description

[Detailed Description of the Invention] [Industrial Field of Application] Regarding the invention, photographic material, thermal transcription method,
More specifically, we will introduce a new thermal transfer recording material containing a cyan dye that has particularly excellent hue, light fastness, and thermal diffusivity, and a thermal transfer recording method that can efficiently form images using the material. k” related.

■Prior art and inventions or problems to be solved] Conventionally, color recording technologies such as the inkjet method, the electrophotographic method, and the thermal transfer method have been considered as methods for obtaining color hard copies. Among them, the thermal transfer type has advantages such as easy operation and maintenance, miniaturization of the device, low cost, and low running cost.

In this thermal transfer method, a transfer sheet (thermal transfer recording material) consisting of a support and a heat-fusible ink layer is heated with a heat-sensitive head, and the heat-fusible ink layer is transferred to an ink-like transfer sheet (image-receiving material). ) and the support ↓
, an ink layer containing a heat-diffusible dye (sublimable dye) is provided on the transfer sheet. Depending on the power type (sublimation transfer type J type) or the latter thermal diffusion transfer type, the amount of transferred dye can be changed depending on the heat energy of the thermal head. This is advantageous for full-color recording since it is possible to control the Wi tone of one image.

However, the dye used in the thermal transfer recording material is important, and the color tone of this dye affects the speed, image quality, storage stability of the image, etc. of the thermal transfer recording material. make a big impact.

It is desirable that this type of dye has the following properties: (a) Easy thermal diffusion under heat-sensitive recording conditions (head temperature, heating time).

(b) Color reproduction 1-1 Observe the preferred hue.

(c) Heating temperature during recording "C" No thermal decomposition.

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

(E) 9″-L suction X4 coefficient or larger.

(f) J and can be easily added to thermal transfer recording materials.

(g) Synthesis or something easy.

(-5) Good solubility in solvents.

(i) The resulting image should have excellent fixing properties; however, a thermal transfer recording material using a dye that satisfies the above conditions has not yet been developed.

For example, regarding the cyan dye for thermal transfer M4A materials, JP-A No. 59-788!
0-1307:15 No. 6 Togawa No. 31.292.
No. 60-239289, No. 61-1, No. 9395, No. 61-354194, No. 61-31292, No. 61
No.-31467, No. 61-35994, No. 61 1
No. 48269, No. 62-1'1191, No. 61912
No. 88, No. 6391287, and No. 61290793 disclose 10'nodoquinone dyes, anthraquinone color charts, azomelane dyes, etc., and these dyes satisfy the above-mentioned conditions. ).

The present invention consists of 1. Number information i! It is done for the good of the people.

An object of the present invention is to provide a thermal transfer recording material N and a thermal transfer recording method using a dye that satisfies the above conditions, particularly a cyan dye that has two heat-diffusible hues and excellent light resistance.

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

In addition, the present invention as set forth in claim 2 provides a heat-sensitive transfer recording material having a layer containing a cyan dye represented by the following general formula [1] on the support L. 'Layer the materials, heat the thermal transfer recording material according to the image information, and each time the cyan dye is diffused and transferred to the image-receiving material side', the image is transferred to the image-receiving material-1-1. It is a heat-sensitive transfer recording material υ, which is characterized by forming and bending.

[However, in formula 1, Kl is Ryo Kinohara, Ryo Halogen Hara f,
Al;:1;-l group, cycloalkyl group, aryl group, alkenyl group, aralhale group, alkoxy group, aryloxy group, cyano group, anruamino group, alkylthio group, arylrvguo group, sulfonyl It represents an amino group, a ureido group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, an acyl group, and an amino group. R2 represents a halogen radical f, an alkoxy group or an aryloxy group.

R: I and R4 represent an alkyl group, m is 1-
・Represents the integer 3. Furthermore, R1 and R1 and R3 and R
4 may be bonded to each other to form a ring. Also, m or 2
Below 1. In the case of an integer of , the groups of R' may be bonded to q' to form a 'C ring. ] Hereinafter, the general formula [I] will be explained in more detail.

R' is a hydrogen atom, a halogen atom (for example, chlorine K f-
, fluorine atoms, etc.), alkyl groups (such as methyl groups,
]:, del group, isobutylene group, n-methyl group, etc.)
, cycloalkyl groups (e.g., cyclopentyl group, cyclohexyl group, etc.), aryl groups (e.g., phenyl group, etc.), alkenyl groups (e.g., 2-propenyl group, etc.), aralkyl groups (e.g., pencil group, 2-phenethyl group, etc.), Alkoxy groups (e.g. methoxy, ethoxy, impropoxy, n-butoxy), aryloxy groups (e.g. Jnoxy), cyano groups, acylamino groups (e.g. acetylamino, propionyl) (such as amino group), alkylthio group (such as methylthio group, ethylbution group, n-butylthio group)
, arylthio group (e.g. phenylthio group), sulfonylamino group (e.g. methanesulfonylamino group, benzenesulfonylamino group), urei) group (e.g. 3-methylureido group, 3,3-dimethylureido group,
1.3-dimethylureido group), carbamoyl group (
For example, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group), sulfamoyl group (
For example, eralsulno, .(=yl group, dimethylsulfamoyl group, etc.), alkoni dicarbonyl group (e.g. metho-central dicarbonyl group, ethoxycarbonyl group, etc.),
Aryloxycarbonyl groups (for example, J-dicarbonyl group), sulfonyl groups (for example, methanesulfogol group, ), enylsulfonyl group), acyl groups (for example, acedel group, propanoyl group, (eg, yl group, etc.), amino group (eg, methylamino group, ethylamino group, dimethylamino group, etc.).

These groups may have a substituent, and C as the substituent is an alkyl group (for example, a methyl group, an ethyl group, a l-
・Rifluoromethyl group (and), aryl group (and λ)
, T, nyl group), alkoxy group (for example, ethoxy group, ethoxy group, etc.), amino3. (for example, λ is a methylamino group or ethylamino group), acylamino group (for example, an acetylamino group, etc.), sulfo, sulfo group (for example, methanesulfonyl group, etc.), alkoxycarbonyl group (for example, a methanesulfonyl group, etc.), an alkoxycarbonyl group (for example, a methanesulfonyl group, etc.) carbonyl group), cyano group,
Examples include nitro groups and halogen atoms (the ``t'' means chlorine and fluorine atoms).

R1 containing these substituents or R1 having no substituents preferably has 12 or more carbon atoms, particularly preferably 8 or less carbon atoms.

Examples of the alkoxy group represented by R2 include an ethoxy group, an ethoxy group, an isopropoxy group, and an n-ethoxy group, and an alkoxy group having an R prime number of 8 or more is particularly preferred.

Examples of the aryloxy group represented by R2 include λ and Lnoxy groups, and the benzene ring may have any substituent.

The M substituent on the benzene ring is preferably a substituent having 8 or less carbon atoms.

As the halogen source f represented by R2, for example, λ is salt,
Examples include S atom and bromine atom, preferably bromine f.

Specific representative examples of the cyan dye represented by the general formula [I] are shown in Figure 1. All cyan dyes satisfy the conditions (A) to (S) mentioned above, and among them, Excellent in heat diffusivity, color and light resistance.

- The cyan dye represented by the general formula [I], that is, the dye according to the present invention, can be synthesized using a known synthesis method, ie, the general formula [1]
1] and a phenol derivative represented by the general formula F [I
It can be produced by an oxidative coupling reaction with a P-phenylenecyamine derivative or a P-aminophenol derivative represented by [11].

(R1) (In formula 1, R1, R2, R3 and R4 have the same meanings as defined in the general formula [I] above.) This oxidative coupling reaction is allowed to proceed under basic conditions F. The reaction medium may be any of a solvent, an aqueous stone solvent, and an aqueous solution.

The oxidizing agent may be any oxidizing agent that has a potential that can oxidize P-phenylenecyamine derivatives or P-aminophenol derivatives, regardless of whether they are organic or inorganic, such as silver halide, hydrogen peroxide, It is possible to use inorganic oxidizing agents such as manganese, potassium persulfate, and oxygen, and organic oxidizing agents such as N-bromosuccinimide and chloramine T.

In addition to the synthesis method described in L, the cyan dye according to the present invention is also produced by electrode reaction.

When based on this electrode reaction, V current, voltage, supporting electrolyte,
It is necessary to appropriately select L' for the solvent, electrode, etc.

The heat-sensitive transfer recording material of the present invention comprises a layer containing a cyan dye represented by the general formula [I] (sometimes referred to as a heat-sensitive layer) as a support 1. It will be set up in

The dye content in the heat-sensitive layer is preferably O.OS to 10 per liter of support.

The heat-sensitive layer is formed by dissolving the dye or two or more dyes together with a binder in a solvent, or by dispersing them in the form of fine particles in a solvent, or by a hot-melt method. It can be formed by preparing a coating material, coating the coating material on a support, and drying it appropriately.

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

Examples of the binder include cellulose-based, polyacrylic acid-based, polyvinyl alcohol-based, and polyvinylpyrrolidone-based water-soluble polymers, acrylic resin, methacrylic resin, polystyrene, polycarbonate, polysulfone, polyneedle sulfone, polyvinyl butyral, polyvinyl acetal, and nitro. "J" refers to cellulose, ethyl cellulose, etc.

One or more of these binders 1-7 can be used not only by dissolving them in a typical solvent, but also by dispersing them in a latex form.

The amount of binder used is 0.0 per meter of support.
5 to 30 g is preferred.

The solvent for preparing the paint is wood, alcohol (
(e.g. ethanol, propatool), cellosols (
and λ is acetic acid, and aromatic compounds (and λ is toluene,
A-silene, chlorobenzene), ketones (e.g.
Examples include Hutlach F. Lofran, dioxane), chlorinated solvents (eg, chloroform, 1-lichlorethylene), and the like.

The support may be one that has good J-method stability and can withstand the heat of the thermal head during recording. A heat-resistant glass film such as polyamide or polycarbonate is preferably used.

The thickness of the support is preferably 2 to 3 μm, and the support has a partial layer for the purpose of improving adhesion with the binder and preventing transfer and dyeing of the dye to the support. It's okay to stay.

Furthermore, a slipping layer may be provided on the back side of the support (the side opposite to the heat-sensitive layer) ζ' for the purpose of preventing the heat and the viscosity of the support.

The heat-sensitive transfer material of the present invention has heat-sensitive layer 1 in JP-A-5G-1.
This heat-fusible compound, which may have a heat-fusible layer, is described in Publication No. 06997. 1" colorless or white compounds are preferably used, such as waxes such as carnauba wax, beeswax, and campri wax, higher fatty acids such as stearic acid and behenic acid, alcohols such as A. silitol, and γ. Ya1
- Amides such as amide, benzamide, ), 1-nil
・Ureas such as flare, cylindrical, and 1-dil/a can be mentioned.

These heat-melting layers may contain a polymer such as polyvinylpyrrolidone, polyvinylfural, or saturated polynisnal in order to enhance the retention of the five dyes.

According to the thermal transfer recording material of the present invention, as described below, -
・If it is possible to obtain a cyan dye image with gradation using a seed dye, or if it is applicable to full-color image recording,
Containing the cyan dye according to the present invention → "curing cyan heat-sensitive layer,"
A total of 3 layers, a magenta heat-sensitive layer containing a heat-diffusible magenta dye and a heat-sensitive layer containing a heat-diffusible yellow dye, are sequentially and repeatedly coated on the same surface of the support. It's so sad to be there.

A further heat sensitive layer containing a U-2 black imaging material may be added to the above three layers, for a total of four layers, which may be sequentially and repeatedly deposited on the same surface of the support.

In the heat-sensitive transfer recording method of the present invention, T is h-large when the heat-sensitive layer of the heat-sensitive transfer recording material and the image-receiving material are superimposed, and the cyan dye is received from the heat-sensitive layer. By moving to the side slope and fixing ζ', the image-receiving material J-ζ is formed.

The six ways of image formation will be explained with reference to the drawings. In FIG. 2 (A), the cyan dye is contained in the photosensitive layer 2 of the photosensitive/thermal transfer recording material 3 consisting of a support 1 and thermal N2. 1±-
Then, this cyan dye is, for example, → Tomaru・7 +・
The J-7 image receiving material 5 is heated by heat from the heating resistor 4a of 4
"Diffusion transfer I" is fixed in the image receiving layer 7 of the support 6. In this case, if the cyan dye is contained in the heat-fusible layer 8 provided on the surface of the heat-sensitive M2, the heat from the heat-generating resistor 4a of the thermal spatula l'4 will cause Heat melting + containing cyan dye
'I Substance 8a causes cohesive failure t, l or interfacial peeling 4
- then move to the image receiving material 3 side t1.

3. The image-receiving side used in the present invention is generally made of paper, plastic sack film, or paper-plastic film composite as a support. copolymer resins with other seven polymers (such as P''-acetate), polybutyral, polyvinylpyrrole, polycarbonate, etc. The above polymer layer is formed.

Also, sometimes the special holiday itself is used as an image-receiving material.

The image-receiving layer may contain a basic compound and /1 or a thickening agent.

As for the basic compound, there are no particular restrictions whether it is inorganic or organic, for example, calcium carbonate, sodium carbonate, 1lium chloride, alylamine, arylamine, etc. are used. That's possible.

As a dyeing agent, a compound having a tertiary a-mino group, a compound having a nitrogen-containing heterocyclic group, or a 4-
Compounds having these quaternary cation groups can be mentioned.

[Example] Next, the present invention will be specifically explained based on Examples, but the present invention is not limited thereto.

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

Heat-diffusible dye (c-i)...10g Nitrocel [I......15g Methyl ethyl ketone...200yn f) - Thermal transfer recording material - Apply the above paint to a polyethylene derephthalate film (support) with a thickness of 4.5 μm using a wire parser so that the coating amount after drying is 1.0z/m 2 and dry. A heat-sensitive transfer recording material was obtained by forming a heat-sensitive layer on a polyethylene prephthalate film.

In addition, 1. On the back side of the polyethylene derephthalate film, a nitrocellulose layer containing a silicone modified urethane resin (SP-2105, manufactured by I-Kikaku Co., Ltd.) was provided as an anti-dicking layer.

The image-receiving material polyethylene was laminated on the inner surface of the paper, and the polyethylene layer I on one side contained a white pigment (Ti, 02) and a blue tint. ] -1- of the image-receiving layer and apply 0 silicone oil.
．． 15g/1ru2 containing chloride resin +=t
It was coated at a weight of 5 g/m 2 to obtain an image-receiving material.

The structure of this image-receiving material is explained with a drawing as shown in Fig. 3.
1a and llb are laminated, and a polyvinyl chloride layer 12 is laminated on the polyethylene layer 1.1a on the 4 side.

Thermal Transfer Recording Method The thermal transfer recording material and the above-mentioned image receiving material are stacked so that the coated surface of the thermal transfer recording material faces the image receiving surface of the receiving material, and a thermal spatula is applied from the sticking 11 layer side of the thermal transfer recording material. Image recording was performed by applying l='.

Maximum reflection density of the obtained image, absorption characteristics (secondary absorption on the short wave side), image quality: ii′+! The measurement results for +(il luminosity) are shown in Table 1.The recording conditions and measuring force method are as follows.

1 scan 1. Sub-scanning line V: valley/8 totu) -/ mm notation
Recording voltage: -0.6W/heating time: 20m5ecc applied energy: approx. 11. ．． 2X 10-
'J) to 2m5ec (applied energy approximately 1.12X
The heating time was adjusted stepwise between 1.0 and 3 J).

Maximum reflection density: C was measured using an optical densitometer [1-Chiki Co., Ltd. PC^-55 model].

Absorption characteristics - Comparative example 1 is used as a standard △, and those with high chroma as seen by FI viewing are 0. The lowest one was marked as X.

Image stability: Evaluated by irradiating the sample for 96 hours using a xenon J-F meter.

(Example 2 = 5) Except that cyan dyes C-2, (? The conditions were the same as in Example 1 (a thermal transfer recording material and an image-receiving material were prepared, and a portrait was formed in the same manner. ), and the measurement results of image stability (light resistance) are shown in Table 1.

(Comparative Example 1.2) The same conditions as in Example 1 were used, except that the cyan dye in Example 1 (2 types of comparative dyes A-1 and A-2, indicated by "b" were used in the -1f range), respectively. A heat-sensitive transfer recording material and an image-receiving material were prepared, and images were formed in the same manner.

Table 1 shows the measurement results of the maximum reflection density, absorption characteristics (secondary absorption on the short wave side), and image stability (light resistance) of the obtained images.

Comparative dye A-1: Comparative dye A-2 (total) 0 Good f, Slightly poor, Poor From Table 1, in each example using the cyan dye according to the present invention, each comparative example using the comparative dye This comparison shows that it is possible to obtain a cyan image with high density and excellent absorption characteristics and image stability.

(Example 6) A yellow heat-sensitive layer, a magenta heat-sensitive layer, and a cyan heat-sensitive layer were sequentially coated on the same support as in Example 1 to prepare a heat-sensitive transfer recording side slant.

However, the cyan heat-sensitive layer has the same structure as in Example 1 (with,
The structures of the yellow heat-sensitive layer and the magenta heat-sensitive layer are as shown below.

One yellow heat-sensitive layer - Bainta -, Borich'Nilnodzilla - J, +1 Ki violet 0
．． 9g/rn2 Yellow dye, has the structure shown in F. Bar-magenta heat-sensitive layer binder Nitrocellulose, +1 weight 0.9g /
m 2 magenta dye, the structure shown in t゛ is 4 (+1 + 0.6
g/m2 F, t -N----Et G, Bg/m2 Using the above thermal transfer recording side diagonal and the same receiving and image material as Example 1, a video printer (-11- units) Manufactured by Seisakusho, V
When thermal transfer was carried out using Y-100), a full-color image having very good WI tonality, color development PI, and image stability was obtained.

(Example 7) An intermediate layer was added to the cyan ink layer 1 on the thermal transfer recording side of Example 6.
An aqueous solution containing 5 g, Borich'elpyrrolidone, 7 g, and 0.3 g of a hardening agent of the following structural formula, 1O0Pn, Q was coated on a pl-ruamide grade of 0.5 g/vn. .

A hardening agent is further added to the intermediate layer as a heat-melting outer layer.
rn”) and an antioxidant with the structural formula t’
゜Ig/m') and J-5 vinyl monophosphate copolymer vinegar #t"+", Le content [20 plying%, coating amount 0゜2 g/
0.2g 7m of carbanal wax containing 1o2)
A thermal transfer recording material was prepared by applying ``'') by the 4N-melnot coating method.

did.

Ultraviolet inhibitor 4 0■ N Mana Antioxidant: 0CaH+γ OC, 8,7 Thermal transfer was carried out using a video printer in the same manner as in Example 6 using the clam thermal transfer recording material and white plain paper as an image receiving material. .

As a result, a full-color image with excellent color reproducibility and gradation can be obtained.

[Effects of the Invention] The heat-sensitive transfer silver material of the present invention is formed by providing a layer containing a heat-diffusible cyan dye of 48% on a support.
It is possible to obtain images with outstanding heat resistance and light resistance.

Further, in the heat-sensitive transfer recording method of the present invention, using the above-mentioned heat-sensitive transfer recording material at 21°C, the following features are possible: pleasant images can be efficiently formed.

[Brief explanation of the drawing]

FIG. 1 shows the structural formula of a typical cyan dye according to the present invention. FIGS. 2(A) and 2(B) are explanatory diagrams of the principle of the thermal transfer recording method of the present invention. FIG. 3 is a sectional view showing the structure of an image receiving material used in one embodiment of the present invention. DESCRIPTION OF SYMBOLS 1...Support, 2...-Thermosensitive layer, 3...Thermal transfer recording material, 4...The-marhet', 5...Image receiving material, 6...Support, 7. ...Image receiving layer, 8... Heat-melting layer, 8a... Heat-melting substance, 9... Heat-sensitive transfer material, 1.111... Paper, 11a, ob... Polyethylene layer, 12 ...Polyvinyl chloride layer.

Claims (2)

[Claims] (1) A heat-sensitive transfer recording material comprising, on a support, a layer containing a cyan dye represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R^1 is a hydrogen atom, a halogen atom,
Alkyl group, cycloalkyl group, aryl group, alkenyl group, aralkyl group, alkoxy group, aryloxy group, cyano group, acylamino group, alkylthio group, arylthio group, sulfonylamino group, ureido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl basis,
Represents an aryloxycarbonyl group, a sulfonyl group, an acyl group, or 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 is 1
Represents an integer from ~3. Furthermore, R^1 and R^3 and R^
3 and R^4 may be bonded to each other to form a ring, or when m is 2 or more, the R^1 groups may be bonded to each other to form a ring. ] (2) An image-receiving material is superimposed on the layer of a heat-sensitive transfer recording material having a layer containing a cyan dye represented by the general formula [I] according to claim 1 on a support, and the heat-sensitive transfer recording material is used to convey image information. 1. A thermal transfer recording method, characterized in that an image is formed on an image-receiving material by heating the cyan dye according to the temperature of the image-receiving material to diffuse and transfer the cyan dye to the image-receiving material.