JPH01174490A - Red coloring matter for thermal sublimation transfer - Google Patents

Abstract

PURPOSE:To enhance solubility of a coloring matter in a solvent at the time of preparing an ink and enhance stability of the coloring matter to heat, light, moisture and chemicals, by synthesizing an anthraquinone red coloring matter for thermal sublimation transfer of a specified general formula. CONSTITUTION:1-Amino-2-chloro-4-hydroxyanthraquinone of formula I and a phenol of formula II (R is methyl, methoxyl or a halogen) ere heated in an aprotic polar solvent in the presence of a deoxidizer. By this, a red coloring matter tor thermal sublimation transfer of formula III (R is the same as that in formula II) can be obtained. The coloring matter is highly soluble in solvents, has an excellent property for preparation of an ink therefrom and excellent sublimability, and is free of migration thereof in a substrate or a contaminating property.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a red dye for heat-sensitive sublimation transfer.

More specifically, the present invention relates to a red dye that has good dyeing and color development properties and excellent fastness, particularly in a method of obtaining a record by sublimation transfer by heating with a thermal head.

The dye of the present invention can be used to obtain color hard copies from CRT color displays, color facsimile machines, magnetic cameras, etc. using the transfer type heat-sensitive recording method (Nikkei Electronics, February 13, 1984 issue), which is a means of recording information. It is a dye suitable for

(Prior art and problems to be solved by the invention) As a red dye for angry heat sublimation transfer recording, Japanese Patent Application Laid-Open No. 60-13
1293, the following general formula (A) (wherein -X- is 20-
or -S-, -8- is a linear or branched alkylene group, alkylene-〇-alkidine group, alkylene-3〒alkylene group, cyclohexylene group, phenylene group, -anthraquinone dye is disclosed. However, the energy required during transfer is large and the cost of the machine increases, which is undesirable.

Furthermore, known 1-amino-2-phenoxy-4-hydroxyanthraquinone (C1, Nll [1isp Re
d60) is also used, but the problem with making it into an ink is that it does not dissolve completely in the solvent, and recrystallization occurs when the ink sheet dries, resulting in an uneven transfer sheet with coarse crystals precipitated. Further, the sublimability, dyeing property and fastness are also unsatisfactory.

(Means for Solving the Problems) The present inventors have conducted intensive studies to solve the above problems, and have found that they are easily soluble in solvents, have excellent suitability for ink formation, and have excellent sublimation properties. The present invention was completed by discovering a dye that has no migration or staining properties.

That is, the present invention is a red color dye for heat-sensitive sublimation transfer represented by the following general formula (■) (wherein R represents a methyl group, a methoxy group, or a halogen atom).

In formula (1), R includes a methyl group, a methoxy group, and halogen atoms such as fluorine, chlorine, bromine, and iodine.

The dye represented by the formula -m < 1) is synthesized according to a conventional method by combining l-amino-2-chloro-4-hydroxyanthraquinone represented by the following formula (I[) and a phenol represented by the following formula (III). Obtained by heating in an aprotic polar solvent in the presence of a deoxidizing agent.

[R is the same as the above general formula (1). ] As a method for producing a leisurely transfer recording ink using the dye of the present invention, the dye may be mixed with an appropriate resin, solvent, etc. to prepare the recording ink. In addition, as a thermal transfer method,
Examples include a method in which the ink obtained above is applied onto a suitable base material to create a transfer sheet, the sheet is placed on a recording medium, and then the sheet is heated and pressed from the back side with a heat-sensitive recording head.

The resin for adjusting the above ink may be one that is used in ordinary printing inks, such as rosin, phenol, xylene, petroleum, vinyl, polyamide, alkyd, nitrocellulose, Oil-based resins such as alkyl celluloses, or water-based resins such as maleic acid, acetic acid, acrylic acid, casein, shellac, and glue are currently used. In addition, solvents for ink adjustment include alcohols such as methanol, ethanol, propatool, and butanol, cellosolves such as methyl cellosolve and ethyl cellosolve, aromatics such as benzene, toluene, and xylene, ethyl acetate, and butyl acetate. esters such as acetone, methyl ethyl ketone, ketones such as cyclohexanone, ligroin, cyclohexane,
Hydrocarbons such as kerosene, dimethylformamide, etc. can be used, but when using a water-based resin, water or a mixture of water and the above-mentioned abrasions can also be used.As a base material for applying the ink, Condenser paper, thin paper such as glassine, and plastic films with good heat resistance such as polyester, polyamide, and polyimide are suitable, but these base materials improve the efficiency of heat transfer from the thermal recording head to the dye. A thickness of about 5 to 50 μm is appropriate.

Examples of recording materials include polyolefin resins such as polyethylene and polypropylene, halogenated polymers such as polyvinyl chloride and polyvinylidene chloride, vinyl polymers such as polyvinyl alcohol, polyvinyl acetate, and polyacrylic ester, polyethylene terephthalate, Polyester resins such as polybutylene terephthalate, polystyrene resins, polyamide resins, copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, ionomers, cellulose resins such as cellulose diacetate and cellulose triacetate, polycarbonates Examples include fibers, woven fabrics, films, sheets, and molded products made of polysulfone, polyimide, and the like.

Particularly preferred are fabrics, sheets or films made of polyethylene terephthalate.

In addition, in the present invention, by using plain paper coated or impregnated with the resin to which acidic fine particles such as silica gel are added, or paper laminated with a resin film, or special processed paper treated with acetylation. Good recording with excellent image stability is possible under high temperature and high humidity conditions. Furthermore, synthetic paper made from various resins can also be used.

Furthermore, by heat-pressing and laminating, for example, a polyester film on the transfer recording surface after transfer recording, it is possible to improve the color development of the dye and to stabilize the recording during storage.

(Functions and Effects) The anthraquinone red dye represented by the general formula (1) of the present invention has the R position in the phenoxy group at the meta position, which is a necessary condition for transfer dyes compared to ortho and para isomers. Excellent solubility in solvents during chemical reaction.

Furthermore, during thermal transfer, the amount of dye sublimation transfer can be controlled by changing the energy applied to the thermal head, making gradation recording easy and suitable for full-color recording.

Furthermore, since it is stable against heat, light, moisture, chemicals, etc., it does not undergo thermal decomposition during transfer recording, and the obtained recording has excellent storage stability.

Furthermore, since the dye of the present invention has good solubility in a flux and good dispersibility in water, it is easy to prepare a uniformly dissolved or dispersed ink with high concentration, and as a result, an ink with good color density can be obtained. It is a practically valuable dye that can be used to record records.

(Example) Hereinafter, the present invention will be explained in detail in Examples using a compound of general formula (I) produced by a conventional method.

In Examples, "1 part" indicates Juyabe.

Example-1 (i) Ink preparation method 1-Amino-2(3-methylphenoxy)-4-hydroxyanthraquinone 3-part polybutyral resin
4.5 Methyl ethyl ketone
46.25 Toluene 4
6.25 The ink was prepared by partially treating the pigment mixture of the above composition with a paint conditioner for about 30 minutes using a glass piece.

(ii) How to create a transfer sheet Using the gravure proofing i (plate depth 30uII+), apply the above ink onto a 9nt thick polyethylene terephthalate film whose back side has been heat-resistant treated, and dry 2 Cloth 1 at 1°0g/
It was applied and dried to give rrf.

(iii) Preparation of recording material Polyester resin (vylon 103 manufactured by Toyobo Tg = 47°C)
0.8 parts EVA polymer plasticizer (Elvaloy 741p Mitsui Polychemical Tg-37
°c) 0.2 parts Amino-modified silicone 0.04 parts (KF-857
Shin-Etsu Chemical Co., Ltd.) Epoxy-modified silicone 0.04 part (K
F-103 manufactured by Shin-Etsu Chemical Co., Ltd.) Methyl ethyl ketone/toluene/cyclohexane (weight ratio 4:4:2) 9.0 parts or more were mixed, the coating liquid was adjusted, and synthetic paper (Yubo FPIJ150 manufactured by Tamago Yuka Co., Ltd.) was mixed. Bar coater (RK Pr1nt)
Coat Ina, manufactured by truments,
It was coated using Round 1) at a dry ratio of 4.51/rrf and dried at 100°C for 15 minutes.

(iv) Transfer recording The transfer sheet and the recording material are placed one on top of the other with their respective ink-coated surfaces and coating liquid-coated surfaces facing each other, and a voltage applied to the thermal head from the back side of the thermal transfer sheet is 10V, and a printing time is 4.0V. Recording was performed under millisecond conditions, and a red record with a color density of 1.9 was obtained.

The color density was measured using a densitometer R manufactured by Macbeth Co., Ltd. in the United States.
It was measured using a D-514 model (filter: Wratten Nα58).

Color density was calculated using the following formula.

Color density = j! o'g+. (Io/I) 1o = Intensity of reflected light from standard white reflector ■ - Intensity of reflected light from test object In addition, the light resistance test of the obtained record was performed using a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.). ) at a black panel temperature of 63 degrees Celsius, there was almost no discoloration after 40 hours of irradiation, and the image stability was excellent even under high temperature and high humidity conditions.

In addition, fastness was determined by leaving the obtained recorded image in an atmosphere at 50°C for 48 hours, and determining the sharpness of the image and the coloring when the surface was rubbed with white paper.The sharpness of the image did not change. Moreover, the white paper was not colored either, and the fastness of the image B was good.

Examples 2 to 3 In place of the pigment used in Example 1, the pigment #4 shown in Table 1 manufactured by a conventional method was used, and the ink was prepared in the same manner as in Example 1. When a transfer sheet was prepared, a recording material was prepared, and transfer recording was performed, a clear red transfer recorded image with the color density shown in Table 1 was obtained.

Further, the light fastness test of the obtained recording and the fastness of the recorded image were good as in Example-1.

Table-1 Comparative Example-1 1-amino-2-phenoxy-4-hydroxyanthraquinone was used instead of the anthraquinone pigment of the present invention used in Example-1, and the ink was adjusted in the same manner as in Example-1. However, the dye was not completely dissolved in the solvent and some of the dye remained as coarse crystals.

Furthermore, although the recording material was prepared, coated, and dried in the same manner as in Example 1, coarse particles precipitated and an uneven transfer sheet was obtained. When transfer recording was performed using this transfer sheet in the same manner as in Example 1, a non-uniform transfer recording with unevenness was obtained, and the quality of the overall image was not good.

Comparative Examples 2 to 3 1-amino-2(2-methylphenoxy)-4-hydroxyanthraquinone and 1-amino-2(4-methoxyphenoxy)-4-hydroxyanthraquinone instead of the azitraquinone dye of Comparative Example-1 As in Comparative Example-1, adjust the ink, prepare the recording material, apply it,
Drying and transfer recording were performed, but the results were the same as in Comparative Example 1', and the overall quality of the image was not good.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents a methyl group, a methoxy group, and a halogen atom.) For red heat-sensitive sublimation transfer Pigment.