JPS60229786A - Heat transfer thermal recording - Google Patents

Abstract

PURPOSE:To obtain an image stable and excellent in the hue, saturation and the density by combining a transfer body having a coloring material layer containing a specified sublimating dye and an image receiving body having an electron accepting substance. CONSTITUTION:At least one kind of sublimating dyes 23 as given by the formulas I, II and III (wherein, X represents hydrogen atom or a methyl group and R and R' each represent 1-4C alkyl group) is applied on a substrate 21 together with a binder 24 to obtain a transfer body 2 by forming a coloring material 22. On the other hand, an inage receiving body 1 has an electron accepting substance 14 applied on the substrate 13 together with a high polymer based binder 15. The coloring material layer 22 is arranged to face an image accepting layer 11 of an image receiving body 1 and heated selectively with a thermal head 4 or the like to form an image on the image accepting layer 11 sublimating the sublimating dye 23. The electron accepting substance herein used shall be an inorganic acid based color developer such as silica acid clay and/or an organic acid based color developing agent such as phenol resin.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a transfer-type thermal recording method used in video printers and the like that forms characters and images on a receiver using electrical signals from a thermal head and the like.

Conventional structure and problems In the transfer type thermal recording method using a heat source controlled by an electric signal such as a thermal head, the coloring material layer 2 is
A transfer body 2 having a substrate 2 and a substrate 21, and an image receptor 1 having an image receiving layer 11 and a substrate 13 are sandwiched between a drum 3 and a heat source 4 such as a thermal head, and a coloring material is applied to an image in accordance with an electric signal. A color notebook copy is obtained by transferring onto layer 11. The structure of the receptor used in this method is the substrate 1
An image receiving layer 11 is provided on top of the image receiving layer 3. Image receiving layer 11
varies depending on the content of the coloring material used; in the case of a sublimable basic dye-type coloring material or its color former, an activated clay layer is added, and in the case of a sublimable disperse dye-type coloring material, a high-grade material such as polyester or acetate is added. It is known to use layers of molecular materials.

Furthermore, basic dyes have a more mellow color tone and greater sublimation ability than disperse dyes or oil-soluble dyes, and are optimal coloring materials for heating means with limited heat source size such as thermal heads. There were major problems with layer and image stability.

On the other hand, disperse dye type coloring materials have a good reputation for their environmental stability, but they have low sublimation ability and require the use of three primary colors: bluish cyan, reddish magenta, and yellow.

Purpose of the Invention The transfer type thermal recording method of the present invention improves the hue, saturation, and density of images by using an image receptor containing an electron-accepting substance as a transfer body having a sublimable disperse dye with a large sublimation ability. The purpose is to improve the image quality and provide stable images.

Structure of the Invention The structure of the present invention is based on the following general formula (1), (■
).

At least one sublimable dye represented by (Ill)
The method is characterized in that a transfer body having a coloring material layer containing a coloring material and an image receptor having an electron-accepting substance are selectively heated while facing each other to form an image on the image receptor.

(In the formula, X represents a hydrogen atom or a methyl group, and R and R' each represent a methyl group, an ethyl group, a linear or branched propyl group, or a butyl group.) Invention K shows the transfer type thermal recording method, and the same components as in FIG. 1 are given the same numbers. The color material layer 22 of the transfer body 2 has the general formula (1).

At least one of the colored dyes 23 represented by (II) and (III) is coated together with a binder 24 on a substrate 21, which faces the image-receiving layer 11 of the image receptor 1. Here, the image-receiving layer 11 is a layer containing an electron-accepting substance 14, and is composed of a substance containing either one or both of an inorganic acid-based color developer and an organic acid-based color developer.

Here, as the inorganic acid color developer, substances such as silica acid clay, activated clay, and finely powdered silicate can be used.

Further, as the organic acid color developer, substances such as phenol resin, metal salts of salicylic acid derivatives, acrylic acid, methacrylic acid, and sulfonic acid can be used.

Incidentally, such an electron-accepting substance 14 is a polymeric binder 1
5 are coated on the substrate 13 of the image receptor 1. The image is
As in FIG. 1, only the sublimable dye is sublimated by a heat source 4 controlled by an electric signal such as a thermal head, and color can be developed and recorded in the image-receiving layer 11 containing an electron-accepting substance 14. Here, the role of the electron-accepting substance 14 is as follows:
Compared to the case where the image-receiving layer uses only a polymeric material such as polyester or acetate, this method moves the dominant wavelength of the dye or the complementary dominant wavelength on the chromaticity diagram to the longer wavelength side and increases the density of one color. be. Therefore, red has a magenta color, and blue has 777 colors.

Specific examples of the sublimable dyes represented by the general formulas (1), (n), and (1) include the following.

(1) exhibiting cyan color 1.5-bis(methylamine)-4,8-naphthoquinone, 1.6-
Bis(ethylamino)-4,8-naphthoquinone, 1.6
-bis((n)-propylamino)-4,8-naphthoquinone, 1,5-bis((iso)-propylamine)-
4,8-naphthoquinone, 1. s-bis((n)-butylamino)-4,8-naphthoquinone, 1,5-bis((i
go)-butylamino)-4,8-naphthoquinone, 1-
Methylamino-5-ethylamino-4,8-naphthoquinone, 1-methylamino-5-(n)-propylamino-
4,8-naphthoquinone, 1-methylamino-5-(n)
-Butylamino-4,8-naphthoquinone, 1-methylamino-5-(iso)-propylamino-4,8-naphthoquinone, ethylamino-5-(n)-propylamino-4,8-naphthoquinone, 1- ethylamino-5-(t
l)-Butylamino-4,8-naphthoquinone, 1-(n
) Propylamino-5-(n)-butylamino-4,8
- Naphthoquinone.

(n) exhibiting a yellow color 4-(2,
2-dicyanovinyl)-N,N-dimethylaniline, 4
- (2,2-dicyanovinyl)-N.

N-diethylaniline, 4-(2,2-dinanovinyl)-N,N-di(n)-propylaniline, 4-(21
2-dicyanovinyl)-N,N-di(iso)-propylaniline, 4-(2,2-dicyanovinyl)-N,N
-di(n)-butylaniline, 4-(2,2-dicyanovinyl)-N,N-di(iso)-butylaniline, 4
- (2,2-dicyanovinyl)-N,N-di(sea
)-butylaniline, 3-methyl-4-(2,2-dicyanovinyl)-N, N-dimethylaniline, 3-methyl-4-(2,2-dicyanovinyl)-N.

N-diethylaniline, 3-methyl-4-(2,2-dicyanovinyl)-N, N-di(n)-propylaniline, 3-methyl-4-(2,2-dicyanovinyl)-N,
N-di(iso)-propylaniline, 3-methyl-4
-(2,2-dicyanovinyl)-N,N-di(n)-butylaniline, 3-methyl-4-(2,2-dicyanovinyl)-N,N-di(iso)-butylaniline, 3 −
Methyl-4-(2,2-dicyanovinyl)-N,N-di(8ec)-butylaniline, 4-(2,2-dicyanovinyl)-N-ethyl-N-(n)-propylaniline, 4 -(2,2-Zinanovinyl)-N-ethyl-
N-(n)-butylaniline, 4-(2゜2-dicyanovinyl)N-methyl-N-(n)-propylaniline, 4-(2,2-dicyanovinyl)-N-methyl-N'
-(n)-Butylaniline, 3-methyl-4-(2,
2-dicyanovinyl)-N-methyl-N-(n)-propylaniline, 3-methyl-4-(2,2-dicyanovinyl)-N-methyl-N-(n)-butylaniline, 3-methyl -4-(2,2-dicyanovinyl)-N-
Ethyl-N-(n)-furobylaniline, 3-methyl-4-(2,2-dinanovinyl)-N-ethyl-N
-(n)-phthylaniline.

(Ill) exhibiting a magenta color 4-
) +77 anovinyl-N, N-dimethylaniline,
4-) Licyanovinyl-N, N-diethylaniline, 4
-Tricyanovinyl-N,N-di(n)-propylaniline, 4-tricyanovinyl-N,N-di(iso)-
Propylaniline, 4-tricyanovinyl-N, N-di(n)-butylaniline, 4-tri7anovinyl-N,
N-di(iso)-butylaniline, 4-tri7anovinyl-N, N-di(89C)-butylaniline, 3-methyl-4-)IJ/anovinyl-N.

N-dimethylaniline, 4-tridianovinyl-N-methyl-N-(n)-propylaniline, 4-tricyanovinyl-N-methyl-N-(n)-butylaniline,
4-) Dicyanovinyl-N-ethyl-N-(n)-furopylaniline, 4-1-dicyanovinyl-N-ethyl-N-(n)-phthylaniline, 4-tricyanovinyl-N-ethyl-N -(iso)-butylaniline, 4
-1-anohinyl-N-ethyl-N-(sea)-butylaniline, 4-tricyanovinyl-N-(n)-
Propyl-N-(n)-butylaniline, 3-methyl-4-1cyanvinyl-N-methyl-N-ethylaniline.

The ink for forming the coloring material layer includes a pigment represented by the general formula (1), (It), or (II), a resin with a high melting point or softening point, a solvent or a solvent such as water, and a non-sublimated material. It can be made by mixing with sexual particles.

The resin used for preparing the above ink may be those used in ordinary printing inks, such as rosin-based, phenol-based, xylene-based, petroleum-based, vinyl-based, polyamide-based,
Oil-based resins such as alkyd-based, nitrocellulose-based, alkylcellulose, alkylcelluloses, ether-based, and ester-based resins, or water-based resins such as maleic acid-based, acrylic acid-based, casein, shellac, and glue can be used, but more specific examples may be used. Particularly effective are polycarbonates, polysal-7ones, polyphenylene oxides, polyarylates, cellulose derivatives, etc., which have high melting points or softening points. In addition, as solvents for ink preparation, alcohols such as methanol, ethanol, gropanol, butanol, cellomelfs such as methyl cellosolve and ethyl cellosolvenato, aromatics such as benzene, toluene and xylenato, esters such as butyl acetate, Ketones such as acetone, methyl ethyl ketone, and cyclohexanone; hydrocarbons such as ligroin, cyclohexane, and keromene;
Halogenated hydrocarbons such as dimethylformamide, methylene chloride, chlorobenzene, and chloroform can be used, but when using an aqueous resin, water or a mixture of water and the above-mentioned solvents can also be used.

A more specific example will be described.

Example 1 6 parts by volume of magenta sublimable dye represented by the structural formula 1, 6 parts by volume of polycarbonate, 1 o of dichloromethane
o Volume parts and silica particles with an average particle size of 5 μm were mixed in different amounts and stirred separately using a Pollumi I, and the dispersion was coated on a 10 μm thick condenser paper using a wire parser to obtain a dye transfer material 2. .

Also, S t O2, Aft 203. on high quality paper. Mg
Finely powdered silicate mainly composed of O, Fe2O3 and styrene-butadiene rubber as a binder in a weight ratio of 8:2.
The image receptor 1 is coated with a blade coater at a ratio of I was able to obtain

The situation is shown in Figs. 3 and 4. In the chromaticity diagram of FIG. 3, M' is the case when the image receptor is a polyester film, and M is the chromaticity point according to the present invention. In addition, in the recording density characteristics shown in FIG. 4, A is a polyester film image receptor, and B is a characteristic according to the present invention, when applied power P = 0.7 W/dot pulse width 7 ms in a 4 dot/parrot thermal head. A saturation concentration of D-13 could be obtained.

Example 2 A solution prepared by dissolving about 1 inch of a sublimable dye represented by the following formula 2 and polycarbonate as a binder at a weight ratio of 1:1 was applied onto an 8 μm polyester film using a wire bar. The coating and drying was used as transfer body 2, and S 102 was applied onto art paper.

A fine powder containing AIO, MgO, and Fe2O3 as main components was coated using a blade coater with a liquid obtained by mixing and dispersing phenylphenol and formalin in a weight ratio of 4:16:80 and drying. By using the image receptor 1 as an image receptor 1 and selectively heating them with a thermal head while facing each other, it was possible to obtain an image with cyan color gradation on the image receptor 1. As shown in Figure 3, similar to Example 1, C
' point can be moved to the zero point using the image receptor according to the invention.

Example 3 The chromaticity characteristics are shown in Y in FIG. 3 when a yellow sublimable dye represented by the above general formula (3) was used and a transfer member and an image receiver having the same structure as in Example 1 were used.

Y′ is for a polyester film receiver,
In the case of yellow, the change in the dominant wavelength is smaller than that of magenta and cyan.

Example 4 777 colors represented by the structural formulas (1), (2), and (3).

For each of the magenta and yellow sublimable dyes, a paint condenser was prepared using glass beads with 5 parts by volume of the dye, 6 parts by volume of polysulfone, 100 parts by volume of monochlorobenzene, and 20 parts by volume of alumina particles with an average particle size of 6 μm. The ink was adjusted by mixing for 3゜q, and the ink was applied sequentially in cyan, magenta, and yellow onto the transfer substrate of Example 1 using a gravure printing machine (plate depth: 3゜μm). It was used as a transcript. By using this transfer body and recording three colors in a superimposed manner on the recording paper using a thermal head under conditions similar to the recording conditions described above, it was possible to obtain an image close to color printing.

Effects of the invention (1) The reddish magenta or bluish cyan sublimable colored dye used in the present invention can be moved to the dominant wavelength or complementary dominant wavelength side on the chromaticity diagram of the dye used. It is possible to obtain the original maze/cyan hue. Therefore, it is possible to eliminate the decrease in sublimation ability caused by changing the wavelength characteristics of the dye itself.

(2) The coloring ability (sublimation ability) of the dye used can be increased, the capacity of a heat source such as a thermal head can be reduced, and the lifespan can be extended.

(3) Since a dispersed or oil-soluble dye having the above chemical structure is used, images with excellent environmental resistance can be obtained.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing a conventional transfer type thermal recording method, FIG. 2 is a sectional view showing a thermal recording method according to an embodiment of the present invention, and FIG. 3 is a sectional view showing a chromaticity point in an embodiment of the present invention. Chromaticity diagram to explain,
FIG. 4 is a diagram illustrating recording density characteristics in one embodiment of the present invention. 1...image receptor, 2 transfer body, 11...receptive image layer, 1
4...Electron accepting substance, 16...Polymer binder, 23
-...Sublimable dye. Figure 1 Figure 2 Castle

Claims (1)

[Claims] (1) The following general formulas (1), (n),
At least one sublimable dye represented by (I[l)
A transfer type thermosensitive recording method, in which a transfer member having a coloring material layer containing a colorant and an image receptor having an electron-accepting substance are selectively heated while facing each other, and an image is formed on the image receptor. ONHR R'HN 0 (wherein, X represents a hydrogen atom or a methyl group, and R and R' each represent a methyl group, an ethyl group, a linear or branched propyl group, or a glutyl group) (2) Color The transfer type thermosensitive material according to claim 1, wherein the material layer contains two or more sublimable dyes having different substituents in each of the general formulas (1), (ff), or (Ill). Recording method. (3) Claims in which three coloring material layers containing at least one type of sublimable dye selected from general formulas (1), (If), and (Ill) and having different hues are sequentially arranged. 2. The transfer type thermal recording method according to item 1. (4) Three coloring material layers containing at least one sublimable dye selected from the general formulas (1), (II), ([[l), and the general formulas (1), (II
2. The transfer type heat-sensitive recording method according to claim 1, wherein the fourth coloring material layer selected from at least one coloring material layer selected from each of (1) and (If) is arranged in a plane-sequential manner. (6) The transfer type thermal recording method according to claim (1), wherein the electron-accepting substance contains one or both of an inorganic acid color developer and an organic acid color developer. (6) The transfer type thermal recording method according to claim 6, wherein at least one of silica acid clay, activated clay, and fine powder silicate is used as the inorganic acid color developer.