JPH02175293A - Sublimable transfer recording anthraquinone dye - Google Patents

Abstract

PURPOSE:To control sublimable transfer amount of dye and to facilitate gradation recording by altering energy to be applied to a heat sensitive head at the time of heat transfer by using specific anthraquinone cyan dye. CONSTITUTION:The quantity of sublimation starting heat has no correlation directly to molecular weight itself, but relates to mutual action among colorant molecules and to mutual action between dye molecules and ink binder resin. Even if the molecular weight of the dye is slightly increased, the dye having satisfactory solubility to ink solvent and lower melting point is desired, and the dye having mutual action to the binder resin for ink to be small in the degree not lose preservation stability after a ribbon is manufactured is most desirable. Dye represented by a formula (I) exceeds 400 of molecular weight, but obtains relatively desirable sublimating speed. In the formula, R1 is alkoxycarbonylalkyl group, alkylcarbonylalkyl group having normal chain or branch, R2 is hydrogen atom, lower alkyl group, alkoxy group, alkenyl group, trifluoromethyl group, having normal chain or branch, halogen atom.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a minoan color sublimation transfer recording dye having the general formula (+) [wherein RI is an alkoxycarbonyl alkyl group which may be linear or branched]. , represents an alkylcarbonylalkyl group, and R2 represents a hydrogen atom, a lower alkyl group that may be linear or branched, an alkoxy group, an alkenyl group, a trifluoromethyl group, or a halogen atom. It is something.

[Prior art and problems to be solved by the invention] The thermal transfer method using sublimation dyes involves coating a thin condenser paper or PET film several microns thick with sublimation dyes in the form of ink, and then selectively applying the sublimation dyes using a thermal head. It is one of the thermal transfer printing methods in which the image is heated and transferred onto recording paper, and is currently used as a means for recording (hard copy) various types of image information.

The sublimable dye used here has a rich color range, excellent color mixing properties, strong dyeing power, and relatively high stability. However, the amount of sublimated dye depends on thermal energy, and after dyeing It has a great feature that other printing methods do not have, in that density can be controlled in an analog manner.

However, there are very few dyes that have been proposed so far that satisfy all the conditions such as heat resistance, light resistance, sublimation speed, hue, ribbon stability, etc., and it is difficult to find a dye that satisfies the optimal conditions as a sublimable dye. has been recycled.

(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors discovered a compound represented by the general formula (I) and completed the present invention.

That is, the present invention provides a compound of the general formula (I) [wherein R1 represents a straight-chain or branched alkoxycarbonylalkyl group or an alkylcarbonylalkyl group, and R2 represents a hydrogen atom, a straight-chained or branched lower Indicates an alkyl group, an alkoxy group, an alkenyl group, a trifluoromethyl group, and a halogen atom. ] is an anthraquinone dye for sublimation transfer recording.

The present invention will be explained in detail below.

In the present invention, R5 is an alkoxycarbonylalkyl group such as a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, n, a propylcarbonylmethyl group, an iso-propylcarbonylmethyl group, a methoxycarbonylethyl group, an ethoxycarbonylmethyl group, or a methylcarbonylmethyl group. , ethylcarbonylmethyl group, propylcarbonylmethyl'S, 15O-propylcarbonylmethyl group, methylcarbonylethyl group, ethylcarbonylethyl group, and other alkylcarbonyl groups.

R1 is a hydrogen atom, or a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, ter-
Examples include lower alkyl groups such as butyl groups, alkoxy groups such as methoxy groups, ethoxyno groups, propoxy groups, alkenyl groups such as vinyl groups, propenyl groups, butenyl groups, trifluoromethyl groups, and halogen atoms such as fluorine, chlorine, and bromine. It will be done.

Conventionally, anthraquinone-based sublimation transfer dyes with a molecular weight exceeding 400 tended not to be given much attention because of the large amount of heat required to initiate sublimation. According to research, the amount of heat at which sublimation starts has no clear direct correlation with the molecular weight itself, but is rather related to the interaction between the same dye molecules and the interaction between the dye molecules and the binder resin for ink. It was discovered.

In other words, even if the molecular weight of the dye increases somewhat, it should have good solubility in the ink solvent and a low melting point, and furthermore, it should be such that interaction with the ink binder resin does not affect the storage stability after ribbon production. It has become clear that the dye having the smallest value is the best.2 The dye represented by the formula (I) of the present invention satisfies the above conditions and is relatively A good sublimation rate was obtained.

The dye represented by formula (I) of the present invention can be produced by a conventional method.
It can be easily obtained by using l-amino-4-bromoanthraquinone-2-carboxylic acid as a raw material, esterifying it with a carboxylic acid ester or a chloride of a ketone, and causing a condensation reaction with an aniline.

(i) 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 form the recording ink.As a thermal transfer method,
A method of applying the ink obtained above to a suitable board to create a transfer sheet, overlapping the sorted material with a recording medium, and then heating and pressurizing the sheet with a thermal recording head from the back side, In this way, the dye on the sheet is transferred onto the recording medium.

The resin used for adjusting 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, and alkyl celluloses, or water-based resins such as maleic acid-based, acrylic acid-based, casein, shellac, and glue can be 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 xolene, and ethyl acetate and butyl acetate. esters such as acetone, methyl ethyl ketone, ketones such as cyclohexanone, hydrocarbons such as ligroin, cyclohexane, kerosene, dimethylformamide, etc. can be used, but when using an aqueous resin, water or water and the above solvents can be used. It is also possible to mix and use them.

Substrates for applying ink include thin paper such as condenser paper and glassine paper, polyester, polyamide,
A plastic film with good heat resistance such as polyimide is passed through, and the thickness of these base materials is suitably about 5 to 50 μm in order to improve the efficiency of heat transfer from the heat-sensitive recording head to the dye.

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, and polyethylene terephthalate. Polyester resins such as butylene 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, Fibers made of polysulfone, polyimide, etc.
Examples include woven fabrics, films, sheets, and molded products.

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

In addition, in the present invention, plain paper coated or impregnated with acidic particles equivalent to silica gel added to the resin, paper laminated with a resin film, or special processed paper treated with acetylation are used. By doing so, good recording with excellent image stability under high temperature and high humidity conditions can be achieved. It is also possible to use films of various resins or synthetic papers made from them.

Further, after the transfer recording, for example, a polyester film is hot-pressed and laminated on the transfer recording surface, thereby improving the color development of the dye and stabilizing the storage of the recording.

(Functions and Effects) During thermal transfer, the anthraquinone cyan dye represented by the general formula (I) of the present invention can control the sublimation transfer amount of the dye by changing the energy given to the thermal head. Easy to record and suitable for full color recording.

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

In addition, since the pigment of the present invention has good solubility in organic solvents and good dispersibility in water, it is easy to prepare a uniformly dissolved or dispersed ink with high concentration, resulting in an ink with good color density. It is a practically valuable dye that can be used to record records.

(Example) Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 A compound of the following formula (A) was synthesized according to a conventional method, and ink was adjusted, a transfer sheet, and a recording material were prepared as described below, and transfer recording was performed. The maximum absorption wavelength (λwax) of this compound in chloroform was 660 nm.

(I) Ink preparation method Pigment of the above formula (A) 3-part polybutyral resin 4,5〃Methyl ethyl ketone
46.25 Toluene
46.25 The ink was prepared by mixing the pigment mixture having the above composition with a paint conditioner for about 30 minutes using a glass piece.

(ii) How to make a transfer sheet Using a gravure proofing machine (plate depth 30 μm), apply the above ink to a 98-part thick polyethylene terephthalate film whose back side has been heat-resistant treated, and apply 1 liter of dry coating to 1.0 g/n? Apply it and let it dry.

(iii) Preparation of recording material Polyester resin 0.8 parts (vyl
on 103 Toyobo Tg=47'C) EVA polymer plasticizer 0.2 parts (Elvaloy 741
pMitsui Polychemicals Tg=-37°C) Amine-modified silicone 0.04 parts (KF
-857 Shin-Etsu Chemical Co., Ltd.) Epoxy-modified silicone 0.04 part (NiF
-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 PPGI 150 manufactured by Tamago Yuka Co., Ltd.) was mixed. Bar coater (RK Pr1n)
Manufactured by Coat Instruments, Inc.
It was applied at a dry rate of 4.5 g/n (NCLI) and dried at 100'C for 15 minutes.

(Iv) Transfer recording The above-mentioned transfer sheet) - Lay the above-mentioned recording material on top of each other with their respective ink-coated surfaces and coated M2 cloth facing each other, and apply a voltage of 10ν to the thermal head from the back side of the thermal transfer sheet for a printing time. Recording was performed under the condition of 4.0 milliseconds, and the color density was 1.
85 cyan records were obtained.

The color density is measured using Dentometer R manufactured by Macbeth Co., Ltd. in the United States.
Measurement was carried out using Model D-514 (Filray Nilanten 5g).

Color density was calculated using the above formula.

Color density = ffiog+o(io/I)to - Intensity of reflected light from standard white reflector ■ - Intensity of reflected light from test object In addition, the light fastness test of the obtained record was performed using a xenon fade meter (Suga Test (manufactured by Kishi Co., Ltd.) at a black panel temperature of 63±2°C, 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, the fastness was determined by leaving the 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. Furthermore, the white paper was not colored and the fastness of the recorded image was good.

Example-2 A compound of the following formula (B) was synthesized according to a conventional method.

Maximum absorption wavelength (λm) of the compound in chloroform
ax) was 660n-.

In the same manner as in Example 1, the ink was adjusted, a transfer sheet, and a recording material were prepared, and transfer recording was performed to obtain a cyan recording with a color density of 1.80.

All of these records were subjected to a light fastness test in the same manner as in Example 1, and the records showed almost no change and were excellent in image stability under high temperature and high humidity conditions.

Further, a fastness test was conducted in the same manner as in Example 1, but the sharpness of the image did not change, the white paper did not become colored, and the fastness of the recorded image was good.

Examples 3 to 9 Anthraquinone cyan pigments shown in Table 1 were produced in the same manner as in Example 1, and the ink was prepared in the same manner.
A transfer sheet was prepared, a recording material was prepared, and transfer recording was performed to obtain each record shown in Table 1.

All of these records were subjected to a light fastness test in the same manner as in Example 1, and the records showed almost no change, and Sample 2 was also excellent in image stability under high temperature and high humidity.

Further, a fastness test was conducted in the same manner as in Example 1, but the sharpness of the image did not change, the white paper did not become colored, and the fastness of the recorded image was good.

(Margin below)

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R_1 is an alkoxycarbonylalkyl group or an alkylcarbonylalkyl group that may be linear or branched. and R_2 represents a hydrogen atom, a lower alkyl group that may be linear or branched, an alkoxy group, an alkenyl group, a trifluoromethyl group, or a halogen atom. ] Anthraquinone dye for sublimation transfer recording.